JP2003027046A - Aqueous dispersion as water/oil repellent and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an aqueous dispersion as a water/oil repellent being an aqueously dispersed water/oil-repellent composition being easily treated and highly safe and exhibiting an excellent water/oil repellent effect in spite of its low fluorine content and to provide a method for producing the same. SOLUTION: There is provided a method for producing an aqueously dispersed water/oil repellent containing a polymer (X) containing e.g. a polyfluoroalkyl group on each terminal by performing emulsion polymerization in the presence of (A) an acyl peroxide having e.g. a polyfluoroalkyl group on each terminal, represented by the formula: RfC(=)OOC(=O)Rf (wherein Rf is a polyfluoroalkyl group or a polyfluorocycloalkyl group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous dispersion for a water / oil repellent and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polymer obtained by polymerizing a monomer having a polyfluoroalkyl group is dispersed in an aqueous medium to obtain an aqueous dispersion, or an organic solvent is dissolved to obtain an organic solution. Alternatively, there is known a technique of treating a textile product or the like with a solvent dispersion liquid dispersed in an organic solvent to impart water and oil repellency to the surface thereof. In recent years, in particular, an aqueous dispersion has been recommended because of problems such as working environment and environmental impact. As such a water-dispersed water- and oil-repellent agent, an aqueous dispersion in which a polymer having a polyfluoroalkyl group in its side chain is dispersed in an aqueous medium is known (Japanese Patent Laid-Open No. 10-204777, JP-A-11-92752, JP-A-2000-1
No. 60149, etc.). However, in order to obtain the desired water / oil repellent effect, the fluorine content of the water / oil repellent component contained in the aqueous dispersion must be usually 50% by mass or more,
The water / oil repellency effect was small relative to the fluorine content.

[0003]

DISCLOSURE OF THE INVENTION The present invention is a water- and oil-repellent composition in a water-dispersed form which is easy to treat and highly safe, and has a smaller fluorine content than the prior art. Provided are a water dispersion for a water and oil repellent agent that exhibits an excellent water and oil repellency, and a method for producing the same.

[0004]

The inventors of the present invention have such a small water- and oil-repellent effect with respect to the fluorine content that the water- and oil-repellent polyfluoroalkyl group is on the polymer side. Since it exists as a chain, it was considered that the cause was poor orientation on the surface of the object to be treated. Therefore, the present inventors
As a result of diligent research into a structure capable of efficiently orienting a polyfluoroalkyl group, by emulsion polymerization using an acyl peroxide having a polyfluoroalkyl group at both ends,
It was found that a water- and oil-repellent agent in a water-dispersed form having excellent water- and oil-repellent efficiency can be obtained.

That is, the first aspect of the present invention is that an acyl peroxide (A) containing a polyfluoroalkyl group or a polyfluorocycloalkyl group represented by the following formula (1):
Is used to produce an aqueous dispersion for water and oil repellents, which comprises a polymer (X) having a polyfluoroalkyl group or a polyfluorocycloalkyl group at both ends. RfC (= O) OOC (= O) Rf (1) (In the formula, Rf represents a polyfluoroalkyl group or a polyfluorocycloalkyl group.)

In the production method of the first aspect, a raw material composition containing a monomer (B), a surfactant (C) and water (D) is emulsified under pressure, and then the acyl peroxide (A) is added. It is preferable to add and carry out emulsion polymerization.

In the production method of the first aspect, it is preferable to further add a radical polymerization initiator (E) to carry out emulsion polymerization.

A second aspect of the present invention is an aqueous dispersion for a water and oil repellent produced by the production method of the first aspect.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The water dispersion for water and oil repellents of the present invention and the method for producing the same are described in detail below. In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. (Meta)
The same applies to expressions such as acrylamide. The production method according to the first aspect of the present invention is an acyl peroxide having a polyfluoroalkyl group or a polyfluorocycloalkyl group (hereinafter, referred to as “Rf group”) at both ends represented by the following formula (1) ( It is characterized by emulsion polymerization using A). RfC (= O) OOC (= O) Rf (1) (In the formula, Rf is a polyfluoroalkyl group or a polyfluorocycloalkyl group.)

In the present invention, the Rf group means that at least two hydrogen atoms of an alkyl group or a cycloalkyl group in which an etheric oxygen atom or a thioetheric sulfur atom may be present between carbon-carbon bonds are fluorine atoms. A group substituted with. The Rf group preferably has 1 to 10 carbon atoms, and particularly preferably 3 to 8 carbon atoms. When the Rf group is an alkyl group, it may have a linear structure or a branched structure, and a linear structure is preferable. In the case of a branched structure, the branched portion is preferably present at the terminal portion of the Rf group and is a short chain having 1 to 4 carbon atoms. Further, in the Rf group, a part of the fluorine atom may be substituted with another halogen atom, and the other halogen atom is preferably a chlorine atom. In this case, the number of fluorine atoms after substitution is
[(Number of fluorine atoms in Rf group) / (total number of hydrogen atoms and other halogen atoms contained in corresponding alkyl group or cycloalkyl group having the same carbon number as Rf group)] ×
When expressed as 100 (%), it is preferably 60% or more, and particularly preferably 80% or more. Further, the Rf group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group), a group having a perfluoroalkyl group at the terminal portion,
Alternatively, a group containing a perfluorocycloalkyl group is preferable.

The Rf group is preferably a group represented by the following formula (2) or a group containing a perfluorocyclohexyl group. - In _{(CF 2) s X ··· (} 2) Equation (2), s is an integer from 1 to 10, X is either a fluorine atom, a chlorine atom or a hydrogen atom.
The group represented by formula _{(2) - (CF 2)} 3 F, -
_{(CF 2) 4 F, -} (CF 2) 5 F, - (CF 2)
_{6 F, - (CF 2)} 7 F, - (CF 2) 8 F, - (CF
₂ ) Perfluoroalkyl groups represented by ₉ F and-(CF ₂ ) ₁₀ F are particularly preferable. When the Rf group is these, the water and oil repellency of the polymer (X) is excellent.

The method of emulsion polymerization is not particularly limited and can be carried out by a known method, such as a monomer (B) and a surfactant (C).
It is preferable to emulsify a raw material composition containing water and water (D) under pressure, and then add the acyl peroxide (A) to carry out emulsion polymerization.

The monomer (B) to be reacted with the acyl peroxide (A) may be a known or well-known monomer. Among them, a monomer having one or two polymerizable unsaturated groups is preferable, and a monomer having one polymerizable unsaturated group is particularly preferable. The monomer (B) may be used alone or in combination of two or more. As the monomer (B), a monomer having at least one group selected from an amide group, an acetylacetoxy group, a blocked isocyanate group, a hydroxyl group and an Rf group can be used. Here, the blocked isocyanate group is a group having a structure in which the isocyanate group is blocked, and specifically, it is described in JP-A-200
0-256302 or Japanese Patent Application No. 2001-580
The monomers exemplified in No. 92 are mentioned.

Examples of the monomer having an amide group include N-methylol (meth) acrylamide, N-morpholino (meth) acrylamide, N-alkyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-dialkyl (meth) acrylamide. , N-cycloalkyl (meth) acrylamides, N-alkoxymethylol (meth) acrylamides, N-aryl (meth) acrylamides, N-alkoxyalkyl (meth) acrylamides and the like. Examples of the monomer having an acetylacetoxy group include acetylacetoxy (meth) acrylate and acetylacetoxyethyl (meth) acrylate. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and 2,3-dihydroxy. Propyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, N -Alkoxymethyl acrylamide, p-hydroxyphenyl (meth) acrylamide, polyoxyalkylene (meth) acrylate whose terminal is substituted with a hydroxyl group, and the like. As the monomer having an Rf group, a monomer in which the above Rf group is bonded to an alcohol residue portion of (meth) acrylate is preferable, and a monomer represented by the following formula (4) is particularly preferable. Specific examples thereof include the monomers described in JP-A 2000-160149. _{Rf-Q-OCOCR = CH 2} ··· (4) ( wherein, Rf is Rf group, Q is a divalent organic group, R is hydrogen atom or a methyl group.)

In addition to the above, as the monomer (B), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth)
Alkyl (meth) acrylates such as acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (Meth) acrylate, polyoxyalkylene (meth) acrylate such as 2-hydroxy-3-acryloyloxypropyl methacrylate, monoolefin, vinyl halide, vinylidene halide, carboxylic acid vinyl ester, styrene, substituted styrene, alkyl vinyl ether, (Substituted alkyl) vinyl ether, vinyl alkyl ketone, diolefin, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, aziridinylalkyl (meth) acrylate Polyoxyalkylene mono (meth)
Acrylate monomethyl ether, polyoxyalkylene di (meth) acrylate, (meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate, allyl glycidyl ether, carboxylic acid allyl ester, N-vinylcarbazole, N-methylmaleimide, maleic acid Examples thereof include dialkyl ester and substituted aminoalkyl (meth) acrylate. Monomer (B)
May be appropriately selected from those exemplified above according to the purpose, and adjusts or improves the adhesiveness to the object to be treated, the crosslinkability, the film forming property, the flexibility, the antifouling property or the stain removal property. To do.
For example, if a (meth) acrylate having a long side chain is used, it is possible to impart flexibility to the fiber. Further, when a monomer having an amide group, an acetylacetoxy group, a blocked isocyanate group or a hydroxyl group is used, the adhesiveness to the object to be treated is excellent.

As the surfactant (C), one or more kinds selected from nonionic surfactants, cationic surfactants and amphoteric surfactants containing neither an aromatic group nor a fluorine atom can be used. . The surfactant (C) preferably contains a nonionic surfactant because the stability of the latex after emulsification is particularly excellent, and the content of the nonionic surfactant in the surfactant (C) is preferably 60-10
It is particularly preferably 0% by mass. As the nonionic surfactant, a nonionic surfactant (C ¹ ) consisting of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether or polyoxyalkylene monoalkapolyenyl ether, 1 in the molecule
A nonionic surfactant (C ² ) composed of a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups and exhibiting emulsifying property, and polyoxyethylene in which two or more oxyethylenes are continuously connected. A nonionic surfactant (C ³ ), which is composed of a compound in which a part and a part in which two or more oxyalkylene having 3 or more carbon atoms are continuously connected are connected and both ends are hydroxyl groups, amine oxide in the molecule Examples thereof include a nonionic surfactant (C ⁴ ) having a moiety and a nonionic surfactant (C ⁵ ) composed of a fatty acid ester of polyol. Examples of the cationic surfactant include a cationic surfactant composed of a substituted ammonium salt such as stearyltriethylammonium chloride.
Examples of the amphoteric surfactant include amphoteric surfactants such as alanines, aliphatic amide betaines, and acetic acid betaines. As the surfactant (C), more specifically, the compounds exemplified in JP-A 2000-160149 can be used. The addition amount of the surfactant (C) is preferably 1 to 20 mass% with respect to the monomer (B),
2 to 15 mass% is more preferable, and 3 to 10 mass% is particularly preferable. If the amount of the surfactant (C) added is too small, the stability of the latex may decrease, and conversely, if it is too large, the water- and oil-repellent wet friction durability may decrease. However, when the monomer (B) contained in the raw material composition contains a self-emulsifying monomer, the content of the surfactant (C) may be reduced.

The content of water (D) in the raw material composition is 3 with respect to the monomer (B) from the viewpoints of storage stability of the latex, easiness of control of reaction during production, transportation cost and the like.
0 to 95 mass% is preferable, 35 to 95 mass% is more preferable, and 40 to 90 mass% is particularly preferable. In addition to water, a water-soluble solvent (F) can be added to the raw material composition. As the solvent (F), water 100
The solubility in g is not particularly limited as long as it is 10 g or more, but propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and tripropylene glycol. One or more solvents selected from the group consisting of propylene glycol monomethyl ether are preferably mentioned in terms of water / oil repellency, storage stability and safety. When water (D) and solvent (F) are used in combination, the addition amount of solvent (F) is
100 mass% or less is preferable with respect to a monomer (B), and especially 0-80 mass% is preferable. Freezing stability of the latex is improved by adding a water-soluble solvent, but if the amount added is too large, the durability of water and oil repellency against repeated washing may be reduced.

In addition to the above-mentioned components (B), (C) and (D), a chain transfer agent and a pH adjusting agent may be added to the raw material composition for the purpose of controlling the molecular weight during polymerization. As the chain transfer agent, aromatic compounds or mercaptans are preferable, and alkyl mercaptans are particularly preferable. Specific examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer. The addition amount of the chain transfer agent is appropriately changed depending on the desired molecular weight of the polymer (X). Examples of the pH adjusting agent include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate, sodium thiosulfate and sodium tetraborate, and organic bases such as triethylamine, triethanolamine, dimethylethanolamine and diethylethanolamine. To be The addition amount of the pH adjusting agent is preferably 0.05 to 2% by mass, and 0.1 to 2% by mass with respect to the total of water (D) and solvent (F).
Is more preferable. In particular, it has a polymerization rate of 0.
It is preferably adjusted to 2 to 1.0% by mass.

The raw material composition is preferably emulsified under pressure. Although pre-emulsification may be performed by stirring or the like before emulsification, the pre-emulsification is not necessarily required in the present invention. When emulsifying under pressure, it is preferable to use a high-pressure emulsifying device such as an APV homogenizer, hydroshear, or microfluidizer. Gauge pressure during emulsification is 1 to 50M
Pa (MPa indicates megapascal) is preferable, and the temperature of the raw material composition is preferably 40 to 80 ° C. For emulsification under pressure, the raw material composition may be placed under pressure, but may be stirred if necessary. A latex is produced by emulsifying the raw material composition. When emulsified under pressure, the average particle size of the monomer particles contained in the latex is small, thermodynamically stable, and most of the monomer (B) can react during polymerization. The average particle size of the monomer particles in the latex after pressure emulsification is preferably in the range of 0.1 to 300 nm, particularly preferably in the range of 100 to 250 nm.

When the monomer (B) is liquid or solid under the emulsification conditions under normal pressure or under pressure, it is preferable to add it to the raw material composition at the time of emulsification and simultaneously emulsify and polymerize. When the monomer (B) is a gas under the emulsification conditions under normal pressure or under pressure, after emulsifying the raw material composition containing the other monomer (B) which is not a gas, the monomer (B) is fed into the latex by a self-pressure or a liquid feed pump. It is preferably introduced and polymerized.

The latex of the raw material composition thus obtained is emulsion-polymerized by adding the acyl peroxide (A). If necessary, the acyl peroxide (A) may be added after being dissolved in fluorine-containing and / or chlorine-containing hydrocarbons such as pentafluorodichloropropane, tridecafluorohexane, methylene chloride and the like. Acyl peroxide (A)
The amount of addition of the monomer (B) to the acyl peroxide (A)
Is added in a molar ratio (preparation) of 1 to 500, particularly 2 to
It is preferably adjusted in the range of 100. When this ratio is from 2 to 100, a large amount of a product due to self-decomposition of acyl peroxide does not occur, and the yield of the target polymer (X) having Rf groups at both ends is high, which is preferable. . Moreover, the molecular weight of the obtained polymer can be adjusted by adjusting this ratio. For example, if this ratio is decreased and the amount of acyl peroxide (A) used (charged amount) is increased relative to that of the monomer (B), a low molecular weight polymer can be obtained, and this ratio is increased. When the used amount (charged amount) of the acyl peroxide (A) is lower than that of the monomer (B), a high molecular weight polymer is obtained.

In the production method of the first aspect, it is preferable to add a radical polymerization initiator (E) to the raw material composition in addition to the acyl peroxide (A), and carry out emulsion polymerization. The reaction rate of the monomer can be improved by adding the radical polymerization initiator (E). The radical polymerization initiator (E) is preferably a water-soluble or oil-soluble polymerization initiator, and is a general-purpose initiator such as an azo-based, peroxide-based (excluding acyl peroxide (A)), redox-based initiator. Can be used depending on the polymerization temperature. The radical polymerization initiator (E) is preferably water-soluble, and particularly preferably an azo compound and a salt thereof, such as 2,2′-azobis [2- (2-imidazolin-2yl) propane] and its hydrochloric acid. Examples thereof include salts and acetates. When the salt of the azo compound is thus used, the salt may be previously formed and then added, or the above compound and an organic acid such as hydrochloric acid or acetic acid may be added separately.

By emulsion-polymerizing the raw material composition in this manner, a polymer (X) having a polyfluoroalkyl group or a polyfluorocycloalkyl group at both ends and having a monomer unit of the monomer (B) as a constitutional unit To obtain an aqueous dispersion in which is dispersed in an aqueous medium. The polymer (X) is preferably
It is a polymer represented by the following formula (5). However, equation (5)
In the above, a polymer containing an Rf group at an arbitrary ratio only at one end may be contained, and the polymer (X) obtained by using two or more kinds of the monomer (B) in combination is a block polymer. It may be a random polymer. Rf- (B) _n- Rf ... (5) (In formula, Rf is a Rf group, B is a monomer unit of a monomer (B), n is an integer of 1-500, Preferably it is 5-.
It is an integer of 100. )

The fluorine content of the polymer (X) is 5 to 60.
Mass% is preferable, 10-50 mass% is more preferable,
15-40 mass% is especially preferable. Further, the polymer (X)
The average particle size of 10 to 1000 nm is preferable,
500 nm is more preferable, and 10 to 300 nm is particularly preferable. If the average particle size is less than 10 nm, a large amount of a surfactant is required to obtain a stable aqueous dispersion, the water and oil repellency is reduced, and discoloration occurs when the dyed fabric is treated. . If the average particle size exceeds 1000 nm,
The particles settle in the aqueous medium. The average particle size can be measured by a dynamic light scattering device, an electron microscope or the like. According to the production method of the first aspect, the polymer (X) having a fluorine content and an average particle diameter within the above ranges can be obtained in high yield. According to the production method of the first aspect of the present invention, an aqueous dispersion for a water and oil repellent agent is obtained in which the polymer (X) having Rf groups at both ends is stably dispersed in an aqueous medium. The aqueous dispersion thus obtained is the polymer (X) which is a water / oil repellent component.
Has excellent dispersibility in an aqueous medium, and the side chain has Rf
Since the Rf group has a higher orientation than the group having a group and the adhesiveness to the object to be treated is high, an excellent water / oil repellency effect can be imparted.

A second aspect of the present invention is an aqueous dispersion for a water and oil repellent produced by the production method of the first aspect, wherein the polymer (X) is water (D) and, if necessary, water-soluble. It is an aqueous dispersion liquid dispersed in an aqueous medium composed of a hydrophilic solvent (F). This aqueous dispersion may contain an unreacted product, a by-product, a decomposed product of acyl peroxide (A), and the like, which are produced during emulsion polymerization. The content of the polymer (X) in the water dispersion for water and oil repellents of the second aspect is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 35% by mass.
Is particularly preferable. The preferred ranges of the fluorine content and the average particle size of the polymer (X) are as described in the first aspect. The content of the solvent (F) with respect to the water (D) in the aqueous medium (the amount of the solvent (F) / the amount of the water (D)) is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, 0-1
0 part by mass is particularly preferred.

The water dispersion for water and oil and oil repellents of the second aspect provides excellent stability and water and oil and oil repellency durability when used in combination with other additives. The polymer blender, other water repellents, other oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, cross-linking agents, and other additives may also be included. The water dispersion for water and oil repellents of the second aspect can be applied as it is to the object to be treated as a water and oil repellent, but depending on the purpose and application, water and / or a water-soluble solvent can be optionally added. It is also possible to dilute it to a concentration of and apply it to the object to be treated.

As a method of applying to the object to be treated, any method can be adopted depending on the kind of the object to be treated or the preparation form of the composition. For example, a method of applying it on the surface of the object to be processed by a coating method such as dip coating or spraying and drying it is adopted. Further, if necessary, it may be applied together with an appropriate cross-linking agent and subjected to heat treatment such as curing. When it is applied to a textile fabric such as nylon or polyester, the solid content is 0.1 to 3 in order to obtain appropriate water / oil repellency, to maintain the texture of the fabric, or from an economical point of view.
Mass% is preferable, and 0.5-2 mass% is especially preferable.
In order to exhibit sufficient water and oil repellency, heat treatment such as curing (temperature is 80 to 200 ° C., time is 30 to
It is preferable to perform this for 300 seconds.

The object to be treated with the fiber treatment composition of the present invention is mainly fiber or fiber woven fabric, but other than these, such as glass, paper, wood, leather, fur,
It may be used for treating asbestos, bricks, cement, metal and its oxides, ceramic products, plastics and the like. Examples of fibers include synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, natural fibers such as animal and vegetable fibers, glass fibers, carbon fibers, and inorganic fibers such as asbestos fibers. , Or a mixed fiber thereof.

In the water dispersion for water and oil repellents according to the second aspect of the present invention, the polymer (X) can be stably dispersed in the water dispersion.
The water dispersion for water and oil repellents of the second aspect has excellent water and oil repellency when the fluorine content of the polymer (X), which is a water and oil repellent component, is as low as about 50% by mass or less. Can be given.

Furthermore, the water dispersion for water and oil repellents of the second aspect can be mixed with another fluorine-based water and oil repellent having a water and oil repellent effect and applied to the object to be treated. The fluorine-based water / oil repellent may be any of known water-based water / oil repellents. As the water-based water and oil repellent, for example, Asahi Guard AG710, AG480, AG925, AG78
0 (Asahi Glass Co., Ltd.) can be used. The mixing ratio of the water dispersion for water and oil repellents of the second aspect and other fluorine-based water and oil repellents is preferably 1: 100 to 100: 1 in terms of the solid content concentration of both, and 5: 100 to 100 :. 5 is more preferable, and 10:
100 to 100: 10 is particularly preferable. These mixtures can be further diluted with water and / or a water-soluble solvent to a desired concentration and applied to the object to be treated. The method of applying the object to be treated is as described above. Since the polymer (X), which is the water / oil repellent component contained in the water / oil repellent aqueous dispersion of the second aspect, has excellent adhesiveness to the object to be treated, it is a known fluorine-based water / oil repellent agent. Addition to the above improves the washing durability of known fluorine-based water and oil repellents.

[0031]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Unless otherwise specified,% and parts represent mass% and mass part, respectively. [Example 1] Stearyl acrylate 32.4 g, hydroxyethyl acrylate 0.7 g, polyoxyalkylene glycol monomethacrylate (Blenmer PEP manufactured by NOF CORPORATION) 0.7 g, and polyoxyethylene oleyl ether as a nonionic surfactant were dissolved in water. 20%
13.8 g of an aqueous solution, 6.9 g of a 10% aqueous solution of stearyl triethylammonium chloride as a cationic surfactant dissolved in water were added, and 25.8 g of water and 17.2 g of acetone were added. This mixture is mixed with a high pressure emulsifier (APV
The product was emulsified at a pressure of 5000 psi using a 8.30H type manufactured by the company. The obtained emulsion was placed in a 2000 mL four-necked flask, and the temperature was controlled at 30 ° C. under a nitrogen atmosphere, and di (perfluoroheptanoyl) peroxide as an acyl peroxide having a polyfluoroalkyl group was used as a fluorine solvent AK
-225, manufactured by Asahi Glass Co., Ltd.) was slowly added dropwise with 24 g of a 30% solution. Then, when reacted at 55 ° C. for 12 hours, a white latex was obtained. When the solid content concentration of this latex was measured, it was 25.1%. Here, the solid content concentration is considered to be almost equal to the total concentration of the produced polymer (X), the surfactant (C) and the radical polymerization initiator (E). The average particle size of the polymer measured with a dynamic light scattering particle size measuring device ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) was 0.30 μm. further,
Take 10 g of the obtained latex and use 100 m of ethanol.
L was added and stirred to precipitate the polymer, which was separated by filtration and washed with ethanol. After drying it,
Fluorine analysis of the obtained polymer gave 10.5.
%Met. Furthermore, when the obtained polymer was dissolved in THF and the molecular weight was measured by gel permeation chromatography, the weight average molecular weight was 3,500.

[Example 2] 2,2'-azobis (2-methylpropionamidine) as an azo radical polymerization initiator together with an acyl peroxide having a polyfluoroalkyl group
A white latex was obtained in the same manner as in Example 1 except that 0.10 g of the dihydrochloride was added. The obtained latex has a solid content concentration of 35.1% and an average particle size of 0.22 μm.
Met. After the obtained latex was precipitated and dried in the same manner as in Example 1, the product was subjected to fluorine analysis to find that it was 11.5%. Further, the molecular weight of the polymer was measured in the same manner as in Example 1. As a result, the weight average molecular weight was 5,000.
Met. The obtained latex was diluted with water to prepare 300 g of a solution having a solid content of 1%. A polyester tropical cloth was dipped in this solution as a test cloth, and the cloth was squeezed between two rubber rollers to adjust the wet pickup to 80% by mass, and then 110 ° C. for 90 seconds and then 170 ° C. for 60 seconds with a pin tenter. Cured. When the water repellency of the obtained test cloth was evaluated by the following alcohol method, the number of kits shown in Table 1 was grade 4.

<Evaluation of water repellency (alcohol method)> Droplets of a 2-propanol aqueous solution kit having different concentrations (diameter of about 4 m
m) was gently placed on the test piece and evaluated by the highest number of kits that did not cause wetting for 30 seconds (Table 1). The larger the number of kits, the better the water repellency.

[0034]

[Table 1]

Example 3 Latex 1.6 obtained in Example 2
g and a fluorine-based water and oil repellent AG480 (manufactured by Asahi Glass Co., Ltd.)
15 g was diluted with water to prepare 300 g of an aqueous solution.
A polyester tropical cloth was dipped in this aqueous solution as a test cloth, and the cloth was squeezed with two rubber rollers to make the wet pickup 75%, and then cured with a pin tenter at 110 ° C. for 90 seconds and then at 170 ° C. for 60 seconds. The test cloth thus obtained was evaluated for oil repellency and water repellency. The oil repellency is evaluated by AATCC-Test Met.
Hod 118-1997, and the oil repellency numbers shown in Table 2 were used. Water repellency is evaluated according to JIS-L109
2 1992 Spray test (JIS method)
The water repellency numbers shown in Table 3 were used. The water repellency was also evaluated by the alcohol method, and the kit numbers shown in Table 1 were used. As a result, the oil repellency is grade 5, and the water repellency (JI
The S method) was 100, and the water repellency (alcohol method) was 9th grade.

[0036]

[Table 2]

[0037]

[Table 3]

The test cloth was evaluated for oil repellency and water repellency after washing. Washing is JIS L 10
92: 1998 5.2a) 3) In accordance with the C method, washing was performed at home equivalent to 5 times of washing (referred to as "HL-5"). For the washing, a fully automatic repeated washing tester (manufactured by Daiei Kagaku Seiki Co., Ltd., trade name “AWS-30”) and a detergent (Kao Co., trade name “Attack”) were used. Drying after washing was air-dried overnight at a temperature of 25 ° C. and a humidity of 60% RH. As a result, the oil repellency after washing is grade 2, and the water repellency (JI
The S method) maintained 80, and the water repellency (alcohol method) maintained 8th grade.

[0039]

EFFECTS OF THE INVENTION According to the production method of the present invention, the polymer (X) having excellent water and oil repellency and excellent adhesiveness to an object to be treated is stably dispersed in an aqueous medium. A water and oil repellent dispersion for water is obtained. The water dispersion for water and oil repellents of the present invention,
By adding it to another fluorine-based water and oil repellent, it is possible to improve the washing durability of the other fluorine-based water and oil repellent.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 201/04 C09D 201/04 D06M 15/277 D06M 15/277 15/295 15/295 F term (reference) 4H020 BA13 4J011 AA05 KA14 KA15 KA20 KB22 KB29 4J015 BA06 4J038 CB031 CC021 CD021 CD081 CE011 CE051 CG141 CG151 CG171 CH031 CH051 CH121 CH141 CH171 CH201 CH241 CH251 CK011 DB221 KA06 KA06 CAT06 PC02 PC03 PC02 PC08 PC03 PC04 PC02 PC03 PC04 PC09 PC04 PC08 PC03 PC04 PC08 PC03 PC04 PC09 PC04 PC09 PC04 PC08 PC03 PC04 PC08 PC03 PC04 PC09 PC04 PC03 PC04 PC08 PC03 PC04 PC09 PC08 PC03 PC04 PC02 PC03 PC04 PC08 PC03 PC04 PC08 PC03 PC04 PC08 PC03 PC04 PC09 PC04 PC03 PC04 PC09 PC04 PC08 PC03 PC04 PC09 PC02 PC03 PC04 PC09 PC02 PC03 PC04 PC02 PC03 PC04 PC08 PC03 PC04 PC03 PC04 PC02 PC03 PC04 PC08 PC03 PC04 PC03 PC04 PC08 PC03 PC04 PC08 PC03 PC04 PC09

Claims (4)

[Claims] 1. An emulsion polymerization is carried out using an acyl peroxide (A) having a polyfluoroalkyl group or a polyfluorocycloalkyl group at both ends represented by the following formula (1), and a polyfluoroalkyl group or A method for producing an aqueous dispersion for a water / oil repellent, which comprises a polymer (X) having a polyfluorocycloalkyl group. RfC (= O) OOC (= O) Rf (1) (In the formula, Rf is a polyfluoroalkyl group or a polyfluorocycloalkyl group.) 2. A method of emulsifying a raw material composition containing a monomer (B), a surfactant (C) and water (D) under pressure, and then adding the acyl peroxide (A) to carry out emulsion polymerization. The method for producing an aqueous dispersion for a water and oil repellent according to claim 1. 3. The method for producing an aqueous dispersion for a water / oil repellent according to claim 2, which further comprises adding a radical polymerization initiator (E) to carry out emulsion polymerization. 4. An aqueous dispersion for a water and oil repellent produced by the method according to claim 1, 2 or 3.