JP4930058B2 - Fluorine-containing water and oil repellent composition - Google Patents

Description

  The present invention relates to a water / oil repellent composition capable of imparting excellent water / oil repellency to an object to be treated.

Conventionally, an addition polymerizable monomer (hereinafter, the addition polymerizable monomer is simply referred to as a monomer) containing a polyfluoroalkyl group (hereinafter, the polyfluoroalkyl group is referred to as an R ^f group) is used as a polymerization unit. Homopolymers and copolymers (hereinafter referred to as polymers in the sense of homopolymers and copolymers) are treated as organic solvent solutions or aqueous dispersions into textiles, paper, etc. A technique for imparting water and oil repellency is known.

Among them, an aqueous medium dispersion in which a polymer having a monomer having the structure of formula (1) as a polymerization unit is dispersed in an aqueous medium (water or a mixed solvent such as water and a water-soluble organic solvent) is a water / oil repellent composition. Is widely used.
^{_{CH 2 = CR 1 COOCH 2 CH}} 2 (NR 2 SO 2) m (CF 2) n F (1)
(In the formula, m represents 0 or 1, n represents an integer of about 6 to 12, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom, a methyl group, or an ethyl group.)

As a method for producing this aqueous medium dispersion, there are known a method of producing by emulsion polymerization, a method of producing a polymer by emulsifying and dispersing the polymer in an aqueous medium in the presence of a surfactant, and the like.
In a commonly used water and oil repellent, n in the formula (1), that is, the carbon number of the perfluoroalkyl group is substantially 8 or more. Such a carbon number of 8 or more perfluoroalkyl groups (hereinafter, carbon atoms mark the 8 or more perfluoroalkyl groups with long chain R ^F group.) The polymer having as a side chain, a long chain R ^F group It is known that there exists a microcrystalline melting point derived from Due to the strong crystallinity of this long chain ^RF group, the surface of the long chain ^RF group is effectively aligned, so that a polymer containing a monomer having the structure of formula (1) as a polymer unit has excellent water and oil repellency. It is said that this is a major factor.

However, a monomer containing a long chain R ^F group as a side chain (hereinafter, a monomer containing a long chain R ^F group as a side chain is referred to as a crystalline R ^F group-containing monomer) is generally different from other monomers. Since the compatibility is extremely poor, many organic solvents are required to obtain a homogeneous copolymer. Moreover, treatment of textiles such as a polymer containing them, possibly due to the strong side-chain crystallinity long chain R ^F group, it is known that soft texture of the object is impaired.

In conventional water and oil repellent, washing, dry cleaning, in order to impart a high durability against friction is a high melting point derived from the crystallites of the R ^F group Among crystalline R ^F group-containing monomer (usually when 70 ° C. or higher) crystalline R ^F although the use of group-containing monomers are essential, high-temperature treatment above the melting point of the perform repellent highly homogeneous coating process microcrystals generally This is necessary and may cause problems such as a decrease in dyeing fastness, hardening of the texture, and discoloration in the processing of textile products, which is not preferable.

In recent years, EPA (United States Environmental Protection Agency) has been working on environmental / biological compounds containing perfluoroalkyl groups having 8 or more carbon atoms, including compounds having the structure of formula (1), from the viewpoint of environmental conservation and health and safety. Concerning PFOS (Perfluorooctane Sulfonate) and PFOA (Perfluorooctanoic Acid), which are compounds that can be decomposed in the environment, expressed concern about accumulation in the body and announced that scientific research on PFOA will be strengthened (See EPA report “PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS” (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)).

In recent years, due to considerations for the work environment and the global environment, there is little impact on the ozone layer, such as water-based and oil-repellent media mainly composed of water, alcohol-based solvents, petroleum-based solvents called weak solvents, or hydrofluorocarbons. There is a demand for the use of fluorinated solvents. However, in the case of water and oil repellent for a polymer composed of conventional crystalline R ^F group-containing monomer as a main component, solubility, from the viewpoint of the dispersibility, aromatic, ketone, the so-called strong solvent of ester such as Further, there is a problem that it is necessary to use a fluorine-based solvent that has a great influence on the ozone layer, such as a chlorine-based solvent and a chlorofluorocarbon.

For these reasons, the following techniques have been proposed as water and oil repellents that do not contain long chain ^RF groups. For example, polyacrylate polymers having perfluoropolyether chains (WO02-103103, WO03-99904). A polymer composed of a monomer containing an R ^f group having 6 or less carbon atoms (hereinafter, the R ^f group having 6 or less carbon atoms is referred to as a “short-chain R ^f group”) does not contain fluorine having side chain crystallinity. Copolymer with monomer (WO02-83809), copolymer with monomer not containing ^Rf group having crosslinkable functional group (WO04-35708), sulfone containing ^Rf group having 4 or less carbon atoms There are polymers of amide acrylate (Special Table 2003-513123), and copolymers with vinylidene chloride or vinyl chloride (WO03-62521). However, no water- and oil-repellent agents that give satisfactory practical performance have been found.

  On the other hand, for the purpose of improving performance as a water and oil repellent, such as imparting high durability, and for the purpose of economy, a technique using a mixture of a plurality of polymers and a technique using composite particles of a plurality of polymers are known. For example, a crosslinkable polymer containing a blocked isocyanate group is used as a blender or a polymer extender to improve durability and fixability by using it together with other fluorine-free polymers (Japanese Patent Laid-open No. 54-128992, JP-A-10-501306), and those in which a cationic polymer such as a polyamine polymer is mixed (JP-A-6-49319, JP-A-2002-220539).

Further, a combination of a polymer containing fluorine and a polymer not containing fluorine (Japanese Patent Publication No. 49-42878, Japanese Patent Laid-Open No. 61-264081, US Pat. No. 3,378,609, US Pat. No. 4043964), polymers containing different fluorine contents or different fluorine contents. Combination (Japanese Patent Laid-Open Nos. 49-24890, 5-279541, 2000-160148, 2002-201463, US Pat. No. 3,347,812), involved in affinity and binding properties with chlorine atoms and hydroxyl groups Examples thereof include those that limit the amount of monomers having a structure (JP-A 2000-282015, JP-A 2003-13364). These are basically polymers that have a high fluorine content and are highly effective in reducing the surface energy of the object to be processed by segregating on the surface, and the object to be processed because of the low fluorine content or the presence of specific functional groups. It is a combination with a polymer that is considered to have higher affinity and binding properties. The reason why it is possible to improve the durability without impairing the water and oil repellency by such a combination of polymers is that the interface between the outermost surface portion and the base material due to the difference in fluorine content, etc. Some polymer composition distribution occurs, and the polymer is considered to exist in the outermost surface (high amount of fluorine). High water and oil repellency is exhibited by the polymer, and the affinity with the base material is higher (less fluorine content). It is reasonable to consider that the durability is realized by the presence of a large amount of polymer at the interface with the substrate. The technology in this field, represented by these known examples, basically has the functions required for other functions without impairing the water / oil repellency inherent to the polymer having R ^f groups, particularly crystalline R ^F groups. and it performs the improvement of the water-repellent repellent polymer containing only short chain ^the R ^f group of which is a water and oil repellency is inferior to the polymer containing crystalline R ^F group-containing monomers in the homopolymers The effect of improving oil performance has not been reported.

In addition, for the purpose of imparting high durability and improving performance as a water and oil repellent, such as low-temperature film-forming properties, a homopolymer is a copolymer containing a non-fluorinated monomer having a specific glass transition temperature (T _g ). Techniques for making polymers are known. For example, a copolymer (JP 60-152585, JP 9-328677) containing a non-fluorinated monomer whose homopolymer T _g is below a specific temperature as a polymerization unit, and the T _{g of the} homopolymer. in there specific copolymer comprising as polymerized units a non-fluorine-containing monomers such that above a temperature (JP 62-577, JP 63-27585), also homopolymers _{T g} of a specific temperature or higher copolymer (JP 53-50078) and the like are known comprising both certain such non-fluorine-based monomer and homopolymer non-fluorine-containing monomers such as T _g is below a certain temperature, as polymerized units . Further, a homopolymer T _g of it is water and oil repellent containing a composite particle comprising a particular temperature or higher monomers as polymerized units are known to be imparted water and oil repellency high even substrates under mild heat treatment conditions (Unexamined-Japanese-Patent No. 7-278442). However, all the text of the specification, and monomers of high The T _g disclosed in the examples are those containing no fluorine, focusing on the T _g of the fluorine-containing monomers and does not show its effect. In addition, the effect is only expressed in the composite particles. These can be said to be focused on the selection of non-fluorinated monomers that basically constitute polymers.

Further, the performance of the relationship between the water and oil repellent for T _g and fibers fluoromonomer, according to Roitman et al study, and T _g of homopolymer of fluorine-containing (meth) acrylate is 25 ° C. or higher oil repellency _{T g} is pointed out that significantly inferior to that of less than 25 ℃ (J.N.Roitman et al, Textile Res.J., 43,500 (1973) ). Thus, polymers the T _g of the homopolymer comprises a fluorine-containing monomer is 25 ℃ or higher, it had never been used practically as a water- and oil-repellent far.

An object of the present invention is to provide a water / oil repellent composition that can be used as an alternative to a water / oil repellent containing a compound having the structure of the formula (1) as a polymerization unit. That is, the polymer component despite constituted only polymer containing no crystalline R ^F group-containing monomer as polymerized units, water and oil repellent composition which can impart excellent water and oil repellency to a substrate To provide things.

The present invention
(A) a fluorine-containing monomer (a ¹ ) having a glass transition temperature (T _g ) of a homopolymer of 50 ° C. or more, and a fluorine-containing monomer (a ¹ ) that is present if the T _{g of the} homopolymer is less than 50 ° C. (a a polymer having a ²⁾ as polymerized units, is at least 50% by weight, based on the total of polymer, and (B) homopolymer _{T g} of quantities and ^{(a 1) (a 2)} of ^{(a 1)} a polymer having a fluorine-containing monomer optionally present at 50 ° C. or higher (a ^1), and homopolymer T _g of fluorine-containing monomer is less than 50 ° C. the (a ²⁾ as polymerized units, ( providing a ²⁾ amount (a ¹⁾ and (a ²⁾ total comprising polymer exceeding 50% by weight of the fluorine-containing water repellent oil repellent composition of the.

The inventor has studied in detail the mechanism of the water and oil repellency and the strengthening method. As a result, the fluorine-containing monomer whose T _g (glass transition temperature) of the homopolymer is 50 ° C. or higher (hereinafter, the fluorine-containing monomer whose T _{g of the} homopolymer is 50 ° C. or higher is referred to as “high Tg-containing F monomer”. ) As a main constituent (for example, 50% by mass or more, for example 55% by mass or more, particularly 60% by mass or more, particularly 80% by mass or more and 100% by mass or less) of the copolymer, fluorinated monomer homopolymer T _g of is less than 50 ° C. (hereinafter, which homopolymer T _g of the mark the fluorinated monomer is less than 50 ° C. "low T _g F-containing monomer".) the main component (e.g., By using a copolymer of more than 50% by weight of the copolymer, for example 55% by weight or more, particularly 60% by weight or more, especially 80% by weight or more, and 100% by weight or less) Water repellency In such balancing oil repellency, it found that the performance of more than the case of single use of them may impart to a substrate, excellent water and oil repellency without the use of crystalline R ^F group-containing monomer to be treated The above-mentioned problem of giving was solved, and the present invention was completed. The reason why the water / oil repellency is improved by the polymer blend as described above is not necessarily all clarified, but the most reasonable explanation is as follows.

  For example, when treating a fabric with a water / oil repellent agent, the surface of the fiber constituting the fabric is referred to as (a) a region in which the fibers are in contact with each other and (b) a region in which the fibers are not in contact with each other. There are two types of areas.

Since the contact angle of water on the surface treated with a water / oil repellent is generally large, only a part of the surface of the fabric is in contact with water when water repellency is sufficiently exhibited in a water repellency test. (B) is considered to be in contact with water. In order to develop high water repellency, it is necessary to suppress the environmental responsiveness such as the hydrophilic part in the polymer molecule moving to the surface and orienting by contact with water, which is a measure of the micro-brown mobility of polymer chains. high T _g it is desirable. Also important in this case, portions having a large contribution for water repellency in the polymer chain, i.e., is to suppress the movement of the domain that the fluorine-containing monomer are continuous, high T _g monomer containing no fluorine (the homopolymer than increasing the T _g of the entire polymer by copolymerization with T _g is 50 ° C. or more monomers) of, it is effective to polymer to a high T _g fluorinated monomer as a main component.

On the other hand, the contact angle of oil on the surface treated with the water / oil repellent is smaller than that of water, and it is considered that the oil is uniformly in contact with the surface of the cloth in the oil repellent test. Therefore, the presence or absence of minute defects in the water / oil repellent polymer film formed on the fiber greatly affects the oil repellent performance. In particular, the region (a) where the fiber and the fiber contact each other is likely to cause a mechanical coating defect due to the mechanical load, and when the defect occurs, the liquid is likely to enter the void due to capillary action. In order to improve oil repellency, it is important to reduce defects in the polymer film in this region. Generally, amorphous polymers rigid half the below T _g temperature, to become brittle, when treated fabric with high T _g polymer, liable defect occurs in the polymer coating in susceptible regions of mechanical load, It is considered that sufficient oil repellency cannot be exhibited. Therefore, in order to improve oil repellency, it is not desirable that the polymer present in the region (a) has a very high _Tg , and it is desirable that the polymer has some flexibility.

This has no side chain crystallinity, in comparison between the fluorine-containing acrylate homopolymers fluorine content not much, T _g is high is higher water repellency poor oil repellency, whereas, T _g is The low ones explain well the experimental fact that oil repellency is high but water repellency tends to be low. Furthermore, to be considered polymers whose main constituent a low T _g F-containing monomer has a high fluidity in comparison to the polymer of the high T _g F-containing monomer as a main component, such as cloth with water- and oil-repellent treatment process of, in particular during the heat treatment, moved by capillary action, thought to become abundant in regions of the fabric (a), conversely, the polymer of the high T _g F-containing monomer as a main component is fluidized It is considered that most of them remain in the region (b) because of their low nature. That is, when subjected to a treatment to the fabric by mixing the polymer of the polymer and low T _g F-containing monomer to the high T _g F-containing monomer as a main component as a main component, important oil repellency, such as by a suitable heat treatment polymer in (a) region of the fiber surface, which appears to have a Do effects whose main constituent a low T _g F-containing monomers are, for seems (b) region to have a significant effect on water repellency high T _It is considered that many polymers having _g- containing F monomer as a main constituent are present. This is because, by blending the polymer, it is possible to significantly improve the performance as compared with the case where each polymer is used alone or copolymerized. It is believed that there is.

  As described above, the conventional technology using a combination of different polymers in the water / oil repellent can be explained in many cases by the concept of role sharing at the interface between the outermost surface portion and the substrate in the water / oil repellent polymer coating. On the other hand, such an explanation is difficult in the present invention, and can be understood only by assuming a completely new principle as described above.

The T _g of the homopolymer of the F-containing monomer constituting the polymer is an appropriate measure of molecular motion in a domain in which the F-containing monomer is considered to contribute greatly to the water / oil repellency in the polymer chain. However, movement of the polymer molecules at the interface in order to differ from the bulk state, T _g of the homopolymer in order to micro-Brownian motion of the domains containing F monomer present in the outermost surface are continuous are frozen at room temperature above room temperature In the present invention, the temperature of 50 ° C. that separates the high Tg monomer and the low Tg monomer is considered reasonable in that respect.

  The expression model of water and oil repellency based on the above consideration is a rational model for improving the water and oil repellency by the polymer blend in the present invention, but is a model simplified to explain the phenomenon at the present time. However, corrections and changes may be made in the future. However, it goes without saying that this does not affect the present invention.

Since the water / oil repellent composition in the present invention does not have a long-chain ^RF group which has been conventionally essential for obtaining sufficient water / oil repellent performance, the texture of the side chain is reduced. There is no concern and excellent water and oil repellency can be imparted to the substrate. In particular, it is possible to achieve both water repellency and oil repellency for textiles.

  The water / oil repellent composition of the present invention comprises a polymer (A) and a polymer (B) as essential components, and if necessary, an aqueous medium (C), a surfactant (D), an organic solvent (E), a heat It contains at least one component selected from the group consisting of a curing agent (F), another polymer (G) (for example, non-fluorine polymer), an additive, and the like.

The ratio of the polymer (A) and the polymer (B) in the water / oil repellent composition is such that the ratio of the polymer (A) to the total amount of the polymer (A) and the polymer (B) is 5 to 95% by mass, for example 10 to 90%. It may be such that it is mass%, in particular 20 to 80 mass%. In the following, “part” or “%” represents “part by mass” or “% by mass” unless otherwise specified. Further, the polymer (A) and the polymer (B) do not have to be a single polymer, and may be a combination of two or more types of polymers.
The polymer (A) is a polymer containing a monomer (a) containing fluorine in the molecule and a monomer (b) containing no fluorine atom in the molecule as necessary, and the proportion of the monomer (b) is 40 mass. %, For example, less than 20% by mass. The proportion of monomer (b) in polymer (A) may be 0% by mass. The lower limit of the proportion of monomer (b) in polymer (A) may be 0.1% by weight, in particular 1% by weight.
The polymer (B) is a polymer containing a monomer (a) containing fluorine in the molecule and a monomer (b) containing no fluorine atom in the molecule as necessary, and the proportion of the monomer (b) is 70%. Less than, for example less than 50% by weight, in particular less than 30% by weight. The proportion of monomer (b) in the polymer (B) may be 0% by mass. The lower limit of the proportion of monomer (b) in polymer (A) may be 0.1% by weight, in particular 1% by weight.

Polymer monomer contained in (A) (a), a high _{T g} F-containing monomer ^(a 1), and optionally made of a low _{T g} F-containing monomer ^{(a 2).} The proportion of the monomer (a ² ) in the monomer (a) constituting the polymer (A) is less than 50% by mass, for example, less than 35% by mass, particularly less than 20% by mass. The proportion of the monomer (a ² ) in the monomer (a) constituting the polymer (A) may be 0% by mass or more, for example, 5% by mass or more, particularly 10% by mass or more. Monomer contained in the polymer (B) (a) consists of low _{T g} F-containing monomer ^(a 2), and high _{T g} F-containing monomer as needed ^{(a 1).} The proportion of the monomer (a ¹ ) in the monomer (a) constituting the polymer (B) is less than 50% by mass, for example, less than 35% by mass, particularly less than 20% by mass. The proportion of the monomer (a ¹ ) in the monomer (a) constituting the polymer (B) may be 0% by mass or more, for example, 5% by mass or more, particularly 10% by mass or more.
The monomer (a ¹ ), monomer (a ² ), and monomer (b) used for the polymer (A) or polymer (B) may each be a single monomer or may be composed of two or more types of monomers. . The monomer (a ¹ ), monomer (a ² ), and monomer (b) used for the polymer (B) are the same as those used for the polymer (A), partially the same or different. It doesn't matter.

Moreover, when a polymer (A) and a polymer (B) are copolymers, it is not limited to a random copolymer, A block, a graft copolymer, etc. may be sufficient. In this case, the monomer composition is such that the average value of the polymer satisfies the above conditions.
Incidentally, _{T g} of homopolymer are those measured by (DSC measurement method described in JIS-K-7121-1987) differential calorimetry. The molecular weight of the homopolymer here is about 10,000 or more. This is because, if the molecular weight of the homopolymer is more than 10,000, T _g of homopolymer is because hardly dependent on the molecular weight.

Monomer as a (a ¹⁾ and monomer (a ^2), from the side-chain amorphous fluorine-containing monomer (a ^a), the homopolymer T _g of the 50 ° C. or more monomers or the T _g of the homopolymer is 50 ° C. One or a plurality of monomers that are less than one can be selected and used. The side chain amorphous fluorine-containing monomer (a ^a ) is a monovalent or divalent polymerizable unsaturated group and one or more The amorphous R ^f group (R ^fa group) is a compound bonded directly or indirectly through a bonding group, and is preferably bonded indirectly. As the polymerizable unsaturated group, an alkylene group, particularly an ethylene group is preferable.

As used herein, the amorphous R ^f group (R ^fa group) is generally a perfluoroalkyl group having 6 or less carbon atoms, or a perfluoro group having 30 or less carbon atoms, such as 20 or less carbon atoms, particularly 10 or less carbon atoms. A poly) ether group or a structure in which fluorine atoms are replaced with hydrogen atoms within a range not exceeding 20% of the total number of fluorine atoms contained in these structures. The carbon number of the perfluoroalkyl group may be 1 or more, for example, 2 or more. The carbon number of the perfluoro (poly) ether group may be 3 or more, for example, 5 or more.
The perfluoro (poly) ether group is preferably represented by the structure of the following formula (2).
^{F-R fPFPE - [CF (} CF 3)] e - (CF 2) f - (2)
[Wherein, e represents an integer of 0 to 1, and f represents an integer of 1 to 2. R ^fPFPE represents a perfluoropolyether chain structure, [CF (CF ₃ ) CF ₂ O] _a [CF ₂ CF ₂ CF ₂ O] _b [CF ₂ CF ₂ O] _c [CF ₂ O] _d . However, a, b, c, d each represents an integer of 0-6. Moreover, it is a + b + c + d = 1-6, and the appearance order of each repeating unit is arbitrary. ].

A preferable side chain amorphous fluorine-containing monomer (a ^a ) can be represented by the following general formula (3).
(R ^fa -Y-) _n X (3)
Wherein, n is 1 or 2, X is a polymerizable unsaturated group, and when n is _{^{1 -CR a = CH 2, -Q}} -COCR a = CH 2, -Q- (CH 2) _{^{m -φ-CR a = CH 2}} , a ^-Q-CR a = CH ₂ or ^{-CO-Q-CR a = CH} 2, and when n is ^{2 -Q-COR a = CR a} CO-Q- or _{-Q-COC (CH 2 CO-} Q -) = CH 2 are expressed (here, m is an integer .Q of 0-3 -O -, - S- or -NR ^b - .φ representing the the substituent R ^a represents ^a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group. ^b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ^fa is the above-described amorphous R ^f group, and Y is a divalent organic group or a single bond. ]

A preferable structure of Y which is a divalent organic group can be represented by the following formula (4).
_{- (CH 2) p T (} CH 2) q (CHR a) r - (4)
[Wherein, p and q independently represent an integer of 0 or more, and p + q is an integer of 0 to 22. r is 0 or 1; R ^a is the same as described above. T is a single _{^{bond, -CH = CH -, - CONR}} b -, -OCONR b -, -SO 2 NR b -, - SO 2 -, - NHCONH -, - CH (OH) -, - CH (OCOR a) -, - OCOO -, - COO -, - OCO -, - O -, - S -, - CHR a -, - CHCl -, - CHBr -, - CHI-, cyclohexenylene group, a phenylene group, biphenylene group, ^{_{-CH [(CH 2) s R}} fa] - it represents a. However, s is an integer of 0-2. ]

In general, among side chain amorphous fluorine-containing monomers (a ^a ), compounds having a short side chain or limited side chain mobility due to branching, particularly methacrylates and α-halogen-substituted acrylates the _{T g} of the the homopolymer is more than 50 ° C.. Also, compounds containing greater perfluoro (poly) ether structure of molecular mobility as a side chain, among the side chains amorphous fluorine-containing monomer (a ^a), in particular its acrylate body T _g of the homopolymer is less than 50 ° C. .
Further, when the polymer has a melting point (T _m ), the glass transition temperature T _g is lower than T _m , so that it can be said that the T _{g of the} homopolymer having T _m of less than 50 ° C. is also less than 50 ° C. Furthermore, can be regarded as the polymer with an apparent fluidity at room temperature T _g even when no is seen clearly transition point above DSC measurement is 50 ° C. or less.

_{T g} of the monomer ^{(a 1)} is temperatures above 55 ℃, may be, for example, 60 to 160 ° C.. Monomer (a ²⁾ a T _g is 45 ° C. or less, for example, homopolymers of monomers (a ²⁾ may be one as take molten state at room temperature. The T _g of the monomer (a ² ) may be, for example, −100 ° C. to + 45 ° C., particularly −80 ° C. to + 40 ° C.

As a specific example of the monomer (a ¹ ),
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCCl═CH ₂ (T _g : 65 ° C.),
F (CF ₂ ) ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (T _g : 77 ° C.),
(CF ₃ ) ₂ CHOCOC (CH ₃ ) ═CH ₂ (T _g : 91 ° C.), C (CH ₃ ) (CF ₃ ) ₂ CH ₂ OCOCH═CH ₂ (T _g : 133 ° C.), and the like.
As a specific example of the monomer (a ² ),
F (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCCl═CH ₂ (T _m : 45 ° C.),
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH═CH ₂ (T _m : 42 ° C.),
_{F (CF 2) 6 (CH} 2) 2 OCOCH = CH 2 (T g: -30 ℃),
(CF ₃ ) ₂ CHOCOCH═CH ₂ (T _g : 15 ° C.),
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂ (T _g : 37 ° C.),
_{CF 3 CF 2 CF 2 OCFCF 3} CF 2 OCFCF 3 CH 2 OCOC (CH 3) = CH 2 (T g: -34 ℃) , and the like.

  The polymer (A) and the polymer (B) may be a copolymer using a copolymerizable monomer (b) containing no fluorine atom other than the monomer (a) alone or in combination as required. Is also possible.

Examples of the copolymerizable monomer (b) include the following (hereinafter, acrylates, methacrylates and α-halogen (for example, chloro) substituted acrylates are collectively referred to as acrylate analogs. Acrylamide analogs). The same applies to the notation of body and acrylic acid analogs.) Acrylate analogues; acrylamide analogues (b ¹ ); acrylonitrile analogues; (halogenated alkyl) vinyl ethers such as 2-chloroethyl vinyl ether; olefins such as ethylene, propylene, isoprene, butene, dodecylethylene, hexene, butadiene And dienes; halogen-substituted ethylenes such as vinyl chloride, vinyl bromide, vinylidene chloride and chloroprene; halogen-substituted butadienes such as 2-chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene; Styrenes such as styrene and α-methylstyrene, p-methylstyrene; vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinyl octoate, vinyl dodecanoate, vinyl stearate. Tells; Aliphatic allyl esters such as allyl heptanoate, allyl caprylate, allyl caproate, allyl octanoate, allyl hexanoate; vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N-cyclohexylmaleimide, N -N-alkylmaleimides such as methylmaleimide; (di) alkyl esters such as maleic acid, fumaric acid, crotonic acid, citraconic acid and mesaconic acid.

  Specific examples of acrylate analogs include acrylate analogs having a benzene ring such as phenyl acrylate analogs and benzyl acrylate analogs, and compounds in which a methyl group, a methoxy group, a chlorine atom, or the like is bonded to these benzene rings; Cycloalkyl acrylate analogs such as cyclohexyl acrylate analogs, cyclododecyl acrylate analogs, dicyclopentyl acrylate analogs; methyl acrylate analogs, ethyl acrylate analogs, propyl acrylate analogs, isopropyl acrylate analogs, butyl acrylate analogs, isobutyl Acrylate analog, t-butyl acrylate analog, 3,3-dimethyl-2-butyl acrylate analog, hexyl acrylate analog, octyl acrylate analog, 2-ethyl Alkyl acrylate analogues having a saturated alkyl group having 1 to 12 carbon atoms such as hexyl acrylate analogues, decyl acrylate analogues, lauryl acrylate analogues; dodecyl acrylate analogues, cetyl (meth) acrylates, hexadecyl acrylate analogues, stearyl Acrylate analogs having a saturated alkyl group having 13 to 25 carbon atoms, such as acrylate analogs, isostearyl acrylate analogs, behenyl acrylate analogs, icosyl acrylate analogs, docosyl acrylate analogs, tetracosyl acrylate analogs; Diethylene glycol monoacrylate monomethyl ether analogue, polyethylene glycol monoacrylate monomethyl ether analogue, polypropylene glycol monoacrylate monomethyl ether Analogues, polyethylene glycol-polypropylene glycol monoacrylate monomethyl ether analog, polyethylene glycol monoacrylate analog (2-ethylhexyl) ether acrylate analogs; isobornyl acrylate analogs, adamantyl acrylate analogs Preferred examples include an acrylate analog having a cyclic structure; an acrylate analog having a polydimethylsiloxane group; a chloroethyl acrylate; an acrylate analog having a urethane bond, and the like.

Specific examples of the acrylamide analog (b ¹ ) include acrylamide analogs, N-methylacrylamide analogs, N-stearyl acrylamide, N-cetylacrylamide, N, N-dimethylacrylamide analogs, N, N-diethylacrylamide analogs. N, N-diisopropylacrylamide analog, N-methoxymethylacrylamide analog, N-ethoxymethylacrylamide analog, N-butoxymethylacrylamide analog, N-methylolacrylamide analog, N-butoxymethylolacrylamide analog, Preferable examples include N-butyrolacrylamide analogs, diacetoneacrylamide analogs, methylolated diacetoneacrylamide analogs, and the like.
The monomer (b) may be a monomer having a reactive group other than the polymerizable unsaturated bond, including the acrylamide analog, and examples of such reactive group include an epoxy group, a hydroxyl group, and a carboxyl group. Groups, acid anhydride groups, amide groups, amino groups, alkoxysilyl groups, N-methylol groups, N-alkyloxy groups, isocyanate groups, acryloyl groups, blocked isocyanates, imino groups, cyano groups, groups, etc. Can be mentioned. By copolymerizing these reactive group-containing monomers, adhesion to substrates such as fibers is strengthened, and the effect of improving durability, washing resistance, dry cleaning resistance, etc. is seen. There is also a secondary effect of improving the polymerization stability during emulsion polymerization.

Monomers having reactive groups other than polymerizable unsaturated bonds include blocked isocyanate group-containing acrylate analogs (b ² ); 3-chloro-2-hydroxypropyl acrylate analogs, 2-hydroxyethyl acrylate analogs, 2 Hydroxyl groups such as -hydroxypropyl acrylate analogues, 4-hydroxybutyl acrylate analogues, glycerin monoacrylate analogues, trimethylolpropane monoacrylate analogues, glycerin monoacrylate analogues, 2-hydroxy-3-phenoxypropyl acrylate analogues Acrylate analogues; glycidyl acrylate analogues, aziridinyl acrylate analogues, acrylate analogues with epoxy groups such as aziridinyl ethyl acrylate analogues; N, N, N-stearyldi An acrylate analog having a quaternary ammonium structure such as a tylammonium acrylate analog, an N, N, N-cetyldimethylammonium acrylate analog, a hydroxypropyltrimethylammonium methacrylate methacrylate; a diethylene glycol monoacrylate analog, a polyethylene glycol monoacrylate analog Acrylate analogues having an ether structure such as polypropylene glycol monoacrylate analogues, polyethylene glycol polypropylene glycol monoacrylate analogues; N-stearyl allylaminoethyl acrylate analogues, N-cetylaminoethyl acrylate analogues, N, N-dimethyl Aminoethyl acrylate analogues, N, N-diethylaminoethyl acrylate analogues, N, N-stearyl methacrylate Substituted aminoalkyl acrylate analogs such as tilaminoethyl acrylate analogs, N, N-cetylmethylaminoethyl acrylate analogs; acrylate analogs having a linear unsaturated alkyl group of 3 or more carbon atoms such as allyl acrylate analogs; 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydro An acrylate analog having a carboxylic acid group such as genphthalate; an acrylate analog having a reactive silyl group such as a γ-trimethoxysilylpropyl acrylate analog; an ethylene glycol diacrylate analog, diethylene glycol Cole diacrylate analogue, neopentyl glycol diacrylate analogue, 1,4-butanediol diacrylate analogue, 1,6-hexanediol diacrylate analogue, glycerin diacrylate analogue, 2-hydroxy-3-acroy Polyacrylate analogues such as loxypropyl methacrylate, neopentyl glycol bisacrylate analogues, hydroxypivalate neopentyl glycol diacrylate analogues, polyoxyethylene diacrylate analogues, polypropylene diacrylate analogues; acrylic acid analogues, itaconic acid , Unsaturated carboxylic acids and acid anhydrides such as maleic acid, crotonic acid and maleic anhydride; other acetoacetoxyethyl acrylate analogues, 2- (meth) acryloyloxyethyl acid Sufeto, 2-acrylamido-2-methylpropane sulfonic acid, 4-cyanophenyl acrylate analogs Aminimido group ^{(-CO-NNR 1 R 2 R} 3) containing acrylate analogues, N- vinylcarbazole, triallyl cyanurate, allyl Examples thereof include glycidyl ether and vinyl pyrrolidone.

Further, as the blocked isocyanate group-containing acrylate analog (b ² ), 2-isocyanate ethyl acrylate analog, or an acrylate analog having a functional group capable of binding to an isocyanate group and polyisocyanate (b ³ ) are used. A reaction product obtained by reacting at a ratio in which one or more isocyanate groups remain is preferred.
As the acrylate analog having a functional group capable of bonding to an isocyanate group, an acrylate analog having a hydroxyl group is preferable, and a mono- or diester of an acrylic acid analog and a polyhydric alcohol is particularly preferable. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane-alkylene oxide adduct, and pentaerythritol.

Examples of the polyisocyanates (b ³ ) include aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, and 4,4 ′. -Preferred are alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, bis (isocyanate methyl) cyclohexane, norbornene diisocyanate, and modified products such as nurate modified products, prepolymer modified products, and burette modified products. Aliphatic isocyanates, alicyclic isocyanates, and their nurate modified products, prepolymer modified products, and burette modified products are preferred.

As the isocyanate group blocking agent (b ⁴ ), oximes, alkyl ketoximes, phenols, alkanols, β-diketones, malonic esters, lactams and the like are preferable. For example, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, indazole, methylethylketoxime, cyclohexanone oxime, ε-caprolactam, ethyl acetoacetate, acetylacetone, phenol, cresol, methanol, diethylmalonate, maleic imide, bisulfite 2-butanone Examples include oxime, diethyl malonate, isopropyl alcohol, t-butyl alcohol, maleimide, sodium bisulfite and the like. In particular, 2-butanone oxime, 3-methylpyrazole, 3,5-dimethylpyrazole, cyclohexane oxime, methyl ethyl ketoxime, ethyl acetoacetate, ε-caprolactam, diethyl malonate, pyrazole from the viewpoint of balance of stability or reactivity. preferable.

  Specific examples of the blocked isocyanate group-containing acrylate analog include the following. Compound in which isocyanate group of 2-isocyanatoethyl acrylate analogue is blocked with methyl ethyl ketoxime, Compound in which isocyanate group of 2-isocyanate ethyl acrylate analogue is blocked with ε-caprolactam, 1 of isophorone diisocyanate and 2-hydroxyethyl acrylate analogue : 1 (molar ratio) compound in which the isocyanate group of the reactant was blocked with methyl ethyl ketoxime, and 1: 1 (molar ratio) compound in which the isocyanate group of the isophorone diisocyanate and 2-hydroxypropyl acrylate analogue was blocked with methyl ethyl ketoxime A compound obtained by blocking a 1: 1 (molar ratio) reaction product of norbornene diisocyanate and 2-hydroxyethyl acrylate analog with methyl ethyl ketoxime .

  In the water / oil repellent composition of the present invention, the preparation method of the polymer (A) and the polymer (B) as the active ingredients is not particularly limited. For example, a solution polymerization method using an organic solvent, a non-aqueous dispersion polymerization method, Conventional polymerization techniques such as dispersion polymerization using water as a dispersion medium, emulsion polymerization, suspension polymerization, and bulk polymerization can be employed.

  When the polymerization is performed in an aqueous medium, it is preferable to apply an emulsion polymerization method or a dispersion polymerization method, and an emulsion polymerization method is particularly preferable. In the emulsion polymerization method, it is preferable to start the polymerization after sufficiently emulsifying the monomer using a high-pressure emulsifier or the like. For example, it is possible to improve the yield of the final polymer by mixing and dispersing a mixture of monomer, surfactant and aqueous medium in advance with a homomixer or high-pressure emulsifier before starting polymerization. It is.

  By emulsion polymerization or the like, a liquid (also referred to as a dispersion) in which the polymer (A) is dispersed as particles in an aqueous medium and a dispersion of the polymer (B), or a mixture thereof are obtained. The resulting copolymer solution, dispersion, and emulsion can be used as a composition as is or diluted. A copolymer obtained by solution polymerization, emulsion polymerization, or other polymerization method may be separated, and dissolved, dispersed, or emulsified in a solvent, a dispersion medium, or an emulsification medium as necessary to obtain a composition.

In emulsion polymerization, an aqueous medium (C) is used as a polymerization medium. The aqueous medium (C) is a medium containing water, and water alone may contain an organic solvent as a polymerization auxiliary solvent as desired.
As the organic solvent, one or more water-soluble organic solvents (c) selected from the group consisting of ketones, ethers, alcohols (particularly monohydric alcohols and saturated polyhydric alcohols), and nitrogen compounds are preferable. For ketones, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable. For ethers, saturated polyhydric alcohol monoalkyl ethers, dialkyl ethers, monoalkyl ether monoacyl esters, dioxane and the like are preferable. For nitrogen compounds, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like are preferable. Of these, ether-based organic solvents are most preferable from the viewpoint of low flammability.

  The water-soluble organic solvent (c) can be used alone or in combination. The amount of the water-soluble organic solvent (c) in the aqueous medium is preferably 5 to 100 parts by mass, particularly preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B). If the water-soluble organic solvent (c) is too much, the durability of water and oil repellency against washing may be lowered. Moreover, the quantity of an aqueous medium may be 10-5000 mass parts with respect to 100 mass parts of polymer to superpose | polymerize, for example, 100-1000 mass parts.

Specific examples of the monohydric alcohol used in the aqueous medium include ethyl alcohol and isopropyl alcohol.
The saturated polyhydric alcohol is preferably a compound having 2 to 4 hydroxyl groups. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, Examples include tetrapropylene glycol, hexylene glycol, glycerin, trimethylol ethane, and trimethylol propane.

  Specific examples of (mono or poly) alkyl ethers of saturated polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and acetates thereof; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monopropyl ether and their acetates; triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether and their acetates; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , And their acetates; dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and their acetates; tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and their acetates; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl Ether, propylene glycol dipropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, and tripropylene glycol diethyl ether.

  Of these, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether are particularly preferable. As a reaction product of the saturated polyhydric alcohol and ethylene oxide and / or propylene oxide, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol in which five or more oxypropylene groups are connected are preferable.

  The polymerization reaction to obtain the polymer (A) and the polymer (B) can be initiated by heat, light, radiation, radical polymerization initiator, ionic polymerization initiator, etc., but water-soluble or oil-soluble radical polymerization initiation A general-purpose initiator such as azo, peroxide, persulfate, redox or the like can be used according to the polymerization temperature, and azo compounds and salts thereof are particularly preferable.

  Specific examples of the oil-soluble polymerization initiator include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl4-methoxyvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-isobutyronitrile), benzoyl peroxide, di-tertiary-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxy Pivalate, diisopropyl peroxydicarbonate, t-butyl perpivalate and the like are preferable.

  Specific examples of the water-soluble polymerization initiator include 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis (2-methylpropionamidine) hydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate hydrate, 2,2′-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] hydrochloride, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, sodium peroxide, potassium persulfate, barium persulfate Preferable examples include ammonium persulfate and hydrogen peroxide.

Although the polymerization temperature in emulsion polymerization is not specifically limited, 20-150 degreeC is preferable and 30-80 degreeC is especially preferable.
The molecular weight of the polymer can be determined by a polystyrene conversion value by a gel permeation chromatography method. The mass average molecular weights of the polymer (A) and the polymer (B) are each preferably in the range of 5,000 to 500,000, and particularly preferably 10,000 to 250,000. When the average molecular weight of the polymer is in the range of 5,000 to 500,000, the polymer can sufficiently cover the substrate, so that high water and oil repellency can be imparted and high durability can be obtained.

The molecular weight can be adjusted by using a chain transfer agent, and it is generally desirable to use a chain transfer agent. As the chain transfer agent, alkyl thiols, alkylene dithiols, mercaptans such as thiocyanuric acid or aromatic compounds are preferable, and alkyl thiols are particularly preferable. Specific examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 2-hydroxyethyl mercaptan, lauryl mercaptan, stearyl mercaptan (octadecyl mercaptan) or α-methylstyrene dimer (CH ₂ = CPhCH Preferred examples include ₂ C (CH ₃ ) ₂ Ph [where Ph is a phenyl group]). It is also possible to use SH group-containing silicones.

Emulsion polymerization is preferably performed using a surfactant (D). There is no particular restriction on the surfactant used, nonionic surface active agent (d ^n), cationic surfactants (d ^c), an anionic surfactant (d ^a), amphoteric surfactants (d ^b) known or has one or more known surfactants may be employed, a nonionic surfactant (d ^n), cationic surfactants (d ^c) or amphoteric surfactants are preferred, nonionic of agent ^{(d n)} are preferred. When surfactants having different ionic properties are used in combination, a nonionic surfactant (d ⁿ ) and a cationic surfactant (d ^c ), or a nonionic surfactant (d ⁿ ) and an amphoteric surfactant ( A combination of d ^b ) is preferred. It is also possible to use a polymer surfactant.

  The amount of the surfactant (D) is preferably 0.01 to 30 parts by mass, particularly preferably about 0.5 to 15 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B). If the amount of the surfactant (D) is too small, the stability of the dispersion may be lowered. If the amount is too large, the durability of the water / oil repellency may be lowered, the processing bath compatibility may be lowered, and the dyeing fastness may be reduced. May be damaged. However, when the monomer (b) constituting the polymer contains a self-emulsifying monomer, the amount of the surfactant may be reduced.

The nonionic surfactant (d ^n), a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkyl ether monoacyl esters, polyoxyalkylene monoalkenyl ether or a polyoxyalkylene monoalkyl poly-enyl ether, polyoxyethylene mono (Substituted phenyl) ether condensate, polyoxyethylene mono (substituted phenyl) ether, polyoxyethylene polyoxyalkylene, alkylamine polyoxyethylene, alkylamido polyoxyethylene, alkylamine oxide, alkane (C ₁₂ -C ₁₈ ) Thiol, condensation product of ethylene oxide and alkyl (C ₁₂ -C ₁₈ ) amine, condensation product of ethylene oxide and oleic acid, ethylene oxide and sorbitan monofatty Condensation products and the like with an acid _(C 7 _{-C 18)} can be mentioned.

Specific examples of the nonionic surfactant (d ^n), polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene octyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Isooctyl phenyl ether, polyoxyethylene hexyl phenyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl Phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene Monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmi Tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene polyoxypropylene block polymer, polyglycerin fatty acid ester, polyether-modified silicone oil (trade names: SH3746, SH3748, SH3749, SH3771 (Toray・ Dow Corning Silicone Co., Ltd.)), perfluoroalkylethylene oxide adduct (trade name: Uni In DS-401, DS-403 (manufactured by Daikin Industries, Ltd.), fluoroalkylethylene oxide adduct (trade name: Unidyne DS-406 (manufactured by Daikin Industries, Ltd.)), perfluoroalkyl oligomer (trade name: Unidyne DS- 451 (Daikin Industries, Ltd.).

As the cationic surfactant (d ^c ), it is preferable to use a cationic surfactant made of a substituted ammonium salt. As a cationic surfactant comprising a substituted ammonium salt, a compound in which one or more hydrogen atoms bonded to the nitrogen atom of the ammonium salt are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group having a terminal hydroxyl group Preferred are cationic surfactants comprising, for example, mono (long chain alkyl) amine hydrochloride, mono (long chain alkyl) dimethylamine hydrochloride, mono (long chain alkyl) dimethylamine acetate, mono (long chain alkenyl) Amine salts such as dimethylamine hydrochloride, di (long chain alkyl) monomethylamine hydrochloride, mono (long chain alkyl) trimethylammonium chloride, di (long chain alkyl) dimethylammonium chloride, mono (long chain alkyl) monomethyldi (polyoxy) Ethylene) ammonium chloride, di (long chain alkyl) mono Chirumono (polyoxyethylene) ammonium chloride, mono (long chain alkyl) dibenzyl dodecyl di (hydro polyoxyethylene) ammonium chloride, a quaternary ammonium salt such as methylamine, ethyl sulfate. As the counter ion, chlorine ion, ethyl sulfate ion, or acetate ion is preferable. The carbon number of the long chain alkyl and the long chain alkenyl may be 8-50, for example 12-22.

Specific examples of the cationic surfactant (d ^c), dimethyl mono coconut amine acetate, tetradecylamine acetate, octadecylamine acetate, tallow alkyl propylene diamine acetate salt, N-[2-(diethylamino) ethyl] oleamide Hydrochloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium chloride, trimethyloctadecylammonium chloride, behenyltrimethylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, Benzyltetradecyldimethylammonium chloride, benzyloctade Didimethylammonium chloride, biphenyltrimethylammonium chloride, octadecyldimethylbenzylammonium chloride, octadecyldimethylmonoethylammonium sulfate, methyldodecyldi (hydropolyoxyethylene) ammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, dioleyl Dimethylammonium chloride, alkyl (beef tallow) dimethylbenzylammonium chloride, alkyl (beef tallow) trimethylammonium chloride, tetradecylmethylbenzylammonium chloride, polyoxyethylene dodecyl monomethylammonium chloride, polyoxyethylene lauryl monomethylammonium chloride, alkyl (beef Fat) imidazoline quaternary salt, 1-hydroxyethyl-2-alkyl (tallow) imidazoline quaternary salt, silicone-based cationic surfactant having a siloxane group as a hydrophobic group, fluorine-based cationic surfactant having a fluoroalkyl group as a hydrophobic group Agents (trade name: Unidyne DS-202 (manufactured by Daikin Industries, Ltd.)), among which octadecyltrimethylammonium chloride, octadecyldimethylmonoethylammonium sulfate, mono (long-chain alkyl) monomethyldi (polyethylene glycol) Ammonium chloride, di (tallow alkyl) dimethylammonium chloride, dimethyl monococonut amine acetate and the like are preferable.

When containing amphoteric surface active agent (d ^b) is, alanine compounds, imidazolinium betaines, amide betaines or amphoteric surfactants consisting of acetic acid betaine (d ^b) is preferred. Specific examples of the amphoteric surfactant (d ^b ) include dodecylbetaine, octadecylbetaine, dodecylcarboxymethylhydroxyethylimidazolinium betaine, dodecyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine and the like.

Specific examples of the anionic surfactant (d ^a ) include sodium lauryl sulfate, lauryl sulfate triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine. Sodium cocoyl sarcosine, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, Fluoroalkylcarboxylate (trade name Unidyne DS-101, 102 (manufactured by Daikin Industries, Ltd.)) .

  The water / oil repellent composition of the present invention may contain an organic solvent or an aqueous medium (C) as a medium in addition to the polymer (A) and the polymer (B). As the aqueous medium (C), the same medium as the emulsion polymerization medium described above can be used. When the polymer (A) and the polymer (B) are produced in an aqueous medium (C) such as emulsion polymerization, the medium used for the polymerization can be used as it is, but after polymerization, water or a water-soluble organic solvent (c) One or both may be added, and the water-soluble organic solvent (c) used in this case may be the same as, different from, or partially different from that used during the polymerization. Further, the polymer (A) and the polymer (B) or a solution thereof may be dispersed and emulsified in the aqueous medium (C) together with the surfactant (D) to form a water / oil repellent composition. In this case, the same surfactant (D) as in the emulsion polymerization described above can be used. Moreover, it is also possible to add surfactant (D) to the aqueous dispersion obtained by emulsion polymerization. The content of the aqueous medium (C) is preferably 40 to 98% by mass and more preferably 70 to 90% by mass with respect to the water / oil repellent composition.

A monomer having a short-chain R ^f group used in the present invention is generally more compatible with other monomers not containing fluorine than a monomer having a crystalline R ^F group, and thus is a water-soluble organic solvent in emulsion polymerization. Even if the amount of (c) is small, it is easy to obtain a homogeneous polymer, and since it does not contain any water-soluble organic solvent (c), it is also possible to obtain a water / oil repellent composition with less environmental impact due to volatile organic substances. It is.

  When the aqueous medium (C) is used, the polymer (A) and the polymer (B) are preferably present as dispersed in the medium as fine particles. Usually, the average particle diameter of the fine particles is 10 to 1000 nm, but 10 to 300 nm is preferable, and the particularly preferable particle diameter range is 10 to 200 nm. If the particle size is too small, a large amount of emulsifier or self-emulsifying monomer is required to obtain a stable dispersion, and the water and oil repellency performance is reduced or when dyed fabrics are processed. There is a risk of discoloration. On the other hand, when the particle diameter is too large, it is difficult for the dispersed particles to be stably present in the medium, and there is a possibility of sedimentation, which is not preferable. In the present invention, the average particle diameter can be measured with a dynamic light scattering device, an electron microscope, or the like.

  In the water / oil repellent composition of the present invention, the polymer (A) and the polymer (B) are present in the same particle, but are not present in the same particle, and form separate particles. It may be an intermediate one. In order to obtain a water / oil repellent composition in which the polymer (A) and the polymer (B) are not present in the same particle and form separate particles, for example, the polymer (A) and the polymer (B) In order to obtain a plurality of dispersions composed of different kinds of polymer particles by separately performing a polymerization reaction for each, a method of mixing and preparing each dispersion is preferably used. In addition, in order to obtain a water / oil repellent composition in which the polymer (A) and the polymer (B) are present in the same particle, the polymer (B) is polymerized into the emulsion dispersion of the polymer (A). A method in which a monomer is added all at once or divided into several stages, and then a polymerization initiator is added to carry out the polymerization, a so-called seed polymerization or other multistage polymerization, or a polymer (B) emulsified dispersion with a polymer ( This can be achieved by a method in which a monomer and an initiator for polymerizing A) are added to perform multi-stage polymerization such as seed polymerization. When the polymer (A) and the polymer (B) are present in the same particle, the phase structure is not limited, and may be a homogeneous structure, a so-called core-shell type layer separation structure, sea- A phase separation structure such as an island type phase separation structure or a spinodal type phase separation structure can be freely adopted.

The agent / oil repellent composition of the present invention may contain a thermosetting agent (F). Examples of the thermosetting agent (F) include a blocked isocyanate compound (f ¹ ), an amino resin compound (f ² ), a polymer (f ³ ) not containing a fluorine-containing monomer having a crosslinkable monomer as an essential polymerization unit, and a urethane resin compound. Etc. A blocked isocyanate compound (f ¹ ) and an amino resin compound (f ² ) are preferred.

Here, the blocked isocyanate compound (f ¹⁾ is a compound having no polymerizable unsaturated group, complete the isocyanate groups of the polyisocyanates described above (b ³⁾ in the above blocking agents (b ⁴⁾ A compound having a blocked structure is preferred. Examples of the monomer constituting the polymer (f ³ ) that does not contain a fluorine-containing monomer having a crosslinkable monomer as an essential polymerization unit include an acrylamide analog (b ¹ ) or a blocked isocyanate group-containing acrylate analog (b ² ). Particularly preferred are blocked forms of N-methylolacrylamide and 2-isocyanatoethyl methacrylate.

The amino resin compound (f ² ) is a compound obtained by addition condensation of an amino group-containing compound and a compound having a reactive group with an amino group, such as melamine, guanamine, or urea, alcohols, amines, formaldehyde. And the addition condensates of melamine, guanamine, urea and the like with formaldehyde, and compounds obtained by further addition condensation of alcohols and amines, or derivatives thereof. Specific examples of the amino resin compound (f ² ) include urea resins; alkylated urea resins such as butylated urea resins; melamine resins such as trimethylol melamine and hexamethylol melamine; methylated melamine resins and n-butylated melamine resins. Alkylated melamine resins such as methylated n-butylated melamine resins and i-butylated melamine resins; benzoguanamine resins; n-butylated benzoguanamine resins, i-butylated benzoguanamine resins, methylated n-butylated benzoguanamine resins, etc. Examples include alkylated benzoguanamine resins; butylated urea melamine resins; acetoguanamine resins.

In addition, the amino resin compound (f ² ) in the present invention is preferably one that is substantially soluble in water at room temperature. There are many commercially available amino resin compounds (f ² ) such as those manufactured by Sumitomo Chemical Co., Ltd. (for example, trade name Sumtex Resin), manufactured by Dainippon Ink Co., Ltd., and Mitsui Chemicals. It is available. As for the quantity of a thermosetting agent (F), 5-100 mass parts is preferable with respect to 100 mass parts of polymers (A) + polymer (B), and it is especially preferable to set it as 5-70 mass parts.

In the water / oil repellent composition of the present invention, the polymer (A), the polymer (B), and the above-described polymer thermosetting agent (as a blender, a bulking agent, or for exhibiting various physical properties in the article to be treated). Polymers (G) other than f ² and f ³ ) can be blended. The other polymer (G) may be a non-fluorine polymer. The other polymer (G) is a polymer containing no R ^f group, such as a water-soluble polymer or organopolysiloxane. Examples of the water-soluble polymer include polyacrylamide, polyvinyl alcohol and derivatives thereof.

  Examples of organopolysiloxanes include methyl hydrogen polysiloxanes typified by silicone-based water repellents, terminal OH group-blocked dimethyl polysiloxanes, vinyl group-containing polysiloxanes, and amino groups in side chains typified by silicone softeners, There are various modified silicone oils modified by introducing an epoxy group, a polyether group, a carboxyl group, a hydroxyl group, a trifluoroalkyl group, an alcohol ester group, an alkyl group and the like. The silicone dispersion is a solution in which a silicone resin or silicone rubber in an initial polymerization state is dissolved in a solvent, and is condensed to form a film having a three-dimensional network structure when heated. In this invention, not only what was mentioned above but various organopolysiloxane can be used. These organopolysiloxanes have many types of commercial products. Examples of commercially available products include SH200, PRX413, SH8011, SD8000 (product name of Toray Dow Corning Silicone), KP-801M, KPN-3504 (product name of Shin-Etsu Chemical Co., Ltd.), and the like. The amount of the polymer (G), for example, the amount of the organopolysiloxane is about 0.05 to about 10% by mass, preferably about 0.5 to 5% by mass with respect to the water / oil repellent composition of the present invention. Is preferred.

  The water / oil repellent composition in the present invention contains an antifoaming agent as necessary. In particular, when there is a concern that foaming will increase by containing a surfactant, it is necessary to contain an antifoaming agent. As the antifoaming agent, various water-based ones can be used, for example, lower alcohols such as methanol, ethanol, butanol, etc .; higher alcohols such as amyl alcohol, polypropylene glycol and derivatives thereof; oleic acid, tall oil, mineral oil Oils and fats such as soaps; surfactants such as sorbitan fatty acid esters, polyethylene glycol fatty acid esters and pluronic-type nonionic surfactants; and silicone surfactants such as siloxanes and silicone resins. These may be used alone or in combination. Used. Typical commercial products of antifoaming agents include B-series (Asahi Denka Kogyo Co., Ltd.) such as Adecanate B and Adecanate B1068; SN deformers such as Formaster DL, Nopco NXZ, SN deformers 113, 325, 308, and 368 Series: Dehydran 1293, Dehydran 1513 (manufactured by Sannopco); Furonon SB-110N, SB-210, 510, 551, Aqualen 800, 805, Aqualen 1488 (manufactured by Kyoeisha Chemical Co., Ltd.); Surfynol 104E (Air product) Acetylene-based antifoaming agent manufactured by & Chemical Co., Ltd.); KS-607A (manufactured by Shin-Etsu Chemical Co., Ltd.); FS Antifoam (manufactured by Dow Corning); BYK-020, 031, 073, W (manufactured by Big Chemie); Dehydran 981 (Henkel Hakusuisha); Epan 410, 7 0,720 [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.]; Tego Foamex series (manufactured by Tego Goldschmidt); form Rex -747, TY-10, EP Series (Nicca Chemical Co., Ltd.), and the like. The content of the antifoaming agent is preferably 0.01 to 10% by mass and particularly preferably 0.05 to 5% by mass with respect to the water / oil repellent composition (eg, aqueous resin emulsion).

  In addition, a compound which is considered to have an action of dissolving, swelling or softening the polymer and forming the polymer with a small amount of heat may be used, so-called film forming aid. As a film-forming aid, one or more compounds selected from generally used alcohols, glycol ethers, linear or cyclic silicones, esters, diesters, ketones and ethers are limited. Can be used. These compounds may contain a fluorine atom in the molecule. Examples of specific film-forming aids include methyl acetate, ethyl acetate, butyl acetate, dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, diethylene glycol monoethyl ether acetate, di-n-butyl adipate, butyl Examples thereof include carbitol acetate, octamethyltrisiloxane, decamethylcyclopentanesiloxane, dimethyl phthalate, and diethyl succinate. Usually, the amount of film-forming aid used is in the range of 0.1 to 70 parts by weight, particularly 5 to 60 parts by weight, per 100 parts by weight of the polymer. Further, by using these compounds together with the aqueous medium (C) at the time of emulsion polymerization, a homogeneous copolymer having a small composition distribution can be obtained.

  Furthermore, other additive components can be blended as necessary. For example, other water and oil repellents, stain blockers, softeners, catalysts that promote crosslinking, texture modifiers, penetrants, insect repellents, antibacterial agents, flame retardants, antistatic agents, polishes, antifungal agents, A water absorbing agent, a shrinking agent, a dye, a pigment, a dye stabilizer, an antioxidant, a deoxidizer, a pH adjuster, and the like can be appropriately added and used together.

  However, if the amount of the non-volatile component contained in the water / oil repellent composition relative to the total amount of the polymers (A) and (B) is too large, the sufficient performance as the water / oil repellent may be impaired. . Therefore, the total amount of the polymer (A) and the polymer (B) in the water / oil repellent composition in the present invention is 50% by mass or more, preferably 75% by mass or more based on the total solid content.

  The water / oil repellent composition of the present invention is diluted to an arbitrary concentration according to the purpose and application, and is applied to the article to be treated by any method according to the kind of article to be treated and the preparation form of the composition. Is done. For example, a method of adhering to the surface of the article to be treated and drying by dipping, coating, spraying, padding, roll coating, spin coating or a combination of these methods is employed. As a method for processing the article, a method of immersing the article in a water / oil repellent treatment liquid containing the polymer (A) and the polymer (B) is preferable, but the composition containing the polymer (B) and not containing the polymer (A). A method of immersing an article in a product and then immersing it in a water / oil repellent treatment liquid containing polymer (A) and not containing polymer (B), or water and oil repellent treatment containing polymer (A) and not containing polymer (B) A method of immersing the article in the liquid and then immersing it in a water / oil repellent treatment liquid containing the polymer (B) but not containing the polymer (A) is also preferred. When processing a textile product, it was immersed in the processing liquid prepared so that the total amount of a polymer (A) and a polymer (B) might be 0.01-10 mass%, Preferably it is 0.1-3 mass%. After that, a method of removing the excess treatment liquid with a roll or the like and drying it is effective. By setting the content to 0.01 to 10% by mass, reliable coating and bonding of the fibers are possible, performance is sufficiently imparted, and the texture of the fibers is good. If necessary, it may be applied together with an appropriate crosslinking agent and cured. In addition, it is possible to impart water and oil repellency to them by mixing with polypropylene, nylon or the like and molding and fiberizing them.

  The article to be treated with the water / oil repellent composition of the present invention is not particularly limited, and fiber products such as fibers, fiber woven fabrics, fiber knitted fabrics, and nonwoven fabrics, and ceramics such as glass, plaster, asbestos, bricks, cement, and concrete. Examples include products, leather products such as fur, wood, paper, pulp products, metals and oxides thereof, stone materials, resins, coated surfaces, and plaster. An article treated with the water / oil repellent composition of the present invention has both excellent water repellency and oil repellency, and is excellent in durability. Applications of these items include sportswear, coats, blousons, surgical clothes, work clothes, uniforms and other clothing items, dust masks, shoes, bags, umbrellas, carpets, curtains, wallpaper, tents, building materials, filtration materials, electronics Or an optical system component, an element, etc. are mentioned. In particular, when processed into a textile product, since the film is flexible, it is possible to obtain high-grade water- and oil-repellent functions with excellent washing resistance without impairing the texture, The water / oil repellent composition of the present invention is suitable for treating textile products. Examples of textile products include natural animal and vegetable fibers such as cotton, 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, Preferred examples include inorganic fibers such as glass fibers, carbon fibers and asbestos fibers, or blended fibers thereof, and any form such as fibers, yarns, fabrics, and nonwoven fabrics may be used.

Hereinafter, the present invention will be described more specifically with polymerization examples (1 to 7), examples (1 to 6) and comparative examples (1 to 10), but the present invention is not limited to these examples. Needless to say. In addition, various evaluation in an Example and a comparative example was implemented according to the method and reference | standard shown below. In the table, the symbols (a ¹ ), (a ² ), and (b) after the monomer names represent the category of the monomers (a ¹ ), (a ² ), and (b) described above. .

[Evaluation of water repellency]
The water repellency was shown by the water repellency (see Table 1 below) according to the spray method of JIS-L-1092.

[Evaluation of oil repellency]
The oil repellency is according to AATCC-TM118-1966. Drop the test solution shown in Table 2 below on the test cloth in two places, observe the penetration state after 30 seconds, and give the oil repellency given by the test solution that does not show immersion. The highest point was indicated as the oil repellency number.

Polymerization example 1
A 200 mL glass four-necked reactor equipped with a thermometer, a condenser tube, and a stirring blade was charged with 16.7 g of (CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ) and 100 ml of ethyl acetate, and purged with nitrogen. I did it. The temperature was raised to 60 ° C. in a nitrogen atmosphere, 1.63 g of t-butyl peroxypivalate (Nippon Yushi Co., Ltd., perbutyl PV) was added, and stirring was continued for 5 hours while maintaining the temperature of the reaction solution at 60 ° C. After cooling the reaction solution, it was poured into 300 mL of methanol, and the precipitate was filtered and dried in vacuo at 60 ° C. overnight to obtain 13.7 g of a polymer (polymer P1). T _g of the resulting polymer was 77 ° C..

Polymerization examples 2-7
In Polymerization Examples 2 to 7, polymerization was performed in the same manner as in Polymerization Example 1 with the monomer composition shown in Table 3 below, to obtain polymers P2 to P7, respectively.

The abbreviations in Table 3 represent the following meanings.
5FMA: CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (T _g : 77 ° C.)
HFIP-MA: (CF ₃ ) ₂ CHOCOC (CH ₃ ) = CH ₂ (T _g : 91 ° C.)
9FMA: F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (T _g : 37 ° C.)
6FOMA1: CF ₃ CF ₂ CF ₂ OCFCF ₃ CF ₂ OCFCF ₃ CH ₂ OCOC (CH ₃ ) ═CH ₂ (T _g : −34 ° C.)
StA: Stearyl acrylate

Examples 1-6 and Comparative Examples 1-10
Polymers P1 to P7 obtained by the above method were mixed at a ratio (mass%) shown in Table 4 to prepare a treatment liquid as a 1 mass% solution of the fluorinated solvent HCFC-225. Nylon taffeta cloth (Kanebo Naturine, nylon 6, amber dyed cloth) is immersed in the treatment solution, treated with a centrifuge at 500 rpm for 18 seconds, air dried overnight at room temperature, and then heat treated at 150 ° C. for 5 minutes. The water and oil repellency of the treated fabric was evaluated. The results are shown in Table 5. In addition, + mark in a table | surface shows that it is slightly better than the performance shown by each.

Claims (11)

(A) a fluorine-containing monomer (a ¹ ) having a glass transition temperature (T _g ) of a homopolymer of 50 ° C. or more, and a fluorine-containing monomer (a ¹ ) that is present if the T _{g of the} homopolymer is less than 50 ° C. (a a polymer having a ²⁾ as polymerized units, is at least 50% by weight, based on the total of polymer, and (B) homopolymer _{T g} of quantities and ^{(a 1) (a 2)} of ^{(a 1)} a polymer having a fluorine-containing monomer optionally present at 50 ° C. or higher (a ^1), and homopolymer T _g of fluorine-containing monomer is less than 50 ° C. the (a ²⁾ as polymerized units, ( a quantity (a ¹⁾ and (fluorine-containing water repellent oil repellent composition comprising a polymer exceeding 50% by weight, based on the sum of a ²⁾ of a ^2),
The fluorine-containing monomer (a ¹ ) and the fluorine-containing monomer (a ² ) are represented by the formula (3 ′):
R ^fa —YQ—COCR ^a ═CH ₂ (3 ′)
[In the formula, the R ^fa group does not exceed 20% of the total number of fluorine atoms contained in a perfluoroalkyl group having 6 or less carbon atoms, a perfluoro (poly) ether group having 30 or less carbon atoms, or a structure thereof. Represents a structure in which fluorine atoms are replaced by hydrogen atoms in the range,
R ^a represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms,
Q represents -O-,
Y _{is, - (CH 2) p -} (CH 2) q -
(However, p and q independently represent an integer of 0 or more, and p + q is an integer of 0 to 22.)
A representative. ]
A fluorine-containing water and oil repellent composition represented by:   The polymer (A) further contains a fluorine-free monomer (b) copolymerizable with the fluorine-containing monomer as a polymerization unit, and the mass fraction of the monomer (b) in the polymer (A) is 40 masses. The fluorine-containing water / oil repellent composition according to claim 1, which is less than%.   The polymer (B) further contains, as a polymerized unit, a fluorine-free monomer (b) copolymerizable with the fluorine-containing monomer, and the mass fraction of the monomer (b) in the polymer (B) is 70 masses. The fluorine-containing water / oil repellent composition according to claim 1, which is less than%. The fluorine-containing water / oil repellent composition according to claim 1, wherein the mass ratio of (a ¹ ) :( a ² ) in the polymer (A) is 100: 0. The fluorine-containing water / oil repellent composition according to claim 1, wherein the mass ratio of (a ¹ ) :( a ² ) in the polymer (B) is 0: 100. The fluorine-containing monomers (a ¹ ) and (a ² ) are acrylates or methacrylates containing a perfluoroalkyl group having 6 or less carbon atoms as a side chain, or acrylates substituted at the α-position with a halogen atom. The fluorine-containing water repellent composition according to any one of 1 to 5 . The mass ratio of the polymer (A) to the polymer (B) is 5:95 to 95: 5, and the total ratio of the polymer (A) and the polymer (B) in the total solid content is 50% by mass or more. The fluorine-containing water and oil repellent composition according to any one of to 6 . _{T g} of the monomer ^{(a 1)} is at temperatures above 55 ℃, monomer ^{(a 2)} a fluorine-containing water repellent oil repellent composition according to any one of claims. 1 to 7 _{T g} is 45 ° C. below. The monomer (a ¹ ) is
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCCl═CH ₂ (T _g : 65 ° C.),
F (CF ₂ ) ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (T _g : 77 ° C.),
(CF ₃ ) ₂ CHOCOC (CH ₃ ) ═CH ₂ (T _g : 91 ° C.) and C (CH ₃ ) (CF ₃ ) ₂ CH ₂ OCOCH═CH ₂ (T _g : 133 ° C.)
A monomer selected from the group consisting of
The monomer (a ² ) is
F (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCCl═CH ₂ (T _m : 45 ° C.),
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH═CH ₂ (T _m : 42 ° C.),
_{F (CF 2) 6 (CH} 2) 2 OCOCH = CH 2 (T g: -30 ℃),
(CF ₃ ) ₂ CHOCOCH═CH ₂ (T _g : 15 ° C.),
F (CF ₂ ) ₄ (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂ (T _g : 37 ° C.), and CF ₃ CF ₂ CF ₂ OCCFCF ₃ CF ₂ OCCFCF ₃ CH ₂ OCOC (CH ₃ ) ═CH _{2 (T} g: -34 ℃)
The fluorine-containing water and oil repellent composition according to any one of claims 1 to 8 , which is a monomer selected from the group consisting of: Method of treating a substrate with a fluorine-containing water repellent oil repellent composition according to any one of claims 1-9. Obtained by the method of claim 1 0, the treated substrate.