WO2021131443A1 - Fluoropolymer, production method therefor, water-and-oil repellent composition, and article - Google Patents

Abstract

A fluoropolymer and a water-and-oil repellent composition are provided with which articles having excellent dynamic water repellency are obtained. The articles are less apt to decrease in water-and-oil repellency even after having been exposed to alkaline or other conditions.　The fluoropolymer comprises units based on the following monomer (a) and units based on the following monomer (b). The water-and-oil repellent composition includes the fluoropolymer. Monomer (a): a compound represented by CH₂=CX-R^f, where X is a halogen atom and R^f is a perfluoroalkyl group having 1-8 carbon atoms. Monomer (b): a monomer copolymerizable with the monomer (a).

Description

Fluorine-containing polymer, its production method, water and oil repellent composition and articles

The present invention relates to a fluorine-containing polymer, a method for producing the same, a water / oil repellent composition, and an article.

As a method for imparting water and oil repellency to the surface of an article (textile product, etc.), an article is used using a water and oil repellent composition containing a fluorine-containing polymer having a unit based on a (meth) acrylate having a perfluoroalkyl group. There are known ways to handle. However, the ester bond in the unit based on (meth) acrylate is easily cleaved by hydrolysis with an alkali or the like. Therefore, the perfluoroalkyl group may be lost from the fluorine-containing polymer, and the water and oil repellency of the article may decrease.

As a water-repellent oil-repellent composition that can obtain an article whose water-repellent and oil-repellent properties do not easily decrease even after being exposed to conditions such as alkali, a fluorine-containing weight that does not have a unit based on a (meth) acrylate having a perfluoroalkyl group. Water and oil repellent compositions containing coalescing are known. As a fluorine-containing polymer having a perfluoroalkyl group and not having a unit based on (meth) acrylate, a fluorine-containing polymer having a unit based on (perfluoroalkyl) ethylene is known (Patent Document 1).

International Publication No. 2019/138680

However, the article treated with the water-repellent oil-repellent composition containing the fluorine-containing polymer described in Patent Document 1 has dynamic water repellency, specifically, water repellency against water (rainfall) falling from a high place. Is insufficient. Further, this article has low resistance to repeated immersion in water, and when the article is repeatedly immersed in water, the water- and oil-repellent coating formed on the article may be cracked or peeled off.

The present invention provides a fluorine-containing polymer and a method for producing the same, which can obtain an article having excellent dynamic water repellency, a water / oil repellent composition which can obtain an article having excellent dynamic water repellency, and an article having excellent dynamic water repellency. To do. Further, in the fluorine-containing polymer and the water-repellent oil-repellent composition of the present invention, it is possible to obtain an article whose water-repellent and oil-repellent properties are unlikely to decrease even after being exposed to conditions such as alkali.

The present invention has the following aspects.
[1] A fluorine-containing polymer containing a unit based on the following monomer (a) and a unit based on the following monomer (b).
Monomer (a): A compound represented by _{CH 2} = CX-R ^f.
However, X is a halogen atom and R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms.
Monomer (b): A monomer copolymerizable with the monomer (a).
[2] The ^{fluorine-containing polymer of [1], wherein the R f} is a perfluoroalkyl group having 4 to 6 carbon atoms.
[3] The fluorine-containing polymer of [1] or [2], wherein X is a chlorine atom.
[4] The fluorine-containing polymer according to any one of [1] to [3], wherein the ratio of the units based on the monomer (a) to all the units constituting the fluorine-containing polymer is 20 to 60 mol%. ..
[5] The fluorine-containing polymer according to any one of [1] to [4], wherein at least a part of the unit based on the monomer (b) is a unit based on the following monomer (b1).
Monomer (b1): A compound represented by _{CH 2} = CH-Q or CH ₂ = CHCH _2-Q.
However, Q is a halogen atom or an organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom.

[6] A method for producing a fluorine-containing polymer, in which a monomer component containing the following monomer (a) and the following monomer (b) is polymerized in the presence of a polymerization initiator.
Monomer (a): A compound represented by _{CH 2} = CX-R ^f.
However, X is a halogen atom and R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms.
Monomer (b): A monomer copolymerizable with the monomer (a).
[7] The production method according to [6], wherein the ratio of the monomer (a) to the entire monomer component is 20 to 60 mol%.
[8] The method for producing [6] or [7], wherein at least a part of the unit based on the monomer (b) is a unit based on the following monomer (b1).
Monomer (b1): A compound represented by _{CH 2} = CH-Q or CH ₂ = CHCH _2-Q.
However, Q is a halogen atom or an organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom.
[9] The production method according to any one of [6] to [8], wherein the monomer component is polymerized in an aqueous medium.
[10] The production method according to [9], wherein the monomer component is emulsion-polymerized in an aqueous medium containing a surfactant and the polymerization initiator.

[11] A fluorinated polymer dispersion liquid containing the fluorinated polymer according to any one of [1] to [5] and an aqueous medium in which the fluorinated polymer is dispersed.
[12] The fluorine-containing polymer dispersion liquid of [11] further containing a surfactant.
[13] A water- and oil-repellent composition containing the fluorine-containing polymer according to any one of the above [1] to [5].
[14] The water- and oil-repellent agent composition of [13], which comprises an aqueous medium and the fluorine-containing polymer dispersed in the aqueous medium.
[15] An article in which at least a part of the surface of the base material is treated with the water / oil repellent composition of [13] or [14].

According to the fluorine-containing polymer of the present invention, an article having excellent water and oil repellency, particularly dynamic water repellency, and whose water and oil repellency does not easily decrease even after being exposed to conditions such as alkali can be obtained.
According to the method for producing a fluorine-containing polymer of the present invention, an article having excellent water and oil repellency, particularly dynamic water repellency, and whose water and oil repellency does not easily decrease even after being exposed to conditions such as alkali can be obtained. A fluorine-containing polymer can be produced.
According to the water-repellent and oil-repellent composition of the present invention, an article having excellent water- and oil-repellent properties, particularly dynamic water-repellent properties, and whose water- and oil-repellent properties do not easily decrease even after being exposed to conditions such as alkali can be obtained.
The article of the present invention is excellent in water and oil repellency, particularly dynamic water repellency, and the water and oil repellency is unlikely to decrease even after being exposed to conditions such as alkali.

The meanings and definitions of the terms in the present invention are as follows.
The "unit based on a monomer" is a general term for an atomic group directly formed by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group.
"(Meta) acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth) acryloyloxy group" is a general term for acryloyloxy group and metaacryloyloxy group.
The number average molecular weight (hereinafter, also referred to as “Mn”) and mass average molecular weight (hereinafter, also referred to as “Mw”) of the polymer are gel permeated using a calibration curve prepared using a standard polymethylmethacrylate sample. It is a polymethylmethacrylate-equivalent molecular weight obtained by measuring by chromatography (hereinafter, also referred to as “GPC”).

[Fluorine-containing polymer]
The fluorine-containing polymer according to one aspect of the present invention (hereinafter, also referred to as “polymer A”) is simply a unit based on the monomer (a) (hereinafter, also referred to as “unit (a)”). It includes a unit based on the polymer (b) (hereinafter, also referred to as “unit (b)”).
Monomer (a): A compound represented by _{CH 2} = CX-R ^f.
However, X is a halogen atom and R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms.
Monomer (b): A monomer copolymerizable with the monomer (a).

In the monomer (a), examples of X include chlorine atom, fluorine atom, bromine atom, and iodine atom, and the adhesion between the water-repellent oil-repellent film formed by the water-repellent oil-repellent composition and the base material is improved. A chlorine atom is preferable because it is more excellent and the raw material is easily available.
The carbon number of R ^f is preferably 1 to 6 from the viewpoint of easy conversion to polymer A, availability of raw materials, and easy handling, and 4 to 6 from the viewpoint of water repellency and oil repellency. 6 is more preferable, and 6 is particularly preferable.
R ^f is preferably linear.

Examples of the monomer (a) include CH ₂ = CX-CF ₃ , CH ₂ = CX-CF ₂ CF ₃ , CH ₂ = CX-CF ₂ CF ₂ CF ₃ , CH ₂ = CX-CF (CF _3). ) ₂ , CH ₂ = CX- (CF ₂ ) ₃ CF ₃ , CH ₂ = CX-CF ₂ CF (CF ₃ ) ₂ , CH ₂ = CX-C (CF ₃ ) ₃ , CH ₂ = CX- (CF ₂₎ ) ₄ CF ₃ , CH ₂ = CX-CF ₂ CF ₂ CF (CF ₃ ) ₂ , CH ₂ = CX- (CF ₂ ) ₅ CF ₃ , CH ₂ = CX- (CF ₂ ) ₅ CF (CF ₃ ) ₂ , CH ₂ = CX- (CF ₂ ) ₇ CF ₃ .
As the monomer (a), CH ₂ = CX-CF ₃ , CH ₂ = CX-CF ₂ CF ₃ , CH ₂ = CX-CF (CF ₃ ) ₂ , CH ₂ = CX- (CF ₂ ) ₃ CF. ₃ and CH ₂ = CX- (CF ₂ ) ₅ CF ₃ are preferred, CH ₂ = CX-CF ₃ , CH ₂ = CX-CF ₂ CF ₃ , CH ₂ = CX- (CF ₂ ) ₃ CF ₃ and CH ₂ = CX- (CF ₂ ) ₅ CF ₃ is more preferred, CH ₂ = CX- (CF ₂ ) ₃ CF ₃ and CH ₂ = CX- (CF ₂ ) ₅ CF ₃ are even more preferred, CH ₂ = CCl- (CF 2) ₂ ) ₃ CF ₃ and CH ₂ = CCl- (CF ₂ ) ₅ CF ₃ are particularly preferable.
The monomer (a) may be used in combination of two or more.

The monomer (b) may be copolymerizable with the monomer (a), but at least a part of the monomer (b) is simple because it is easily copolymerized with the monomer (a). It is preferably a monomer (b1). The unit based on the monomer (b1) is also hereinafter referred to as "unit (b1)".
Monomer (b1): A compound represented by _{CH 2} = CH-Q or CH ₂ = CHCH _2-Q.
However, Q is a halogen atom or an organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom.
Examples of the organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom include -OR ⁴ , -OC (= O) R ⁴ , -NHR ⁴ , -NR ⁴ R ⁵ , -SR ⁴ , and a ring. Examples thereof include a nitrogen-containing heterocyclic group in which the constituent nitrogen atom is a bond terminal atom. However, R ⁴ and R ⁵ are independently alkyl groups, cycloalkyl groups, aryl groups or heterocyclic groups, respectively. The alkyl group has, for example, 1 to 22 carbon atoms. The number of carbon atoms forming the ring of the cycloalkyl group is, for example, 3 to 8.
The organic group in Q may have a reactive group such as a hydroxy group, a carboxy group, an amino group or an alkylamino group or a halogen atom, and an ether oxygen atom or a carbonyloxy group at a portion other than the bond terminal. , May have a linking group such as a carbonyl group. Further, it may have a polymerizable carbon-carbon double bond. A hydroxy group is preferable as the reactive group. The organic group in Q preferably does not have a polymerizable carbon-carbon double bond.
^{As Q, a halogen atom, -OR 4} , -OC (= O) R ⁴ is preferable, and a fluorine atom is preferable because it is easy to copolymerize with the monomer (a) and has good adhesion to a base material. , Chlorine atom, —OC (= O) R ⁴ is more preferred. R ⁴ is the same as above.

As the _{compound represented by CH 2} = CH—Q, carboxylic acid vinyl ester, vinyl ether and vinyl halide are preferable. As the vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether are preferable.
As the _{compound represented by CH 2} = CHCH _2- Q, carboxylic acid allyl ester, allyl ether and allyl halide are preferable. As the allyl ether, an alkyl allyl ether and a hydroxyalkyl allyl ether are preferable.
The number of carbon atoms of the acyl group in the carboxylic acid vinyl ester or the carboxylic acid allyl ester is preferably 24 or less, more preferably 2 to 6. It is also preferable to use a carboxylic acid vinyl ester or carboxylic acid allyl ester having an acyl group having 2 to 6 carbon atoms in combination with a carboxylic acid vinyl ester or carboxylic acid allyl ester having an acyl group having 10 to 22 carbon atoms.
The number of carbon atoms of the alkyl or hydroxyalkyl in the alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl allyl ether and hydroxyalkyl allyl ether is preferably 2 to 6.

Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl chloroacetate, and divinyl adipic acid. As the carboxylic acid vinyl ester, vinyl acetate is particularly preferable from the viewpoint of obtaining an article having excellent oil repellency and alcohol repellency.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether and 2-chloroethyl. Examples thereof include vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether.

Examples of the carboxylic acid allyl ester include allyl acetate and diallyl adipate.
Examples of the allyl ether include allyl ethyl ether, diallyl ether, 1,3-diallyloxy-2-propanol, and ethylene glycol monoallyl ether.

Examples of vinyl halides include vinyl chloride and vinyl fluoride.
Examples of the allyl halide include allyl chloride and allyl fluoride.
Other examples of the compound represented by CH ₂ = CH-Q or CH ₂ = CHCH _2- Q include, for example, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, ethyl vinyl sulfide.

As the monomer (b1), a carboxylic acid vinyl ester, a carboxylic acid allyl ester, and an alkyl vinyl ether can be obtained because an article having good copolymerizability with the monomer (a) and excellent oil repellency and alcohol repellency can be obtained. , Alkyl allyl ether, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, vinyl halide and allyl halide are preferable, and carboxylic acid vinyl ester and vinyl halide are more preferable.
As a specific monomer (b1), vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caprylate, vinyl laurate, vinyl stearate, benzoate can be obtained from the viewpoint of obtaining an article having excellent oil repellency and alcohol repellency. Vinyl acid acid, vinyl chloroacetate, ethyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, ethylene glycol monoallyl ether, vinyl chloride and vinyl fluoride are preferable, and vinyl acetate is more preferable.

In the polymer A, at least a part of the unit (b) may be a unit based on the monomer (b) other than the monomer (b1). A monomer (b) other than the monomer (b1) is hereinafter referred to as "monomer (b2)", and a unit based on the monomer (b2) is also hereinafter referred to as "unit (b2)". ..
As the polymer A, a polymer in which at least a part of the unit (b) is the unit (b1) is preferable. The polymer in which at least a part of the unit (b) is the unit (b1) includes a polymer having only the unit (b1) as the unit (b) and a weight having the unit (b1) and the unit (b2). Coalescence is mentioned.
The polymer A may have two or more units (b1). When the polymer A has a unit (b2), it may have two or more units (b2).

Examples of the monomer (b2) include olefins, halogenated olefins other than vinyl halides, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, fluoroalkyl (meth) acrylates, and perfluoro (alkyl vinyl ethers). .. Specifically, ethylene, propylene, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, _{a compound represented by CH 2} = CH-R ^f , methyl (meth) acrylate, ethyl (meth) acrylate, stearyl (meth) acrylate. , Behenyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, N-methylolacrylamide, 2-perfluoro Hexylethyl (meth) acrylate, CF ₂ = _{CFOCF 3} , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ( CF ₃ ) OCF ₂ CF ₂ CF ₃ can be mentioned. In the compound represented by ^{_{CH 2 = CH-R f,}} R f is the same as ^{R f} in the monomer (a).

As the monomer (b2), (meth) acrylate is preferable. However, the polymer A has a unit based on a (meth) acrylate having a perfluoroalkyl group because it is possible to obtain an article whose water and oil repellency is less likely to decrease even after being exposed to conditions such as alkali. It is preferable not to do so. Therefore, as the monomer (b2), a (meth) acrylate containing no fluorine atom is preferable. Examples of the fluorine atom-free (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and lauryl (meth) acrylate. , Stearyl (meth) acrylate, behenyl (meth) acrylate. N-Butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are preferable, and the texture is good when the article is a textile product, because the Tg of the polymer A is lowered and the film-forming property is likely to be good. Lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate are preferable from the viewpoint of easily improving water repellency.

The range of the ratio of the unit (a) to all the units constituting the polymer A (that is, the total of the units including the unit (a) and the unit (b)) is preferably 20 to 60 mol%, preferably 30 to 50 mol. % Is more preferable. When the ratio of the unit (a) is at least the above lower limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent. When the ratio of the unit (a) is not more than the upper limit value, the conversion rate of the polymer A in the polymerization reaction tends to be higher.

When at least a part of the unit (b) is the unit (b1), the range of the ratio of the unit (b1) to all the units constituting the polymer A is preferably 40 to 80 mol%, preferably 50 to 70 mol%. Is more preferable. When the ratio of the unit (b1) is equal to or higher than the lower limit value, the conversion rate of the polymer A in the polymerization reaction tends to be higher. When the ratio of the unit (b1) is not more than the upper limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent.

When at least a part of the unit (b1) is a vinyl halide-based unit, the ratio of the vinyl halide-based unit to all the units of the unit (b) is preferably 1 to 60 mol%, and 5 to 60 mol%. 50 mol% is more preferred, and 10-40 mol% is even more preferred. When the ratio of the unit (b1) is equal to or higher than the lower limit value, the conversion rate of the polymer A in the polymerization reaction tends to be higher. When the ratio of the unit (b1) is not more than the upper limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent.

The ratio of the unit (b2) to all the units constituting the polymer A is preferably less than 20% by mass, more preferably less than 10% by mass, and may be 0% by mass. When the ratio of the unit (b2) is not more than the upper limit value, an article whose water repellency and oil repellency are less likely to decrease even after being exposed to conditions such as alkali can be obtained.

The total ratio of the unit (a) and the unit (b1) to all the units constituting the polymer A is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. When the total ratio is at least the lower limit value, an article whose water and oil repellency is less likely to decrease even after being exposed to conditions such as alkali can be obtained.

The ratio of each unit ^{can be calculated by 1} H-NMR and the reaction rate of each monomer component by gas chromatography. When the conversion rate of the monomer component to the polymer A is high (for example, 90% or more) at the time of producing the polymer A, the ratio of each unit is calculated based on the charged amount of the monomer component. May be good.
The conversion rate is determined by the measured value / theoretical value × 100 from the theoretical value of the mass of the polymer A calculated from the amount of the raw material charged at the time of producing the polymer A and the measured value of the mass of the produced polymer A. Desired.

The Mn of the polymer A is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 12,000 or more. The Mn of the polymer A is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. When Mn of the polymer A is at least the above lower limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are further excellent. When the Mn of the polymer A is not more than the above upper limit value, the water dispersibility of the polymer A is further excellent.

The Mw of the polymer A is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. The Mw of the polymer A is preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less. When the Mw of the polymer A is at least the above lower limit value, the water and oil repellency, the dynamic water repellency, and the repeated water immersion resistance of the article treated with the polymer A are further excellent. When the Mw of the polymer A is not more than the above upper limit value, the water dispersibility of the polymer A is further excellent.

The molecular weight distribution (Mw / Mn) of the polymer A is preferably 1.0 or more, more preferably 1.3 or more, and even more preferably 1.6 or more. The Mw / Mn of the polymer A is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less. When Mw / Mn of the polymer A is at least the above lower limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are further excellent. When Mw / Mn of the polymer A is not more than the above upper limit value, the water dispersibility of the polymer A is further excellent.

The glass transition temperature of the polymer A (hereinafter referred to as “Tg”) is preferably 0 to 80 ° C, more preferably 5 to 70 ° C. When Tg is at least the above lower limit value, the resistance to repeated immersion in water is more excellent. When Tg is not more than the above upper limit value, the film-forming property of the water- and oil-repellent film is more excellent, and the coating property of the base material is excellent.
Tg is the midpoint glass transition temperature determined based on JIS K 7121: 1987 by the differential scanning calorimetry (DSC method).

(Mechanism of action)
Since the polymer A described above contains the unit (a) and the unit (a) has an X at the α-position, the article treated with the composition containing the polymer A has dynamic water repellency. Alternatively, it has excellent resistance to repeated immersion in water. According to the polymer A, an article excellent in both dynamic water repellency and repeated water immersion resistance can be obtained. Further, the article treated with the composition containing the polymer A does not easily deteriorate in water repellency and oil repellency even after being exposed to conditions such as alkali. Also,

[Method for producing fluorine-containing polymer]
In the method for producing a fluorine-containing polymer according to one aspect of the present invention, a monomer component containing the monomer (a) and the monomer (b) is polymerized in the presence of a polymerization initiator.

The monomer (a) and the monomer (b) are as described above.
As the monomer (a) and the monomer (b), those produced by a known production method can be used. As for the commercially available monomer, a commercially available product can be used.
The monomer (a) is, for example, a compound represented by _{CH 2} X-CHX-R ^f by _{adding X 2} (halogen such as _{Cl 2 ) to the compound represented by CH 2} = CH-R ^f. It can be produced by obtaining (step A) and de-HXing the compound represented by _{CH 2} X-CHX-R ^{f (step B).}

In step A, for example, in the presence of a halogenation catalyst, the _{compound represented by CH 2} = CH—R ^f is brought into contact with the gaseous X _2.
Examples of the halogenation catalyst include tertiary amines (trimethylamine, triethylamine, tripropylamine, tributylamine, etc.) and salts thereof (hydrochlorides, etc.), N-substituted amides (dimethylformamide, etc.), and aromatic nitrogen-containing compounds (pyridine). , Methylpyridine, etc.). The amount of the halogenation catalyst used is, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound represented by _{CH 2} = CH-R ^f.
In order to bring the _{compound represented by CH 2} = CH-R ^f into contact with the gaseous X _{2 , for example, X 2} is contained in a solution of the compound represented by _{CH 2} = CH-R ^{f under stirring.} Just blow in the gas. The amount of X _{2 to be} blown is, for example, 1 to 1.2 mol with respect to 1 mol of the compound represented by _{CH 2} = CH-R ^f. The _{time for blowing X 2} is, for example, 0.5 to 24 hours.
The reaction temperature in step A is, for example, 30 to 100 ° C. The reaction time is, for example, 0.5 to 24 hours. Step A is preferably performed under shading.
The reaction product in step A may be directly subjected to step B.

In step B, for example, in the presence of a de-HX catalyst, the _{compound represented by CH 2} X-CHX-R ^f is de-HX.
Examples of the de-HX catalyst include amines such as tertiary amines and aromatic nitrogen-containing compounds such as aromatic nitrogen-containing heterocyclic compounds. Examples of the amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine and salts thereof (hydrochloride and the like). Examples of the aromatic nitrogen-containing compound include pyridine and methylpyridine. The amount of the de-HX catalyst used is, for example, 0.001 to 0.5 mol with respect to 1 mol of the compound represented by _{CH 2} X-CHX-R ^f. When a tertiary amine or an aromatic nitrogen-containing compound is used as the halogenation catalyst, the halogenation catalyst used in step A can be used as it is as a de-HX catalyst.
The reaction temperature in step B is, for example, −10 to 50 ° C. The reaction time is, for example, 0.5 to 12 hours.
Step B is preferably carried out in the presence of a polymerization inhibitor in order to prevent the polymerization of the produced monomer (a). Examples of the polymerization inhibitor include t-butyl catechol, hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like. The amount of the polymerization inhibitor used is, for example, 0.003 to 0.1 parts by mass with respect to 100 parts by mass of the compound represented by _{CH 2} X-CHX-R ^f.
After de-HX, the monomer (a) is usually recovered from the resulting reaction mixture. To recover the monomer (a), for example, an acid is added to the reaction mixture to adjust the pH to 7 or less, and the mixture is allowed to stand. When the pH-adjusted reaction mixture is allowed to stand, the reaction mixture is separated into an oil phase containing the monomer (a) and an aqueous phase. As a method for purifying the monomer (a), a conventionally known method can be used.

The range of the ratio of the monomer (a) to the entire monomer component (that is, the total of all the monomers including the monomer (a) and the monomer (b)) is 20 to 60 mol%. It is preferably 30 to 50 mol%, more preferably. When the proportion of the monomer (a) is at least the above lower limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent. When the proportion of the monomer (a) is not more than the upper limit value, the conversion rate of the polymer A in the polymerization reaction tends to be higher.

The range of the ratio of the monomer (b) to the entire monomer component is preferably 40 to 80 mol%, more preferably 50 to 70 mol%. When the proportion of the monomer (b) is at least the above lower limit value, the conversion rate in the polymerization reaction tends to be higher. When the proportion of the monomer (b) is not more than the above upper limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent.

When at least a part of the monomer (b) is the monomer (b1), the ratio of the monomer (b1) to the entire monomer component is preferably 40 to 80 mol%, preferably 50 to 50 to 80 mol%. 70 mol% is more preferable. When the proportion of the monomer (b1) is equal to or higher than the lower limit, the conversion rate in the polymerization reaction tends to be higher. When the proportion of the monomer (b1) is not more than the above upper limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent.

When at least a part of the monomer (b1) is vinyl halide, the ratio of vinyl halide to the entire monomer (b) is preferably 1 to 60 mol%, preferably 5 to 50 mol%. More preferably, 10 to 40 mol% is further preferable. When the proportion of the monomer (b1) is at least the above lower limit value, the conversion rate of the polymer A in the polymerization reaction tends to be higher. When the proportion of the monomer (b1) is not more than the above upper limit value, the water and oil repellency, dynamic water repellency, and repeated water immersion resistance of the article treated with the polymer A are more excellent.

The ratio of the monomer (b2) to the entire monomer component is preferably less than 20% by mass, more preferably less than 10% by mass, and may be 0% by mass. When the proportion of the monomer (b2) is not more than the above upper limit value, an article whose water repellency and oil repellency are less likely to decrease even after being exposed to conditions such as alkali can be obtained.

The total ratio of the monomer (a) and the monomer (b1) to the entire monomer component is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. When the total ratio is at least the lower limit value, an article whose water and oil repellency is less likely to decrease even after being exposed to conditions such as alkali can be obtained.

Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, and a radical polymerization initiator is preferable. As the radical polymerization initiator, for example, an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based polymerization initiator are used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is preferable, and a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.
The amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer component.

When polymerizing the monomer component, a molecular weight modifier may be used. As the molecular weight regulator, for example, an aromatic compound, a mercapto alcohol, a mercaptocarboxylic acid, and an alkyl mercaptan are preferable, and a mercaptocarboxylic acid or an alkyl mercaptan is more preferable. Examples of the molecular weight modifier include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dima (CH ₂ = C (Ph) CH ₂ C (CH 2 = C (Ph) CH 2 C). CH ₃ ) ₂ Ph, where Ph is a phenyl group).
The amount of the molecular weight adjusting agent added is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may be 0 parts by mass with respect to 100 parts by mass of the monomer component.

Examples of the polymerization method of the monomer component include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a massive polymerization method. Of these, the emulsion polymerization method is preferable. By polymerizing the monomer component by the emulsion polymerization method, the conversion rate of the monomer component to the polymer A is improved without using a solvent other than the aqueous medium, and the molecular weight of the polymer A (Mn, Mw) can be increased.

In the emulsion polymerization method, for example, the monomer component is polymerized in an emulsion containing an aqueous medium, a monomer component and a polymerization initiator. The emulsion may contain a surfactant, if necessary.
Examples of the aqueous medium include the same as the aqueous medium in the water and oil repellent composition described later.
Examples of the surfactant include the same surfactants in the water-repellent and oil-repellent composition described later.

The emulsion can be prepared by mixing an aqueous medium, a monomer component, and a surfactant if necessary, dispersing the emulsion with a homogenizer, a high-pressure emulsifier, or the like, and then adding a polymerization initiator.
The concentration of the monomer component in the emulsion is preferably 20 to 60% by mass, more preferably 30 to 50% by mass. When the concentration of the monomer component in the emulsion is within the above range, the conversion rate of the monomer component to the polymer A can be improved at the time of polymerization of the monomer component, and the molecular weight of the polymer A can be improved. Can be high enough.

The content of the surfactant in the emulsion is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the monomer component. When the content of the surfactant is at least the above lower limit value, the dispersion stability of the emulsion is excellent. When the content of the surfactant is not more than the above upper limit value, the adverse effect of the surfactant on the water and oil repellency of the article treated with the composition containing the polymer A can be reduced.

The conversion rate of the monomer component to the polymer A at the end of the polymerization is preferably 80% or more, more preferably 90% or more. By increasing the conversion rate, the molecular weight of the polymer A is also increased, and the water repellency, oil repellency, dynamic water repellency, and repeated water immersion resistance are also improved. Further, by setting a high conversion rate, performance deterioration due to the residual monomer is suppressed and the amount of fluorine atoms contained in the polymer A is increased, so that water repellency, dynamic water repellency, and repeated water immersion are performed. Good resistance.
In order to make the conversion rate 80% or more, it is preferable to optimize the emulsification composition and the polymerization time.

By polymerizing the monomer component in the emulsion, a dispersion liquid of the polymer A can be obtained.
In the dispersion, the polymer A is dispersed as emulsified particles in the aqueous medium.
In the dispersion, the average particle size of the emulsified particles of the polymer A is preferably 20 to 200 nm, more preferably 40 to 190 nm, and even more preferably 60 to 180 nm. When the average particle size is not more than the upper limit, the water repellency of the article treated with the emulsified particles of the polymer A and the dispersibility of the emulsified particles of the polymer A are more excellent. When the average particle size is equal to or greater than the lower limit, the emulsified particles of the polymer A are more stable with respect to the mechanical share.
The average particle size of the emulsified particles of the polymer A is calculated by the cumulant method analysis from the autocorrelation function obtained by the dynamic light scattering method for the sample obtained by diluting the dispersion liquid of the polymer A with water to a solid content concentration of 1% by mass. Will be done.

After polymerizing the monomer component in the emulsion, the polymer A is recovered from the obtained dispersion, if necessary. The dispersion may be used as it is for the production of a water-repellent oil-repellent composition or the like.

(Mechanism of action)
In the method for producing a fluorine-containing polymer described above, since the monomer component containing the monomer (a) is polymerized, it is possible to produce an article having excellent dynamic water repellency or repeated water immersion resistance. Combined A can be manufactured. In addition, polymer A can be produced, which can produce an article whose water and oil repellency does not easily decrease even after being exposed to conditions such as alkali.

[Water and oil repellent composition]
The water- and oil-repellent agent composition according to one aspect of the present invention (hereinafter, also referred to as "the present composition") contains the polymer A.
The composition typically comprises polymer A and a medium. Examples of the medium include an aqueous medium and an organic solvent, and an aqueous medium is preferable.
The composition may contain a surfactant, if necessary.
The composition may contain other components, if desired.
The present composition is preferably a fluorine-containing polymer dispersion liquid containing the polymer A, an aqueous medium, and a surfactant. The fluorine-containing polymer dispersion liquid also includes the dispersion liquid obtained by the above-mentioned method for producing the polymer A, and the dispersion liquid further diluted with an arbitrary aqueous medium for treating the article.
The present composition may be a fluorine-containing polymer solution containing the polymer A and an organic solvent and not containing a surfactant.

(Aqueous medium)
Examples of the aqueous medium include water and water containing a water-soluble organic solvent.
The water-soluble organic solvent is an organic solvent that can be miscible with water in an arbitrary ratio. As the water-soluble organic solvent, at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols and aprotic polar solvents is preferable. Examples of the alcohol include t-butanol and propylene glycol. Examples of the ether alcohol include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples of the aprotic polar solvent include N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran (hereinafter, also referred to as “THF”), acetonitrile, acetone, 3-methoxy-N, N-dimethylpropanamide, 3-. Examples thereof include butoxy-N, N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. When the liquid medium is an aqueous medium, the water-soluble organic solvent is preferably ether alcohol because it improves the compatibility between the polymer A and the aqueous medium and makes it easy to form a uniform film on the article, and dipropylene glycol is preferable. , Tripropylene glycol and dipropylene glycol monomethyl ether are more preferred.
When the aqueous medium is water containing a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of water.

(Surfactant)
As the surfactant, a surfactant having no fluorine atom is preferable.
Examples of the surfactant include anionic surfactant, nonionic surfactant, cationic surfactant, and amphoteric surfactant.
As the surfactant, since the dispersion stability of the aqueous dispersion containing the polymer A is excellent, the nonionic surfactant is used alone, and the nonionic surfactant and the cationic surfactant or the amphoteric surfactant are used. The combined use or the single use of the anionic surfactant is preferable, and the combined use of the nonionic surfactant and the cationic surfactant is more preferable.
The ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 100/0 to 40/60 (mass ratio), and is 97/3 to 40/60. (Mass ratio) is more preferable.
In a specific combination of a nonionic surfactant and a cationic surfactant, the total amount of the surfactant with respect to 100 parts by mass of the polymer A can be 5 parts by mass or less. The adverse effect on the water and oil repellency of the article treated with the composition can be reduced.

^{Examples of the nonionic surfactant include the surfactants s 1} to s ⁶ described in paragraphs [0067] to [0995] of JP-A-2009-215370.
As the surfactant s ¹ , polyoxyethylene alkyl ether is preferable.
As the surfactant s ² , an acetylene glycol ethylene oxide adduct is preferable.
Surfactant s ^3, polyoxyethylene polyoxypropylene glycol.
Two or more kinds of nonionic surfactants may be used in combination.

Examples of cationic surfactants include surfactants ^{s 7} described in JP 2009-215370 JP paragraphs [0096] to [0100].
As the surfactant s ⁷ , an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group or a polyoxyalkylene chain having a hydroxyl group at the terminal is preferable, and the following formula s ⁷¹ is used. The represented compound s ⁷¹ is more preferred.
[(R ²¹ ) ₄ N ⁺ ] ・ X ^- s ⁷¹
R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the end. .. The four R ^21s may be the same or different, but the four R ^21s are not hydrogen atoms at the same time. X ^- is a counterion.
As X ⁻ , chloride ion, ethyl sulfate ion, or acetate ion is preferable.
Examples of compound s ⁷¹ include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, and di (cowfat alkyl) dimethylammonium. Examples include chloride and dimethylmonococonutamine acetate.
Two or more kinds of cationic surfactants may be used in combination.

Examples of amphoteric surfactants include surfactants ^{s 8} described in JP 2009-215370 JP paragraphs [0101] - [0102]. These may be used alone or in combination of two or more.

^{As a combination of surfactants, the surfactant s 1} is excellent in that the article treated with this composition has little adverse effect on the water and oil repellency and the dispersion stability of the dispersion liquid containing the polymer A is excellent. And ^{a combination of surfactant s 2} and surfactant s ⁷ , or a combination of surfactant s ¹ and surfactant s ³ and surfactant s ⁷ , or surfactant s ¹ and surfactant s ² The combination of the surfactant s ³ and the surfactant s ⁷ is preferable, and the above-mentioned combination in which the surfactant s ⁷ is the compound s ⁷¹ is more preferable.

(Other ingredients)
Examples of other components include a fluorine-containing polymer other than polymer A, a non-fluorine-based polymer, a non-fluorine-based water- and oil-repellent agent, and a water-soluble polymer resin (for example, hydrophilic polyester and its derivatives, and hydrophilic polyethylene. Glycols and derivatives thereof, hydrophilic polyamines and derivatives thereof), cross-linking agents, penetrants (for example, nonionic surfactants having an acetylene group in the center and a symmetrical structure, Dispanol (registered trademark) manufactured by Nichiyu Co., Ltd. ) Series), colloidal silica (for example, Snowtex (registered trademark) series manufactured by Nissan Chemical Co., Ltd., Adeleite series manufactured by ADEKA), defoamer (for example, Orfin (registered trademark) series manufactured by Nissin Chemical Co., Ltd.), FS Antifoam Series manufactured by Toray Dow Corning), film-forming aids, insect repellents, antifungal agents, preservatives, flame retardants, antistatic agents (for example, Directorol series manufactured by Meisei Chemical Co., Ltd.), anti-wrinkle agents, Softeners (eg, silicone emulsions, polyethylene wax emulsions), pH adjusters (eg, diethanolamine, triethanolamine, acetic acid, citric acid) can be mentioned.

When the present composition contains a cross-linking agent, the adhesiveness to the article is likely to be improved.
As the cross-linking agent, an isocyanate-based cross-linking agent, a methylol-based cross-linking agent, a carbodiimide-based cross-linking agent, and an oxazoline-based cross-linking agent are preferable.

Examples of the isocyanate-based cross-linking agent include an aromatic block-type isocyanate-based cross-linking agent, an aliphatic block-type isocyanate-based cross-linking agent, an aromatic non-blocking type isocyanate-based cross-linking agent, and an aliphatic non-block type isocyanate-based cross-linking agent. The isocyanate-based cross-linking agent is preferably an aqueous dispersion type emulsified with a surfactant or a self-aqueous dispersion type having a hydrophilic group.

Examples of the methylol-based cross-linking agent include a condensate or precondensate of urea or melamine and formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, and dicyandiamide. -Formaldehyde condensates, methylol-carbamate, methylol- (meth) acrylamide, and polymers thereof.

The carbodiimide-based cross-linking agent is a polymer having a carbodiimide group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group, an amino group, and an active hydrogen group of an article or the like.
The oxazoline-based cross-linking agent is a polymer having an oxazoline group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group of an article or the like.

Other cross-linking agents include, for example, divinyl sulfone, polyamide and its cationic derivative, polyamine and its cationic derivative, epoxy derivative such as diglycidylglycerol, (epoxy-2,3-propyl) trimethylammonium chloride, N-methyl-N. -Halide derivatives such as (epoxy-2,3-propyl) morpholinium chloride, pyridinium salt of chloromethyl ether of ethylene glycol, polyamine-polyamine-epicrohydrin resin, polyvinyl alcohol or its derivative, polyacrylamide or its derivative, glyoxal resin Examples include anti-wrinkle agents.

When the present composition contains a methylol-based cross-linking agent or a glyoxal resin-based wrinkle-preventing agent, it is preferable to include a catalyst as an additive. Preferred catalysts include, for example, inorganic amine salts and organic amine salts. Examples of the inorganic amine salt include ammonium chloride. Examples of the organic amine salt include aminoalcohol hydrochloride and semicarbazide hydrochloride. Examples of aminoalcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

(Ratio of each component)
When the present composition contains an aqueous medium, the content of the aqueous medium can be appropriately selected according to the desired solid content concentration of the present composition.
When the present composition contains a surfactant, the content of the surfactant is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the polymer A. When the content of the surfactant is at least the above lower limit value, the dispersion stability of the present composition is excellent. When the content of the surfactant is not more than the above upper limit value, the adverse effect of the surfactant on the water and oil repellency and the dynamic water repellency of the article treated with the present composition can be reduced.
When the present composition contains a cross-linking agent, the content of the cross-linking agent is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polymer A.

Immediately after the production of the present composition, the solid content concentration of the present composition is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
The solid content concentration of the present composition is preferably 0.1 to 7% by mass, more preferably 0.2 to 5% by mass when the present composition is used for processing an article.
The solid content concentration is determined by (solid content mass / sample mass) × 100, where the mass of the sample before heating is the sample mass and the mass after drying the sample in a convection dryer at 120 ° C. for 4 hours is the solid content mass. It is calculated.

The method for producing this composition is not particularly limited.
For example, when the present composition is a fluorine-containing polymer dispersion liquid, the dispersion liquid of the polymer A may be obtained by the above-mentioned emulsion polymerization method, and the obtained dispersion liquid may be used as it is as the present composition, and diluted with an aqueous medium. After adjusting the solid content concentration, the composition may be used. Other components may be added to the composition.

(Mechanism of action)
In the present composition described above, since the polymer A contains the unit (a) and the unit (a) has X at the α-position, the dynamic water repellency of the article treated with the present composition or Excellent resistance to repeated immersion in water. It is also possible to obtain an article having excellent both dynamic water repellency and resistance to repeated water immersion. Further, since the polymer A contains the unit (a), the water and oil repellency is unlikely to decrease even after the article treated with the present composition is exposed to conditions such as alkali. Also,

[Article]
In the article according to one aspect of the present invention, at least a part of the surface of the base material is treated with the present composition.
Examples of the base material to be treated with this composition include fibers, fiber fabrics (fiber woven fabrics, fiber knitted fabrics, non-woven fabrics, brushed cloths, etc.), and textile products including fiber fabrics (keywear, rainwear, coats, bruzon, windows, etc.). Breakers, down jackets, sportswear, work clothes, uniforms, protective clothing and other clothing, backpacks, backpacks, bags, tents, zelts, etc.), glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metal , Metal oxides, ceramic products, resin molded products, porous resins, porous fibers. The porous resin is used, for example, as a filter. Examples of the material of the porous resin include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of the material of the porous fiber include glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate.

As the base material, a fiber, a woven fabric, and a textile product including the woven fabric are preferable.
The type of fiber is not particularly limited, but includes natural fibers such as cotton, wool, silk or cellulose, synthetic fibers such as polyester, polyamide, acrylic or aramid, chemical fibers such as rayon, biscous rayon or lyocell, and natural fibers. Examples thereof include blended fibers with synthetic fibers and blended fibers with natural fibers and chemical fibers. Examples of the fiber when the fiber base material is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass and rayon.

The treatment method may be any method as long as the composition can be attached to the article to be treated. For example, when the composition is liquid, the composition is applied to a substrate by a known coating method such as coating, impregnation, dipping, spraying, brushing, padding, size press, roller, etc., and then dried. There is a way to do it. When the base material is a paper base material, a method of applying or impregnating the composition to the paper base material (external addition work) and a method of papermaking a pulp slurry containing the present composition (internal addition work) can be mentioned. ..
The amount of the composition to be attached to the substrate is not particularly limited, but in the case of a fiber cloth, for example, the amount of the composition per unit mass of the fiber cloth is 0.001 to 0.07 g / g in terms of solid content. The amount is preferably 0.001 to 0.05 g / g, and more preferably 0.001 to 0.05 g / g.
Drying may be performed at room temperature or heated, and heating is preferable. When heating, the heating temperature is preferably 40 to 200 ° C. When the present composition contains a cross-linking agent, it is preferable to heat the composition to a temperature higher than the cross-linking temperature of the cross-linking agent for curing, if necessary.

(Mechanism of action)
Since the article of the present invention described above is treated with the present composition, it is excellent in dynamic water repellency or resistance to repeated immersion in water, and is repellent even after being exposed to conditions such as alkali. Water repellency does not easily decrease.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
Examples 1 to 6 are examples, and examples 7 to 12 are comparative examples.

(Ratio of each unit)
After removing the surfactant and the solvent from the fluorinated polymer dispersion obtained in each example, ¹ H-NMR and each monomer by gas chromatography of the fluorinated polymer dispersion obtained in each example. The ratio (mol%) of each unit to all the units constituting the fluorine-containing polymer was calculated from the reaction rate of.

(Solid content concentration)
The solid content concentration of the fluorine-containing polymer dispersion is determined by taking the mass of the sample before heating as the sample mass and the mass after drying the sample in a convection dryer at 120 ° C. for 4 hours as the solid content mass (solid content mass). / Sample mass) × 100.

(Conversion rate)
From the theoretical value of the solid content concentration of the fluorine-containing polymer dispersion calculated from the amount of the raw material charged and the measured value of the solid content concentration of the fluorine-containing polymer dispersion, the monomer is calculated by the actual measurement value / theoretical value × 100. The conversion rate of the components to a fluorine-containing polymer was determined. When the conversion rate was 90% or more, it was evaluated as ◯ (good), when it was 80% or more and less than 90%, it was evaluated as Δ (possible), and when it was less than 80%, it was evaluated as × (impossible).

(Average molecular weight)
<Recovery of fluorine-containing polymer>
6 g of the fluorine-containing polymer dispersion obtained in each example was added dropwise to 60 g of a mixture of 6 g of hexane and 54 g of 2-butanol, and the mixture was stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was separated. To the separated solid, 30 g of isopropyl alcohol (hereinafter, also referred to as "IPA") modified alcohol (manufactured by Imazu, product name: 95% IPA modified alcohol) and 30 g of ion-exchanged water were added and stirred well. After centrifugation at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum dried at 35 ° C. overnight to obtain a fluorine-containing polymer.

<Measurement of Mn and Mw>
The recovered fluorine-containing polymer is dissolved in a mixed solvent containing a fluorine-containing solvent (manufactured by AGC, AK-225) / tetrahydrofuran (hereinafter referred to as "THF") = 6/4 (volume ratio) to concentrate the solid content. A 0.5 mass% solution was prepared and passed through a 0.2 μm filter to prepare an analytical sample. For the analysis sample, Mn and Mw were measured by GPC measurement. The measurement conditions are as follows.
Equipment: Tosoh, HLC-8320GPC,
Column: Made by Polymer laboratories, MIXED-C Length: 300 mm, Outer diameter: 7.5 mm Film thickness: 5 μm,
Mobile phase: AK-225 / THF = 6/4 (volume ratio),
Flow velocity: 1.0 mL / min,
Oven temperature: 37 ° C,
Sample concentration: 1.0% by mass,
Injection volume: 50 μL,
Detector: RI,
Molecular Weight Standard: Polymethylmethacrylate (Mp = 2136000, 955000, 569000, 332800, 121600, 67400, 31110, 13300, 7360, 1950, 1010, and 550).

(Tg)
Approximately 10 mg of the recovered fluorine-containing polymer was measured in a special aluminum pan and used as an analysis sample. For the analytical sample, Tg was measured by DSC measurement. The measurement conditions are as follows.
Equipment: Made by TA Instruments, Q2000,
Temperature program: -20 ° C to 180 ° C, 10 ° C / min, 2 cycles,
Measurement: Tg is calculated from the change in calorific value observed during the second temperature rise.

(Water receding contact angle)
Using DCAT21 (manufactured by DataPhysics), the receding contact angle of the surface of the article with water was measured at 25 ° C. by the Wilhelmy method. The receding contact angle with water is a measure of the dynamic water repellency of the article. The larger the receding contact angle with water, the better the dynamic water repellency.

(N-HD static contact angle)
In accordance with JIS R 3257: 1999 "Test method for wettability of substrate glass surface", droplets of n-hexadecane (hereinafter referred to as "n-HD") were allowed to stand at five locations on the surface of the article. The contact angle of n-HD was measured for each droplet by the static drip method. The droplets were about 2 μL / drop and measurements were taken at 20 ° C. The contact angle of n-HD is indicated by the average value of the measured values at five points. The contact angle of n-HD is a measure of the oil repellency of the article.

(Repeat water immersion resistance)
The article was repeatedly immersed in ion-exchanged water 5 times at a speed of 0.5 mm / sec using a dip coater (device name: F225, manufactured by Asumi Giken Co., Ltd.). After that, the shape of the surface of the article was visually observed and evaluated according to the following criteria.
〇: No change in the appearance of the article surface.
△ It is confirmed that a part of the surface of the article is cracked or peeled off.
× Cracks and peeling are confirmed on the entire surface of the article.

(Monomer (a))
αCl-C6OLF: CH ₂ = CCl- (CF ₂ ) ₅ CF ₃ (manufactured by Shinquest).
αCl-C4OLF: CH ₂ = CCl- (CF ₂ ) ₃ CF ₃ (manufactured by Shinquest).
(Monomer (b))
C6OLF: CH ₂ = CH- (CF ₂ ) ₅ CF ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.).
C4OLF: CH ₂ = CH- (CF ₂ ) ₃ CF ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.).
AcV: Vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.).
PiV: Vinyl pivalate (manufactured by Tokyo Chemical Industry Co., Ltd.).
StV: Vinyl stearate (manufactured by Tokyo Chemical Industry Co., Ltd.).
VCM: CH ₂ = CHCl (manufactured by Yokohama Chemical Co., Ltd.).

(Surfactant)
<Cationic surfactant>
LC18-63: 63% by mass water of alkyl (carbon: 16-18) trimethylammonium chloride and isopropyl alcohol solution (Lipocard 18-63, manufactured by Lion Specialty Chemicals Co., Ltd.).
<Nonionic surfactant>
PEO-30: 10% by mass aqueous solution of polyoxyethylene oleyl ether (about 30 mol adduct of ethylene oxide, manufactured by Kao Corporation, Emargen 430).
P204: Ethylene oxide / propylene oxide polymer (average molecular weight 3330, containing 40% by mass of ethylene oxide, NOF Corporation product name, pronon # 204).

(Medium)
Water: Ion-exchanged water.
DPG: Dipropylene glycol.
(Polymerization initiator)
VA-061A: 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) has a mass of 1, and the mass of acetic acid is 0.8. A 20% by mass aqueous solution of the acetate of VA061 obtained by mixing so as to be.

(Examples 1 to 12)
Monomers other than AcV and VCM, a medium, and a surfactant were added to a 1-liter autoclave equipped with a stirrer in the number of parts (mass parts) shown in Tables 1 and 2 and stirred to obtain a mixed solution. .. The mixed solution was put into a high-pressure homogenizer and pre-emulsified at a pressure of 10 MPa, and then high-pressure emulsified and dispersed at a pressure of 40 MPa to obtain an emulsified solution.
The emulsion was placed in a stainless steel autoclave, and the polymerization initiator was added in the number of parts charged as shown in Tables 1 and 2. The inside of the autoclave was replaced with nitrogen 5 times at a pressure of 0.5 MPa, AcV and VCM were added, the temperature was raised to 45 ° C., and the monomer components were polymerized for 72 hours to obtain a fluorine-containing polymer dispersion. Tables 1 and 2 show the solid content concentration, conversion rate, and Mw, Mn, Mw / Mn, and Tg of the fluorine-containing polymer in the fluorine-containing polymer dispersion liquid. In Tables 1 and 2, the number of copies of the surfactant and the polymerization initiator charged is the total amount including the mass of the solvent.

The fluorine-containing polymer dispersion was diluted with distilled water to adjust the solid content concentration to 1.0% by mass to obtain a water- and oil-repellent composition.
A dip coater (device) is applied to the surface of a glass substrate (ASLAB, SUPER GRADE MICROSCOPE SLIDES; THICK product name, length: 25 mm, width: 75 mm, thickness: 1.0-1.2 mm) with a water-repellent and oil-repellent composition. Name: F255) was applied by reciprocating three times at a speed of 0.5 mm / sec, and dried at 200 ° C. for 10 minutes was used as an article for evaluation. The articles were evaluated for water receding contact angle, n-HD static contact angle and repeated water immersion resistance. The results are shown in Tables 1 and 2.

The articles treated with the water-repellent oil-repellent composition of Examples 1 to 6 containing the fluorine-containing polymer having the unit (a) were excellent in dynamic water repellency, oil repellency and repeated water immersion resistance. ^{Further, since the R f} group is introduced into the fluorine-containing polymer by the unit (a), it can be judged that these characteristics are unlikely to decrease even when exposed to conditions such as alkali.
The water and oil repellent compositions of Examples 7 to 12 are the same as the water and oil repellent compositions of Examples 1 to 6, respectively, except that the chlorine atom at the α-position of the unit (a) is replaced with a hydrogen atom. However, the dynamic water repellency, oil repellency, and repeated water immersion resistance of the article were inferior to those of Examples 1 to 6.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2019-236897 filed on December 26, 2019 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (15)

1. A fluorine-containing polymer containing a unit based on the following monomer (a) and a unit based on the following monomer (b).
   Monomer (a): A compound represented by _{CH 2} = CX-R ^f.
   However, X is a halogen atom and R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms.
   Monomer (b): A monomer copolymerizable with the monomer (a).
2. The fluorine-containing polymer according to claim 1, wherein R ^f is a perfluoroalkyl group having 4 to 6 carbon atoms.
3. The fluorine-containing polymer according to claim 1 or 2, wherein X is a chlorine atom.
4. The fluorine-containing polymer according to any one of claims 1 to 3, wherein the ratio of the unit based on the monomer (a) to all the units constituting the fluorine-containing polymer is 20 to 60 mol%.
5. The fluorine-containing polymer according to any one of claims 1 to 4, wherein at least a part of the unit based on the monomer (b) is a unit based on the following monomer (b1).
   Monomer (b1): A compound represented by _{CH 2} = CH-Q or CH ₂ = CHCH _2-Q.
   However, Q is a halogen atom or an organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom.
6. A method for producing a fluorine-containing polymer, wherein a monomer component containing the following monomer (a) and the following monomer (b) is polymerized in the presence of a polymerization initiator.
   Monomer (a): A compound represented by _{CH 2} = CX-R ^f.
   However, X is a halogen atom and R ^f is a perfluoroalkyl group having 1 to 8 carbon atoms.
   Monomer (b): A monomer copolymerizable with the monomer (a).
7. The production method according to claim 6, wherein the ratio of the monomer (a) to the entire monomer component is 20 to 60 mol%.
8. The production method according to claim 6 or 7, wherein at least a part of the unit based on the monomer (b) is a unit based on the following monomer (b1).
   Monomer (b1): A compound represented by _{CH 2} = CH-Q or CH ₂ = CHCH _2-Q.
   However, Q is a halogen atom or an organic group whose bond terminal atom is an oxygen atom, a nitrogen atom or a sulfur atom.
9. The production method according to any one of claims 6 to 8, wherein the monomer component is polymerized in an aqueous medium.
10. The production method according to claim 9, wherein the monomer component is emulsion-polymerized in an aqueous medium containing a surfactant and the polymerization initiator.
11. A fluorinated polymer dispersion liquid containing the fluorinated polymer according to any one of claims 1 to 5 and an aqueous medium in which the fluorinated polymer is dispersed.
12. The fluorine-containing polymer dispersion liquid according to claim 11, further containing a surfactant.
13. A water- and oil-repellent composition containing the fluorine-containing polymer according to any one of claims 1 to 5.
14. The water- and oil-repellent agent composition according to claim 13, which comprises an aqueous medium and the fluorine-containing polymer dispersed in the aqueous medium.
15. An article in which at least a part of the surface of the base material is treated with the water-repellent oil-repellent composition according to claim 13 or 14.