JPH1192752A - Water / oil repellent composition - Google Patents

Abstract

[PROBLEMS] To provide a water / oil repellent composition excellent in water / oil repellency and durability of water resistance. Kind Code: A1 (Meth) having a polyfluoroalkyl group
A water / oil repellent composition comprising, as an active ingredient, a copolymer of an acrylate, 2-isocyanateethyl methacrylate in which an isocyanate group is blocked, and a vinyl chloride and / or an alkyl (meth) acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent composition excellent in durability of water / oil repellency and durability of water resistance.

[0002]

2. Description of the Related Art In recent years, water- and oil-repellent and water-resistant treatments for clothing and the like have been actively performed, and various compositions containing copolymers having a polyfluoroalkyl group have been provided according to the purpose ( In the present specification, a polyfluoroalkyl group is hereinafter referred to as “R ^f group.” An acrylate and / or a methacrylate is referred to as “(meth) acrylate.” Other (meth) acryls The same applies to acid alkyl esters, etc.).

For example, in sports and outdoor clothing,
It is required to have high water and oil repellency and high durability against water, such as washing, dry cleaning, and abrasion. As a copolymer component for imparting durability, a (meth) acrylate having an ^Rf group, a blocked isocyanate group (Meth) acrylate having a polyoxyalkylene chain and a copolymer of (meth) acrylate having a polyoxyalkylene chain (JP-A-6-27)
9687) has been proposed.

Further, a copolymer of an acrylate having an R ^f group and vinyl chloride (Japanese Patent Publication No. 50-3438) and a polymer of an acrylate having both an R ^f group and an aromatic blocked isocyanate group (JP-A-3-8873) ), A copolymer of a (meth) acrylate having an R ^f group and a (meth) acrylate having an alicyclic or heterocyclic polyisocyanate group having a blocked isocyanate group (JP-A-6-240239) Has been proposed.

As a crosslinking component for improving durability, N-methylolacrylamide (Japanese Patent Publication No. 39-39)
2350), glycidyl methacrylate (Japanese Unexamined Patent Publication No.
8006) and the like.

[0006]

However, all of the conventional compositions have a disadvantage that the durability during washing cannot be obtained satisfactorily.
Copolymers containing polymerized methacrylate units having a polyoxyalkylene group have the drawback that sufficient water repellency and water resistance cannot be obtained. Further, in order to improve durability, a method of using a compound having an R ^f group and a compound having a melamine resin or a blocked isocyanate group at the time of fiber treatment is also known.
There were yellowing of the fabric and hardening of the texture. Further, a method of improving the water resistance by coating with a polyurethane resin or an acrylic resin or the like is also known, but in this case, there is a disadvantage that the feel becomes hard.

The present invention provides a water / oil repellent composition which can impart durable water / oil repellency and water resistance and has no problems such as yellowing of fabric and hardening of texture.

[0008]

According to the present invention, there is provided a copolymer containing the following polymerized unit (a), polymerized unit (b), and at least one selected from polymerized unit (c) and polymerized unit (d). Provided is a water / oil repellent composition containing a polymer as an active ingredient. Polymerized unit (a): a polymerized unit of a (meth) acrylate having an R ^f group. Polymerized unit (b): 2 in which isocyanate group is blocked
Polymerized units of isocyanateethyl methacrylate. Polymerized unit (c): a polymerized unit of vinyl chloride. Polymerized unit (d): a polymerized unit of an alkyl (meth) acrylate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer unit (a) is a polymer unit of a (meth) acrylate having an R ^f group. R ^f
The (meth) acrylate having a group refers to a compound in which an R ^f group is present in an alcohol residue portion of the (meth) acrylate.

The R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms. Further, the R ^f group is preferably a linear or branched group. In the case of a branched group, it is preferable that the branched portion is present at the terminal portion of the R ^f group and is a short chain having about 1 to 4 carbon atoms. The R ^f group may contain another halogen atom other than a fluorine atom. As another halogen atom, a chlorine atom is preferable. Further, the carbon atom in the R ^f group may be substituted with an etheric oxygen atom.

[0011] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 (%)
When expressed by, it is preferably 60% or more, particularly 80%
The above is preferred. Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms (that is, a perfluoroalkyl group) or a group having a perfluoroalkyl group at the terminal portion.

The number of carbon atoms in the perfluoroalkyl group is from 2 to
20 is preferable, and especially 6 to 16 is preferable. 6 carbon atoms
If less than 16, the water and oil repellency of the water and oil repellent composition tends to decrease, if more than 16,
The copolymer becomes solid at room temperature, has high sublimability, and may be difficult to handle.

The (meth) acrylate having an R ^f group is preferably a compound represented by the following formula 1. R ^f -Q-OCOCR = CH ₂ Formula 1

In the formula 1, R ^f represents an R ^f group. Q is 2
It shows a valent organic group. R represents a hydrogen atom or a methyl group. The R ^f group is preferably a group described in the following specific examples and examples.

Q is-(CH ₂ ) _{p + q} -,-(C
_{H 2) p CONH (CH 2} ) q -, - (CH 2) p OC
_{ONH (CH 2) q -,} - (CH 2) p SO 2 NR '
_{(CH 2) q -, -} (CH 2) p NHCONH (CH
_{2) q -, - (CH} 2) p -CH (OH) - (CH 2)
_q- and the like are preferable. Here, R 'represents a hydrogen atom or an alkyl group. P and q each independently represent an integer of 0 or more, and p + q is an integer of 1 to 22. Among these, Q is _{- (CH 2) p + q} -, - (CH 2) p C
ONH (CH _{2) q} -, or _{- (CH 2) p SO 2} N
R ′ (CH ₂ ) _q —, and q is an integer of 2 or more;
Preferably when p + q is 2 to 6, in particular, when p + q is _{2~6 - (CH 2) p +} q -, i.e., an ethylene group - hexamethylene group. It is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q.

Specific examples of the (meth) acrylate having an R ^f group are shown below. Here, R represents a hydrogen atom or a methyl group.

[0017]

Embedded image CF ₃ (CF ₂ ) ₄ CH ₂ OCOCR = CH
₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR = CH ₂ , H (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR = CH ₂ , ( CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR
_{= CH 2, CF 3 (CF} 2) 7 SO 2 N (C 3 H 7) CH 2 CH 2
OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ O
COCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂
OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OCOCR =
CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR
ＣＨCH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH
_{3) - OCOCR = CH 2,} (CF 3) 2 CF (CF 2) 5 CH 2 CH (OH) CH
₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR =
CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ CH ₂ O
COCR = CH _2.

The copolymer of the present invention comprises one polymerized unit (a).
Species or two or more species may be contained. When two or more polymerization units (a) are contained, the mixture is preferably a mixture of (meth) acrylates having R ^f groups having different numbers of carbon atoms.

The polymerized unit (b) is a polymerized unit of 2-isocyanateethyl (meth) acrylate in which an isocyanate group is blocked. By containing polymerized units of 2-isocyanateethyl methacrylate in which isocyanate groups are blocked, not only the durability of water / oil repellency to natural fibers such as cotton is remarkably improved, but also, unexpectedly, polyester, polypropylene, etc. The water- and oil-repellency durability of a substrate having no functional group that reacts with the isocyanate group of the above was also greatly improved.

2- isocyanate group is blocked
Isocyanate ethyl (meth) acrylate can be easily obtained by reacting the isocyanate group of 2-isocyanate ethyl (meth) acrylate with a known or well-known blocking agent.

Examples of the blocking agent for the isocyanate group of 2-isocyanatoethyl (meth) acrylate include alkyl ketoximes, phenols, alcohols, β
-Diketones and lactams are preferred, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butyl alcohol, maleic imide and the like are particularly preferred, and especially alkyl ketoxime such as methyl ethyl ketoxime. And a lactam such as ε-caprolactam or the like, and a blocking agent comprising a compound having a dissociation temperature of 120 to 180 ° C are preferred.

The polymerized unit (c) is a polymerized unit of vinyl chloride. The polymerized unit (d) is a polymerized unit of an alkyl (meth) acrylate. As the (meth) acrylic acid alkyl ester, those containing only one (meth) acryloyl group in one molecule are preferable. As the alkyl group, a linear, branched or cycloalkyl group having 3 to 20 carbon atoms is preferable. Preferably, the hydrogen atom of the alkyl group is not substituted.

Specifically, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl ( Meta)
Acrylate, n-butyl (meth) acrylate and the like can be mentioned.

In the copolymer of the present invention, at least one selected from polymerized units (c) and (d) is used.
The species may include only the polymerized unit (c), include only the polymerized unit (d), or include both the polymerized unit (c) and the polymerized unit (d).

In the present invention, the polymerized unit (a) is represented by R ^f
If it has a group, it may have another group. Also,
The polymerization unit (b) may have another group other than the ^Rf group as long as it has a blocked isocyanate group.

Further, the copolymer of the present invention can be obtained by polymerizing other polymerizable monomers in addition to the above polymerized units (a), (b), (c) and (d). Units may be included. By including polymerized units of other polymerizable monomers, durability of water and oil repellency, adhesion of the copolymer to the substrate, cross-linking and film-forming properties, flexibility, stain resistance, etc. Can sometimes be improved. Examples of other polymerizable monomers include the following.

Ethylene, vinyl acetate, vinyl fluoride, vinylidene halide, styrene, α-methylstyrene,
p-methylstyrene, (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene Glycidyl (meth) acrylate, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, (meth) acrylate having a polysiloxane moiety, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (2-dimethylamino) ethyl (meth) acrylate, hydroxyalkyl (meth) acryl Over doors and the like.

The ratio of each polymerization unit in the copolymer is 9.9 to 90 parts by weight of the polymerization unit (a) and 0.1 to 30 parts by weight of the polymerization unit (b) in 100 parts by weight of the copolymer. , Polymerized units (c) and / or polymerized units (d) in a total amount of 9.9 to
It is preferable to include 90 parts by weight. When other polymerizable monomers are contained, the other polymerizable monomers are copolymer 10
The range of 30 parts by weight or less in 0 parts by weight is preferable.

When the polymerization unit (a) is within the above range, the water / oil repellency is improved, and a sufficient film strength and high durability can be obtained. When the polymerization unit (b) is within the above range, the durability of water / oil repellency is obtained, the adhesion to the substrate is high, and the formation of the coating is favorably affected, so that the water / oil repellency is improved. When the polymerized unit (c) and / or the polymerized unit (d) are within the above range, high water / oil repellency is obtained, and the film-forming property and film strength on the base material are sufficient, and high durability is obtained.

The method for synthesizing the copolymer in the present invention includes (meth) acrylic acid having an ^Rf group, 2-isocyanatoethyl (meth) acrylate having an isocyanate group blocked, vinyl chloride and (meth) acrylate.
At least one selected from alkyl acrylates
A method of copolymerizing a polymerizable monomer mixture containing a seed in the presence of a medium can be employed.

As the method of copolymerization, known or well-known polymerization methods, that is, bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, photopolymerization, solution polymerization, and the like can be adopted. For example, in the case of emulsion polymerization, a method of adding a polymerizable monomer and an emulsifier to a medium comprising water or a mixed solvent of water and a water-soluble solvent, emulsifying the polymerizable monomer, and then polymerizing,
In the case of solution polymerization, a method of dissolving and dispersing a polymerizable monomer in a medium comprising a solvent or a mixed solvent of a solvent and water and polymerizing the same can be adopted.

Solvents used in the polymerization include alcohols such as isopropyl alcohol and 2-butanol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
Glycols such as tripropylene glycol monomethyl ether and ethylene glycol monomethyl ether,
Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane, heptane, toluene, xylene and mineral spirits; hydrofluorocarbons, hydrochlorofluorocarbons and methylene chloride Halogen-based solvents can be used. As a polymerization initiation source, a polymerization initiator such as a peroxide, an azo compound or a persulfate, or an ionizing radiation such as γ-ray can be employed.

The molecular weight of the copolymer obtained by such a synthesis method is preferably from 1 × 10 ³ to 1 × 10 ⁶ . The composition containing the copolymer and the medium can be used as the water / oil repellent composition of the present invention by itself or by adjusting the concentration as needed.

The water / oil repellent composition of the present invention contains the above copolymer as an active ingredient, and is usually a composition containing the above copolymer and a medium. The medium is preferably water, a mixture of water and a solvent, or a solvent, particularly preferably water or a mixture of water and a solvent. The amount of the copolymer in the composition is preferably 1 to 50% by weight, more preferably 1 to 30% by weight. The concentration can be appropriately changed depending on the form at the time of use and the intended state. After obtaining the copolymer, the water / oil repellent composition of the present invention can be prepared in an arbitrary form such as an emulsion, suspension, dispersion, solution, aerosol, gel and the like according to a conventional method.

Further, the water / oil repellent composition of the present invention may contain a compound other than the above-mentioned copolymer. Other compounds include other water repellents and oil repellents, or other polymer blenders, additives such as crosslinking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkles, and the like. When the other compound is contained, the amount of the other compound is preferably 0.01 to 500% by weight based on the above copolymer, particularly preferably 0.1 to 500% by weight.
~ 100% by weight is preferred. The type and amount of the other compound can be appropriately changed according to the treatment purpose of the water / oil repellent and the base material.

The water / oil repellent composition of the present invention can be applied to a substrate by any method. For example, when the water- and oil-repellent composition of the present invention is an aqueous dispersion or a solvent solution, a method of adhering to the surface of a substrate by a known coating method such as dip coating and drying is adopted. Drying may be performed at room temperature or may be heated. When heating, about 40-200 degreeC is preferable. If necessary, curing may be performed.

The object to be treated according to the present invention is an object to be treated having a coating formed on the surface of the substrate by treating the surface of the substrate with the water / oil repellent composition and then drying it. Substrates treated with the water and oil repellent of the present invention include, for example, fibers,
There are fiber woven fabric, fiber knitted fabric, glass, paper, wood, leather, fur, asbestos, brick, cement, ceramics, metal and metal oxide, ceramic products, plastics and the like, and fibers, fiber woven fabric and fiber knitted fabric are preferred. Examples of fibers include cotton,
Animal and plant natural 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; and inorganic fibers such as glass fibers and asbestos fibers. Or a mixed fiber thereof.

[0038]

EXAMPLES Examples 1 and 2 are examples of the synthesis of blocked 2-isocyanatoethyl (meth) acrylate, Examples 3-6.
Are Examples of the present invention, and Examples 7 to 12 are Comparative Examples.

Example 1 A four-necked glass flask was equipped with a reflux condenser, a thermocouple thermometer, and a stirrer, and charged with 155 g (1 mol) of 2-isocyanatoethyl methacrylate, methyl isobutyl ketone as a solvent, and dried. 8 under nitrogen
The temperature was raised to 0 ° C., and 87 g (1 mol) of methyl ethyl ketoxime was added dropwise to carry out a reaction for 2 hours. Thereafter, it was confirmed by IR that the absorption of the isocyanate group had completely disappeared. By the above reaction, 242 g of methyl ethyl ketoxime adduct of 2-isocyanate ethyl methacrylate (hereinafter referred to as MIE) was obtained.

Example 2 A four-neck glass flask was equipped with a reflux condenser, a thermocouple thermometer, and a stirrer. 155 g (1 mol) of 2-isocyanatoethyl methacrylate and methyl isobutyl ketone as a solvent were charged. The temperature was raised to 80 ° C. under dry nitrogen, and 113 g (1 mol) of ε-caprolactam was added dropwise and reacted for 2 hours. Thereafter, it was confirmed by IR that the absorption of the isocyanate group had completely disappeared. By the above reaction, 268 g of 2-isocyanatoethyl methacrylate ε-caprolactam adduct (hereinafter referred to as C
IE. ) Got.

[Example 3] C _n F _{2n + 1} (CH ₂ ) ₂ O was added as a polymerizable monomer to a 100 mL glass polymerization ampoule.
COCH = CH ₂ (where n is an integer of 6 to 16, and the average of n is 9. Hereinafter, referred to as FA) 12.0
g (60 parts by weight), stearyl methacrylate (hereinafter S)
Recorded as TA. ) 7.2 g (36 parts by weight), MIE 0.4
g (2 parts by weight), 0.4 g (2 parts by weight) of 2-hydroxyethyl acrylate (hereinafter referred to as HEA), 12.0 g of acetone, 35.0 g of water, a nonionic surfactant (manufactured by Kao Corporation) Name: Emulgen 920) 1.6 g,
0.6 g of stearyltrimethylammonium chloride,
0.1 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was shaken under a nitrogen atmosphere.
Polymerization was performed at 18 ° C. for 18 hours to obtain a composition containing a copolymer. 1
After 8 hours, the reaction crude liquid was analyzed by gas chromatography to confirm that no polymerizable monomer remained.

A treatment bath was prepared by adding water to the obtained composition containing the copolymer and adjusting the concentration of the copolymer to 0.8% by weight. Tropical cloth made of polyethylene terephthalate (PET) (in the case of water resistance evaluation, ultra-fine fiber high-density polyester taffeta) is prepared as a treatment cloth,
After immersion in the treatment bath, squeeze with mangle and pick up 80
% (62% in the case of water resistance evaluation). Then 110 ° C
And dried at 170 ° C. for 60 seconds. The obtained object was evaluated by the following method. In addition, the durability test of the cloth to be treated is performed according to JIS-L0.
217 The washing was repeated 20 times by the water washing method shown in Appendix 103, and the performance was evaluated after air-drying. Table 1 shows the results.

[Examples 4 to 10] A composition containing a copolymer obtained by polymerizing in the same manner as in Example 3 except that the polymerizable monomers shown in Table 1 were used in the amounts (parts by weight) shown in Table 1. I got Water was added to the obtained composition containing the copolymer to prepare a treatment bath adjusted so that the concentration of the copolymer was 0.8% by weight. Table 1 shows the results. In Table 1, VCL indicates vinyl chloride.

Example 11 A four-necked glass flask was equipped with a reflux condenser, a thermocouple thermometer, and a stirrer, and charged with 130 g (1 mol) of 2-hydroxyethyl methacrylate.
Further, 222 g (1 mol) of isophorone diisocyanate was added, the temperature was raised to 80 ° C. under dry nitrogen, and the temperature was maintained for 3 hours. After stirring for 1 hour, titration confirmed that 50% of the isocyanate groups had been consumed. Further, 87 g (1 mol) of methyl ethyl ketoxime was added dropwise, and the reaction was carried out for 2 hours. Thereafter, it was confirmed by IR that the absorption of the isocyanate group had completely disappeared. According to the above reaction, 439
g of 2-hydroxyethyl methacrylate / isophorone diisocyanate / methyl ethyl ketoxime adduct (hereinafter referred to as MIP) was obtained.

Example 12 Water and an emulsion of a methyl ethyl ketoxime block of diphenylmethane diisocyanate were added to the composition containing the copolymer obtained in Example 9 to obtain a copolymer having a concentration of 0.8% by weight and diphenylmethane diisocyanate. Concentration of methyl ethyl ketoxime block 0.
A treatment bath adjusted to 5% by weight was prepared and evaluated in the same manner as in Example 3. The results are shown in Table 1.

[Evaluation of Water Repellency] The water repellency was evaluated by a spray test according to JIS-L1092. However, those with + (-) in the water repellency class indicate that each property is slightly better (bad). [Evaluation of oil repellency] Performed according to AATCC-TM118.
It was expressed by the oil repellency grade shown in Table 3. The higher the oil repellency rating, the higher the performance. However, +
Those marked with (-) indicate that each property is slightly better (bad).

[Evaluation of water resistance] Water resistance A method (low water pressure method) of JIS-L1092 (a) Hydrostatic pressure method was used. Unit: mm. [Evaluation of yellowing] Fifteen randomly selected testers visually compared the color of the polyethylene terephthalate tropical cloth before the treatment with the color after the treatment to determine whether or not there was any change. The evaluation that gave the most judgment was adopted. [Evaluation of texture] AATCC (1992) Evalua
The presence or absence of curing was evaluated in accordance with the Tion Procedure 5.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

It was confirmed that the same results as in Table 1 can be obtained by using tripropylene glycol monomethyl ether, propylene glycol or dipropylene glycol monomethyl ether instead of acetone.

[0052]

According to the water / oil repellent composition of the present invention, excellent water / oil repellency and water resistance can be imparted. The water and oil repellency and water resistance imparted by the composition of the present invention are hardly changed even by physical influences such as washing, and are excellent in durability. In the cloth treated with the composition, the above-mentioned properties are imparted to a cloth made of synthetic fibers having substantially no reactive group on the fiber surface. Furthermore, the treated fabric has the advantage of no yellowing or hardening of the texture.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09D 175/04 C09D 175/04 D06M 15/277 D06M 15/277 (72) Inventor Takashige Maekawa 1150 Hazawacho, Kanagawa-ku, Yokohama, Kanagawa Prefecture Address Asahi Glass Co., Ltd.

Claims (5)

[Claims] 1. A repellent composition comprising, as an active ingredient, a copolymer containing the following polymerized unit (a), polymerized unit (b), and at least one selected from polymerized unit (c) and polymerized unit (d). Water oil repellent composition. Polymerized unit (a): a polymerized unit of a (meth) acrylate having a polyfluoroalkyl group. Polymerized unit (b): 2 in which isocyanate group is blocked
Polymerized units of isocyanatoethyl (meth) acrylate. Polymerized unit (c): a polymerized unit of vinyl chloride. Polymerized unit (d): a polymerized unit of an alkyl (meth) acrylate. 2. The water / oil repellent composition according to claim 1, wherein the polymerized unit (b) is a polymerized unit of 2-isocyanatoethyl (meth) acrylate blocked with methyl ethyl ketoxime or ε-caprolactam. 3. (Meth) having a polyfluoroalkyl group
A polymerizable monomer mixture containing an acrylate, 2-isocyanateethyl (meth) acrylate in which an isocyanate group is blocked, and at least one selected from vinyl chloride and an alkyl (meth) acrylate is used as a medium. A method for producing a water- and oil-repellent composition, comprising copolymerizing in the presence of a water- and oil-repellent composition. 4. An object to be treated having a coating formed on the surface of a substrate by treating the surface of the substrate with the water / oil repellent composition according to claim 1 or 2, and then drying the composition. 5. The object according to claim 4, wherein the substrate is a fiber, a fiber woven fabric, or a fiber knit.