JPH08291468A - Fluorine-containing water and oil repellent composition and treatment method - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain a fluorine-containing water / oil repellent composition which can be treated by spraying and does not cause treatment unevenness or color unevenness. [Composition] A composition comprising a polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group, and a nonionic surfactant in an aqueous medium, which is spray-treated. Stuff. A treatment method in which such a composition is sprayed onto the surface of the object to be treated so that the weight of the polymer is 20 to 200 g / m ^2, and then the composition is heated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing water / oil repellent composition and a treatment method with the composition. The fluorine-containing water / oil repellent composition of the present invention can be treated even when it is applied to fibers partially retaining water / oil repellency or fibers having partially different water / oil repellency. It has an advantage that it can be applied without causing unevenness.

[0002]

2. Description of the Related Art Fluorine-containing water and oil repellents are widely processed for the purpose of imparting water and oil repellency to textiles such as clothes. Since the water / oil repellency usually decreases with the passage of time of wearing clothes, an organic solvent type treatment agent containing a fluorine-containing compound is used for the purpose of recovering the water / oil repellency. Is being sprayed on.

When the treatment agent is sprayed onto the garment, if the treatment agent is of an organic solvent type, the surface tension of the treatment agent is low, so that the surface of the garment can be uniformly wetted. But,
The organic solvent type treating agent has a problem in working environment such as organic solvent poisoning and may cause a fire when the organic solvent is flammable, and thus a safe processing method has been demanded.

[0004]

A water-dispersion type treatment agent has been proposed as a treatment agent for solving the problem. However, the conventional water-dispersion type treatment agent causes uneven wetting of the clothing surface,
There is a problem that so-called processing unevenness occurs. In addition, the decrease in water / oil repellency does not occur uniformly over the entire clothing, but in reality, it decreases in a certain part and sufficient performance is maintained in a certain part. When a water-dispersed treatment agent is used for such clothes, there is a problem that processing unevenness becomes remarkable.

Further, since the fluorine-containing compound has a low refractive index, it is known that color deepening occurs. The deepening of the color does not cause any particular problem if the entire fabric can be uniformly treated with the treatment agent, but if the treatment is not uniform, it causes color unevenness. In particular, it has been known that deep coloration is remarkable when the fiber woven fabric has a dark color. Therefore, in practice, there is a problem that processing with an aqueous dispersion that is likely to cause uneven treatment cannot be performed.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and involves adding a surfactant having a specific structure to an aqueous dispersion of a fluoropolymer. It was found that even a fiber woven fabric that is partially retained water repellency can be imparted with water and oil repellency without uneven treatment.

That is, the present invention is a composition containing a polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group and a nonionic surfactant in an aqueous medium, and A fluorine-containing water / oil repellent composition, characterized in that the composition is a spray-treated composition. Further, the present invention provides a polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group, and a composition containing a nonionic surfactant dispersed in an aqueous medium, Provided is a treatment method characterized by spraying the surface of an object to be treated so that the combined weight is 20 to 200 g / m ^2, and then heating.

The "polymerizable monomer having a fluorine-containing organic group" of the present invention includes one polymerizable group such as vinyl group and vinylidene group, and one organic group containing at least one fluorine atom. A compound having an individual. The polymerizable group is preferably a vinyl group. Further, the fluorine-containing organic group is preferably a polyfluoro organic group which is an organic group containing two or more fluorine atoms. Further, the polyfluoroorganic group is preferably a polyfluoroalkyl group. The polyfluoroalkyl group means a group in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. In the following, the polyfluoroalkyl group will be referred to as R _f group.

The R _f group preferably has 1 to 20 carbon atoms, and 4
-16 are especially preferable. Further, the R _f group preferably has a linear or branched structure, and when the R _f group has a branched structure, the branched portion is preferably present at the terminal portion of the R _f group. R
The number of fluorine atoms in the _f group is (the number of fluorine atoms in the R _f group)
When expressed by / (the number of hydrogen atoms of the alkyl group having the same carbon number as the R _f group), 60% or more is preferable, and 80% or more is particularly preferable. The R _f group may contain a halogen atom other than a fluorine atom. The halogen atom is preferably a chlorine atom.

Further, the carbon atom of the R _f group may be substituted with an etheric hydrogen atom, a thioetheric sulfur atom or the like. The R _f group is preferably a perfluoroalkyl group in which substantially all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, or a group having a perfluoroalkyl group at the terminal portion. When the terminal portion is other than the perfluoroalkyl group, it is preferable that a hydrogen atom or a chlorine atom be present.

The perfluoroalkyl group is C _n F.
A group represented by _{2n + 1} (where n is an integer of 4 to 16) is preferable, and a group in which n is 6 to 12 is particularly preferable.

[0012] _the R _f group in the specific example as _{C 4 F 9 - [CF 3} (CF 2) 3 -, (CF 3) 2 CF
_{CF 2 -, (CF 3)} 3 C-, and CF ₃ CF ₂ CF
(CF ₃₎ - including structural isomers groups such], C ₅ F ₁₁ -
[For example, CF ₃ (CF ₂ ) ₄ − etc.], C ₆ F ₁₃ −
[For example, CF ₃ (CF ₂ ) ₅ − etc.], C ₇ F ₁₅ −
[For example, CF ₃ (CF ₂ ) _6-, etc.], C ₈ F _17-
[For _{example, CF 3 (CF 2) 7} - , etc.], C ₉ F ₁₉ -
[For example, CF ₃ (CF ₂ ) ₈ − etc.], C ₁₀ F ₂₁ −
[For example, CF ₃ (CF ₂ ) ₉ − etc.], CHF ₂ (C
F ₂ ) _m − (where m is an integer of 1 to 15) and the like can be mentioned, but the invention is not limited thereto.

The polymerizable monomer having a fluorine-containing organic group is preferably a compound having a structure in which the fluorine-containing organic group and the polymerizable group are linked by a divalent bonding group. The divalent linking group includes an ester bond or an ester bond-containing 2
Valuable linking groups are preferred.

Furthermore, in the polymerizable monomer having a fluorine-containing organic group, the R _f group and the vinyl group contain an ester bond.
_Rf group-containing (meth) acrylates of the formula below, which are linked by a valent linking group, are preferred. In this specification, both acrylate and methacrylate are collectively referred to as (meth) acrylate, and similarly, for example, both acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid.

In the formula below, R _f represents the above polyfluoroalkyl group. However, it is assumed that one or more fluorine atoms are bonded to the carbon atom of R _f bonded to A. R _f is preferably a perfluoroalkyl group having 4 to 16 carbon atoms. In addition, A represents a divalent organic group, and the groups described in the following specific examples are preferable. R ⁴ represents a hydrogen atom or a methyl group.

[0016]

## STR1 ## CH ₂ = CR ⁴ --COO-A-R _f

Examples of the R _f group-containing (meth) acrylate include, but are not limited to, the following compounds.

[0018]

## STR2 ## ^{_{CH 2 = CR 4 COOCH 2 CH}} 2 R f CH 2 = CR 4 COOCH 2 CH 2 N (C 3 H 7) COR f CH 2 = CR 4 COOCH (CH 3) CH 2 R f CH 2 = ^{_{CR 4 COOCH 2 CH 2 N (}} CH 3) SO 2 R f CH 2 = CR 4 COOCH 2 CH 2 N (CH 3) COR f CH 2 = CR 4 COOCH 2 CH 2 N (C 2 H 5) SO 2 R ^{_{f CH 2 = CR 4 COOCH 2}} CH 2 N (C 2 H 5) COR f CH 2 = CR 4 COOCH 2 CH 2 N (C 3 H 7) SO 2 R f

The R _f group-containing (meth) acrylate may be used alone or in combination of two or more. When using two or more kinds, it is preferable to use two or more kinds of compounds having different carbon numbers of R _f groups.

The polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group of the present invention (hereinafter referred to as "fluorine-containing polymer") is used for controlling the fluorine content in the polymer. For the purpose, in addition to the polymerized unit of the above-mentioned polymerizable monomer having a fluorine-containing organic group, a polymerized unit of another monomer having a radical-polymerizable unsaturated bond group (hereinafter referred to as a comonomer). It is preferable to include one or more of

As the comonomer, vinyl chloride, stearyl acrylate, ethylene, vinyl acetate, vinyl fluoride, halogenated styrene, α-methylstyrene, p-methylstyrene, (meth) acrylic acid and its alkyl ester, (polyoxyalkylene ) (Meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, methylolated (meth) acrylamide, N
-Methylol (meth) acrylamide, alkyl vinyl ether, (halogenated alkyl) vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, benzyl (meth) acrylate, isocyanate ethyl (meth) Examples thereof include, but are not limited to, acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, maleic anhydride, (meth) acrylate having polysiloxane, and N-vinylcarbazole. Among these, vinyl chloride and stearyl acrylate are preferable as the comonomer.

The amount of the polymerized unit of the R _f group-containing (meth) acrylate contained in the fluoropolymer of the present invention is suitably about 25 to 45% by weight in the polymer as the fluorine content. If it exceeds 45% by weight, the color deepening of the polymer becomes remarkable, and the unevenness of treatment causes the unevenness of color. If it is less than 25% by weight, sufficient water and oil repellency cannot be imparted.

The above-mentioned fluorine-containing polymer is preferably dispersed and contained in an aqueous medium. The particle size of the fluoropolymer in the aqueous medium is 0.05 to 0.3 μ from the viewpoint of dispersion stability.
About m is preferable.

As the method for synthesizing the fluoropolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected. For example, polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization and photopolymerization can be adopted. Of these, in the present invention, it is preferable to polymerize by an emulsion polymerization method. For example, there may be mentioned a method of emulsifying a compound to be polymerized in water in the presence of a surfactant or the like, and causing a polymerization initiation source to act under stirring to polymerize. Examples of the polymerization initiation source include polymerization initiators such as organic acid peroxides, azo compounds and persulfates, and ionizing radiation such as γ-rays.

The surfactant used for the polymerization is
Almost all of various cationic or nonionic surfactants can be used, but since the composition of the present invention contains a nonionic surfactant, it is preferable to employ the surfactant.

The composition of the present invention contains the polymer synthesized by the above method, a nonionic surfactant, and an aqueous medium.
Although a nonionic surfactant is essential as the surfactant, it may contain an anionic surfactant or a cationic surfactant. However, if the amount of the anionic surfactant or the cationic surfactant is too large, the water / oil repellency may be deteriorated. Therefore, when these surfactants are contained, the amount is preferably small. On the other hand, the nonionic surfactant is an essential component mainly for increasing the permeability of the water and oil repellent. It also has the advantage of reducing the bathochromic effect.

As the nonionic surfactant, ethers of polyhydric alcohols are preferable, and polyoxyalkylene monoalkyl ethers are particularly preferable. The oxyalkylene part of the polyoxyalkylene monoalkyl ether is
Oxyethylene and / or oxypropylene are preferred. As the nonionic surfactant, a compound represented by the following formula is particularly preferable. In the following formula, R ⁵ represents an alkyl group or an alkenyl group having 8 or more carbon atoms. s is 5 to 30
And p is an integer of 0 to 20.

[0028]

Embedded image R ⁵ O (C ₂ H ₄ O) _s [CH ₂ CH (CH ₃ ) O] _pH

R ^{5 in the} above formula is a long-chain alkyl group or alkenyl group having 8 or more carbon atoms and may have either a straight chain structure or a branched structure. A branched structure is preferable from the viewpoint of permeability. Moreover, s is an integer of 5 to 30, and an integer of 10 to 20 is particularly preferable. p is preferably an integer of 5 to 10. When s is 4 or less, or p is 21 or more, it becomes poorly soluble in water and does not dissolve uniformly in an aqueous medium, so that the effect of improving permeability may be reduced. Further, if s is 31 or more, the hydrophilicity is increased and the water repellency may be reduced.

Specific examples of the nonionic surfactant are shown below, but the invention is not limited thereto. However, in the following formula, s and p have the same meaning as above, and s is 10 to 20.
Is preferred, and p is preferably an integer of 5-10.

[0031]

Embedded image C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) _s [CH ₂ CH (CH ₃ ) O] _p H C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) _s [CH ₂ CH (CH ₃ )] _{O] p H C 16 H 33} O (CH 2 CH 2 O) s [CH 2 CH (CH 3) O] p H C 12 H 25 O (CH 2 CH 2 O) s [CH 2 CH (CH 3) _{O] p H (C 8 H} 17) (C 6 H 13) CH-O- (CH 2 CH 2 O) s - - [CH 2 CH (CH 3) O] p H C 10 H 21 O (CH 2 CH ₂ O) _s [CH ₂ CH (CH ₃ ) O] _pH

The amount of the nonionic surfactant contained in the composition of the present invention is preferably 0.05 to 2% by weight in the composition. If the amount is too small, there is a problem that the effect is reduced. If it is more than 2% by weight, there is a problem that sufficient water repellency cannot be obtained. The nonionic surfactant is also effective in terms of preventing color unevenness. This effect is an excellent effect that cannot be achieved by adding alcohols such as ethanol and isopropanol.

The aqueous medium in the composition of the present invention includes:
Water or an organic solvent soluble in water and water is preferable, and water is particularly preferable. When the organic solvent is contained, it is preferable to reduce it as much as possible from the viewpoint of working environment. Acetone, ethanol, isopropanol and the like are preferable as the organic solvent when the water-soluble organic solvent is contained.

The amount of the fluoropolymer in the composition is
About 0.2 to 5% by weight is preferable with respect to the total weight of the composition. If the amount of the fluorinated polymer is too small, it is necessary to use a large amount of the composition, and it takes time to dry the medium after the treatment. On the other hand, if the amount of the fluoropolymer is too large, problems such as rough hardening of texture, unevenness of treatment, and unevenness of bathochromic effect may occur.

Further, the composition of the present invention is a composition which is treated by spraying. The treatment by spraying means treating the composition of the present invention in the form of fine droplets.
It is well known in the art as a method of treating a liquid in the form of fine droplets. For example, there is an aerosol spray method in which the above composition is diluted to a solid content concentration according to the purpose, and the composition is filled with a pressurized gas component in a container. Examples of the gas component include LPG gas and carbon dioxide gas, and carbon dioxide gas is preferable. Also, as another method, spray pump method, spray trigger method,
Air pump system, air spray system, EP spray system (double structure container), Excel system, roll-on type, pressurized airless spray system, etc.
Pressurized spray trigger system, spray pump system,
Pressurized airless spray method is preferred.

The amount of the water / oil repellent composition of the present invention applied to the surface of the object to be treated is 20 to 200 g by weight of the fluoropolymer.
/ M ² , preferably 40 to 150 g / m ² . The treatment is carried out by spraying. The average diameter of droplets during spraying is preferably 60 to 150 μm, and 10 μm
Those not containing the following droplets are preferable. If the diameter of the droplets is too large, the target cloth tends to be uneven in wetness, while if it is too small, the rate of adhesion to the target cloth decreases, which is uneconomical. The adhesion ratio (the weight ratio of the water / oil repellent agent adhered to the object to the sprayed water / oil repellent agent) is preferably 60% or more.

After spraying the water and oil repellent, it is preferable to carry out a heat treatment. The heat treatment condition is preferably a temperature that is sufficient for the object to be dried and a water- and oil-repellent coating to be formed, and is usually 65 ° C. or higher, and the upper limit may adversely affect the object. The temperature is not high, and is usually 65 to 180 ° C, preferably 80 to 150 ° C.

As the object to be treated with the water / oil repellent composition of the present invention, various examples can be mentioned without any particular limitation. For example, as an example of a fiber woven fabric or a fiber knit, cotton,
Natural animal and vegetable fibers such as hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, carbon fibers, asbestos fibers, etc. Inorganic fibers, or woven or knitted fabrics of these mixed fibers can be mentioned.

The water- and oil-repellent composition of the present invention can be applied to an object to be partially processed that has water- and oil-repellent properties, or an object to be partially processed which has different water- and oil-repellent properties. Also, excellent water / oil repellency can be imparted uniformly without causing unevenness in processing or color. Further, since it is a spray, there is an advantage that even if the shape of the object to be treated is complicated, it can be easily treated. Further, since no treatment equipment or place is required and the treatment is easy, anyone can use it easily.

[0040]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Further, the water repellency and oil repellency in the following examples are shown by the following scales.

That is, the water repellency is JIS-L-1092.
It is expressed by the water repellency number (see Table 1) by the spray method of No. 1, and the oil repellency is shown in Table 2 by placing a few drops (diameter about 4 mm) on the test cloth in two places and permeating after 30 seconds. Determined by the state (AATCC-TM118-196
6). In addition, the water-repellent number and the oil-repellent number are + (-)
Those marked with indicate that each property is slightly better (bad).

[0042]

[Table 1]

[0043]

[Table 2]

[Evaluation method of color unevenness] Half of a black polyester cloth is pretreated with a water and oil repellent (trade name: Asahi Guard / fluorine water and oil repellent manufactured by Asahi Glass Co., Ltd.), and water repellency of the pretreated portion Test cloths with numbers 50, 70 and 100 were prepared. The test cloth was sprayed with the treatment liquid and compared with the color of the portion not pretreated with the water and oil repellent. The case where no color unevenness was observed was evaluated as ◯, the case where it was clearly observed was evaluated as Δ, and the case where color unevenness was observed was evaluated as x.

[Test cloth] Blue nylon taffeta cloth and black polyester doskin cloth are treated with a water and oil repellent,
A fabric having a water repellency of 0, 70, or 100 and a test cloth having an oil repellency of 0, 2, or 6 were prepared.

[Synthesis Example 1] Perfluoroalkyl ethyl acrylate (C _n F _{2n + 1} CH ₂ CH ₂ OCOCH = C
It is a compound represented by H ₂ , and the average value of n is 9.)
60% by weight, stearyl acrylate 36% by weight, 2-
Hydroxyethyl acrylate 4% by weight, dipropylene glycol monomethyl ether 30% by weight, water 170% by weight, polyoxyethylene monooleyl ether (nonionic surfactant / manufactured by Kao) 8% by weight, distearylmethylamine acetate 0.5 wt% was mixed and dispersed by a high pressure homogenizer. The dispersion was charged into a 1 liter glass reactor equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a nitrogen injection tube, and the internal air was replaced with nitrogen gas. 2,2'-azobis (2-
Add 0.5% by weight of methylpropanamidine) hydrochloride 6
The temperature was raised to 0 ° C. and kept for 7 hours. A stable aqueous dispersion having a solid content concentration of 33% by weight and a particle diameter of 0.2 μm was obtained. The monomer reaction rate was 99% or more.

[Synthesis Example 2] Perfluoroalkylethyl acrylate (C _n F _{2n + 1} CH ₂ CH ₂ OCOCH = C
It is a compound represented by H ₂ , and the average value of n is 9.)
55% by weight, stearyl acrylate 40% by weight, N,
4% by weight of N-dimethylacrylamide, 1% by weight of a compound obtained by blocking the isocyanate group of a 1: 1 (molar ratio) reaction product of isophorone diisocyanate and 2-hydroxyethyl methacrylate with methylethylketoxime,
Dipropylene glycol monomethyl ether 30% by weight, water 170% by weight, polyoxyethylene monooleyl ether (nonionic surfactant / manufactured by Kao) 8% by weight
Were mixed and dispersed by a high pressure homogenizer. This dispersion was reacted in the same manner as in Synthesis Example 1 to obtain a stable aqueous dispersion having a solid content concentration of 33% by weight and a particle size of 0.2 μm. The monomer reaction rate was 99% or more.

[Synthesis Example 3] Perfluoroalkylethyl acrylate (C _n F _{2n + 1} CH ₂ CH ₂ OCOCH = C
It is a compound represented by H ₂ , and the average value of n is 9.)
80% by weight, stearyl acrylate 15% by weight, N,
5% by weight of N-dimethylacrylamide, 30% by weight of dipropylene glycol monomethyl ether, 170% by weight of water, and 8% by weight of polyoxyethylene monooleyl ether (nonionic surfactant / manufactured by Kao Corporation) were mixed, and the mixture was mixed with a high-pressure homogenizer. Dispersed. This dispersion was reacted in the same manner as in Synthesis Example 1 to give a solid concentration of 33% by weight and a particle size of 0.
15 μm latex was obtained. Monomer reaction rate is 99%
That was all.

Example 1 The aqueous dispersion of Synthesis Example 1 was diluted with ion-exchanged water so that the solid content concentration was 1% by weight, and 0.1% polyoxyalkylene isodecyl ether was used as a nonionic surfactant. A weight% was added to obtain a treatment liquid. The treatment liquid was sprayed on the prepared test cloth and dried. The treatment liquid is a hand trigger spray (average mist diameter 80μ
m) was sprayed at a distance of 20 cm to 100 g / m ² . Then, after drying naturally, use a home drier 95
Dry at 5 ° C for 5 minutes.

[Examples 2 to 5] In the same manner as in Example 1, the aqueous dispersions of Synthesis Examples 1 to 3 were diluted to the concentrations shown in Table 3, and the nonionic surfactants shown in Table 3 were respectively added. A treatment liquid was prepared by adding the amount (% by weight) shown in Table 3, sprayed on a test cloth, and dried.

Comparative Example 1 A treatment liquid containing no surfactant in Example 1 was prepared, and sprayed on a test cloth in the same manner as in Example 1 and dried.

Comparative Example 2 A treatment liquid containing 10% by weight of ethanol instead of the surfactant of Example 1 was prepared, and sprayed and dried in the same manner as in Example 1.

[Comparative Example 3] A treating agent using sodium dioctylsulfosuccinate as an anionic surfactant in place of the nonionic surfactant A of Example 1 was prepared in the same manner as in Example 1 and applied to a test cloth. Sprayed and dried.

[0054]

[Table 3]

[0055]

Embedded image Nonionic surfactant A: polyoxyalkylene isodecyl ether [CH ₃ [CH (CH ₃ ) CH ₂ ] ₃ O (CH ₂ CH ₂ O) _s [CH ₂ CH (CH ₃ ) O] _pH , the average value of s is 20, and the average value of p is 10. ] Nonionic surfactant B: a polyoxyalkylene oleyl ether _{[CH 3 (CH 2) 7} CH = CH (CH 2) 8 O (CH 2 CH 2 O) s [CH 2 CH (CH 3) O] p H, the average value of s is 10, and the average value of p is 5. ] Anionic surfactant C: sodium dioctyl sulfosuccinate [(C ₈ H ₁₇ OCO) (C ₈ H ₁₇ OCOCH ₂ ) CHSO ₃ Na]

[0056]

[Table 4]

[0057]

The fluorine-containing water / oil repellent composition of the present invention comprises
It is an excellent composition that can be treated cleanly without causing color unevenness that is considered to be caused by uneven penetration. Also,
The excellent performance can be exhibited even when the object to be processed partially having water / oil repellency or the object to be processed having partially different water / oil repellency is processed. Further, since the water / oil repellent treatment agent can be treated by spraying, it has an advantage that anyone can use it easily.

Claims (7)

[Claims] 1. A composition comprising a polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group and a nonionic surfactant in an aqueous medium, which is spray-treated. 1. A fluorine-containing water / oil repellent composition comprising: 2. 0.2 to 5% by weight of a polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group, and
The fluorine-containing water / oil repellent composition according to claim 1, which comprises a composition containing 0.05 to 2% by weight of a nonionic surfactant. 3. The fluorine-containing water / oil repellent composition according to claim 1, wherein the polymerizable monomer having a fluorine-containing organic group is a (meth) acrylate having a polyfluoroalkyl group. 4. The fluorine-containing water-repellent and water-repellent agent according to claim 1, wherein the fluorine content in the polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group is 25 to 45% by weight. Oil agent composition. 5. A polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group, a (meth) acrylate polymerized unit having a polyfluoroalkyl group, and
The fluorine-containing water / oil repellent composition according to any one of claims 1 to 4, which is a copolymer containing a polymerized unit other than a polymerized unit of a (meth) acrylate having a polyfluoroalkyl group. 6. The fluorine-containing water / oil repellent composition according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether. 7. A polymer containing a polymerized unit of a polymerizable monomer having a fluorine-containing organic group, and a composition containing a nonionic surfactant dispersed in an aqueous medium. Is sprayed onto the surface of the object to be treated so as to have a weight of 20 to 200 g / m ^2, and then heated.