WO2006038493A1 - Fluorine-containing water- and oil-repellent composition - Google Patents

Abstract

A fluorine-containing water- and oil-repellent composition which comprises (A) a polymer comprising units derived from a fluorine-containing monomer (a1) which gives a homopolymer having a glass transition temperature (Tg) of 50˚C or above and optional units derived from a fluorine-containing monomer (a2) which gives a homopolymer having Tg lower than 50˚C with the proviso that the units derived from the monomer (a1) account for at least 50% by mass of the total amount of the units derived from the monomers (a1) and (a2) and (B) a polymer comprising optional units derived from a fluorine-containing monomer (a1) which gives a homopolymer having Tg of 50˚C or above and units derived from a fluorine-containing monomer (a2) which gives a homopolymer having Tg lower than 50˚C with the proviso that the units derived from the monomer (a2) account for more than 50% by mass of the total amount of the units derived from the monomers (a1) and (a2).

Description

 Specification

 Fluorine-containing water and oil repellent composition

 Technical field

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

 Background art

Conventionally, an addition-polymerizable monomer containing a polyfluoroalkyl group (hereinafter, polyfluoroalkyl group is referred to as R ^f group) (hereinafter, the addition-polymerizable monomer is simply referred to as monomer). ) As a polymerization unit (hereinafter, the term polymer is used in the meaning of homopolymer and copolymer) is treated as an organic solvent solution or an aqueous dispersion on textiles, paper, etc. A technique for imparting water repellency and oil repellency to these surfaces 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 water repellent. It is widely used as an oil agent composition.

CH = CR ¹ COOCH CH (NR ² SO) (CF) F (1)

 2 2 2 2 m 2 n

(Wherein, m is 0 or 1, n is an integer of 6 to about 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.)

[0004] 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 the water / oil repellent, n in the formula (1), that is, the number of carbon atoms of the perfluoroalkyl group is substantially 8 or more. Such a carbon number of 8 or more Pafuruo port alkyl group (hereinafter, carbon atoms referred to 8 or more per full O b alkyl long chain R ^F group.) The polymer having as a side chain, long chain R It is known that there is a microcrystalline melting point derived from the ^F group. The strong crystallinity of the long-chain group effectively aligns the surface of the long-chain group. A polymer having a polymer having a structure of formula (1) as a polymer unit is a major factor that has excellent water and oil repellency. It is said that there is. [0005] However, monomers which contain long chain R ^F group as a side chain (hereinafter, referred to monomer containing a long chain R ^F group as a side chain crystalline R ^F group-containing monomer.) Is generally in the other Since the compatibility with the monomer is extremely poor, many organic solvents are required to obtain a homogeneous copolymer. In addition, it is known that when a textile product or the like is treated with a polymer containing them, the flexible texture of the object to be treated is likely to be impaired due to the strong side chain crystallinity of the long chain group.

[0006] In the conventional water and oil repellent, washing, dry cleaning, in order to impart a high durability against friction or the like, the melting point derived from the crystallites of the R ^F group Among crystalline R ^F group-containing monomer High (usually 70 ° C or higher) crystalline R ^F group-containing monomer is indispensable. Highly water- and oil-repellent high-temperature processing above the melting point of microcrystals for uniform coating processing. This is not preferable because it may cause problems such as a decrease in dyeing fastness, hardening of the texture, and discoloration in the processing of textile products.

 [0007] Further, in recent years, EPA (US Environmental Protection Agency) contains 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. It has announced that it will strengthen scientific research on PFOA, expressing concerns about P accumulation, etc., where the compound is a compound that can be decomposed in the environment and in the living body (EPA report “PRELIMINARY RISK ASSESSMENT” OF THE DEVELOPMENTAL T OXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID A ND ITS SALTS (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)

[0008] In recent years, from the consideration of the working environment and the global environment, to the ozone layer such as a water-based and oil-repellent medium mainly composed of water, an alcohol-based solvent, a petroleum-based solvent called a weak solvent, or a hydrofluorocarbon. The use of fluorinated solvents that are less affected by this is required. However, in the case of water and oil repellents mainly composed of polymers composed of conventional crystalline group-containing monomers, from the viewpoint of solubility, dispersibility, etc., so-called strong compounds such as aromatics, ketones, esters, etc. There has been a problem that it is necessary to use a fluorine-based solvent that has a large influence on the ozone layer, such as a solvent, a chlorine-based solvent, and black fluorocarbon.

[0009] For these reasons, the following techniques have been proposed as water and oil repellents that do not contain long chain ^RF groups. For example, polyatarylate poly having perfluoropolyether chains Ma (W02_103103, W003_99904). Polymers consisting of monomers containing R ^f groups with 6 or less carbon atoms (hereinafter R ^f groups with 6 or less carbon atoms are referred to as “short-chain R ^f groups”) include fluorine with side-chain crystallinity. Copolymer with a monomer (WO02-83809), copolymer with a monomer without an ^Rf group having a crosslinkable functional group (WO04-35708), a sulfone containing an ^Rf group having a carbon number of less than There are polymers of amide acrylate (Special Table 2003-513123), and copolymers with vinylidene chloride or butyl chloride (WO03-62521). However, no water- and oil-repellent agents that give satisfactory practical performance have been found.

 [0010] 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 economic efficiency, a technique using a mixture of a plurality of polymers and a technique using composite particles of a plurality of polymers are known. It is. For example, when used simultaneously with other fluorine-free polymers, the durability is improved and the crosslinkable polymer containing a blocked isocyanate group is used as a blender or polymer extender (Japanese Patent Laid-Open Seki 54-128992, JP 10-501306), and polyamine polymers mixed with cationic polymers (JP 6-49319, JP 2002-220539).

[0011] In addition, a combination of a fluorine-containing polymer and a fluorine-free polymer (Japanese Patent Publication No. 49 428 78, Japanese Patent Laid-Open No. 61-264081, US Pat. No. 3,378609, US Pat. No. 4043964), fluorine-containing monomer amount or fluorine content Of different polymers (JP 49-24890, JP 5-279541, JP 2000-160148, JP 2002-201463, US Pat. No. 33 47812), affinity with substrates such as chlorine atoms and hydroxyl groups Examples thereof include those that limit the amount of monomer having a structure that is considered to be involved in binding properties (Japanese Patent Laid-Open No. 2000-282015, Japanese Patent Laid-Open No. 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 treated by segregating on the surface, and the object to be treated 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 such a combination of polymers can improve the durability without impairing the water and oil repellency is that the difference between the fluorine content, etc. Some polymer composition distribution occurs, and it is considered that there is a large amount on the outermost surface (high amount of fluorine), and the polymer exhibits high water and oil repellency and higher affinity with the substrate (fluorine It is reasonable to think that the durability has been realized by the presence of a smaller amount of polymer at the interface with the substrate. The technology in this field, represented by these known examples, basically has the ^Rf group, in particular, the functions required other than that which does not impair the water and oil repellency inherent in the polymer having a crystalline group. and performs the improvement of the homopolymerization crystalline R ^F group-containing monomer water repellent polymer comprising only ^the R ^f group of short-chain which is a water and oil repellency is inferior to the polymer containing the body No effect to improve oil repellency has been reported.

 [0012] Further, for the purpose of improving performance as a water and oil repellent such as imparting high durability and low-temperature film-forming properties, a homopolymer has a non-fluorine-based mode having a specific glass transition temperature (T).

 g

 A technique for preparing a copolymer containing a noma is known. For example, if the homopolymer τ is

 g

 Copolymers containing non-fluorinated monomers as polymerized units at a temperature below (JP 60152585, JP 9 328677), such that the T of the homopolymer is above a specific temperature

 g

 Copolymers containing non-fluorinated monomers as polymerized units (Japanese Patent Laid-Open Nos. 62-577 and 63-2 7585), as well as non-fluorinated monomers and monomers having a T above a specific temperature.

 g

 Both non-fluorinated monomers whose homopolymer T is below a specific temperature are referred to as polymerized units.

 g

 Copolymers contained therein (Japanese Patent Laid-Open No. 53-50078) are known. Furthermore, a water- and oil-repellent agent containing composite particles containing a monomer whose homopolymer T is not lower than a specific temperature as a polymerization unit may be used.

 It is known that high water and oil repellency can be imparted to a substrate even under mild heat treatment conditions (JP-A-7-278442). However, all the high-T monomers disclosed in the text of this specification and the examples do not contain fluorine, and the effect of g g is not shown by focusing on T of the fluorine-containing monomer. In addition, it is said that the effect appears only in composite particles. These can be said to be focused on the selection of non-fluorinated monomers that basically constitute polymers.

[0013] Further, regarding the relationship between T of the fluorinated monomer and the performance as a water and oil repellent for fibers.

 g

 According to the research of Roitman et al., The fluorine-containing (meth) atrelay whose T force is 25 ° C or more

 g

 It has been pointed out that the oil repellency of the homopolymer of Toh is significantly inferior to that of T force less than 5 ° C.

 g

Reru (JN Roitman et al., Textile Res. J., 43, 500 (1973)). Therefore, polymers containing fluorine-containing monomers whose homopolymer T is 25 ° C or higher have been water-repellent so far. It has never been used practically as an oil repellent.

 Disclosure of the invention

 Problems to be solved by the invention

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

 Means for solving the problem

[0015] The present invention provides:

(A) a fluorine-containing monomer (a ¹ ) having a glass transition temperature (T) of a homopolymer of 50 ° C or higher, and

 g

Polymerization of existing fluorine-containing monomer (a ² ) if necessary and T of homopolymer is less than 50 ° C

 g

A polymer having as a unit, as well as polymer, is (a ¹⁾ the amount of (a ¹⁾ and (a ²⁾ a total of 50 mass _^0/0 or more with respect to the

(B) a fluorine-containing monomer (a ¹ ) present if necessary because the T of the homopolymer is 50 ° C or higher, and

 g

And a polymer having a fluorinated monomer (a ² ) having a T of less than 50 ° C as a polymerized unit.

 g

A Lima, quantity (a ¹⁾ and (a ²⁾ Total fluorinated water repellent oil repellent composition comprising a polymer in excess of 50 mass _^0/0 for in (a ²⁾

 I will provide a.

 [0016] The present inventor has studied in detail the mechanism of the water and oil repellency and its strengthening method. As a result, the homopolymer has a T (glass transition temperature) of 50 ° C or higher.

 g

 Ma (hereinafter, the homopolymer's T force is 0. Fluorine-containing monomer having a C or higher is called “high Tg-containing F monomer”)

 g

 . ) 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, 100% by mass or less) Fluorine-containing monomer whose homopolymer T force is less than 0 ° C (hereinafter the homopolymer

 g

 A fluorine-containing monomer having a T of less than 50 ° C is referred to as “low T-containing F monomer”. ) The main component (g g

For example, a copolymer with more than 50% by mass of the copolymer, 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) may be used in combination. Thus, it has been found that the base material can be provided with performance that exceeds water repellency and the balance between water repellency and oil repellency, when used alone, and excellent repellent properties can be obtained without using a crystalline group-containing monomer. The above-mentioned problem of imparting water / oil repellency to an object to be treated has been solved, and the invention has been completed. The reason why water / oil repellency is improved by the above polymer blend is not necessarily clear, but the most reasonable explanation is as follows. It is.

[0017] For example, when a water / oil repellent agent is treated on a cloth, the surface of the fibers constituting the cloth is (a) a region where the fibers are in contact with each other, and (b) a contact between the fibers. There are two types of areas.

 [0018] Since the contact angle of water on the surface treated with the water / oil repellent is generally large, only a part of the surface of the cloth is in contact with water in a state where the water repellency is sufficiently exhibited in a water repellency test or the like. Therefore, it is thought that the area (b) is mainly in contact with water. In order to express high water repellency, it is necessary to suppress the environmental responsiveness when the hydrophilic part in the polymer molecule moves and orients to the surface by contact with water, which is a measure of the micro-brown mobility of polymer chains. It is desirable that a certain T is high. Also important here is the water repellency in the polymer chain.

 g

 This is to suppress the motility of the domain in which the fluorine-containing monomer is continuous, that is, the fluorine-containing monomer does not contain fluorine.

 g g

 Rather than increasing the T of the entire polymer by copolymerization with the monomer

 It is effective to use a polymer containing g g elementary monomer as a main constituent.

 On the other hand, the oil contact angle on the surface treated with the water / oil repellent agent 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 repellency test. Therefore, the presence or absence of minute defects in the water / oil repellent polymer film formed on the fiber greatly affects its oil repellency. In particular, in the area (a) where the fibers are in contact with each other, the mechanical load is easily exerted, so that defects in the polymer coating are likely to occur. Therefore, it is important to reduce the defects of the polymer film in this region in order to improve the oil repellency. In general, amorphous polymers are hard and brittle at temperatures below T, so fabrics are treated with high T polymers.

 g g

If this is done, defects in the polymer film are likely to occur in areas where mechanical loads are easily applied. It is considered that the oil repellency cannot be exhibited. Therefore, in order to improve the oil repellency, the polymer existing in the (a) region has a very high T and is somewhat softer than desirable.

 g

 Desirable, soft state.

[0020] This is because, in comparisons between the fluorine-containing acrylate homopolymers that do not have side chain crystallinity and the fluorine content changes so much, those having a high T have a high water repellency but an oil repellency.

 g

 On the other hand, τ is low, and the thing that oil has high oil repellency but tends to have low water repellency

 g

 Explains the fruit well. Polymers mainly composed of low T-containing F monomers are high T-containing F

 gg Because it is considered to have higher fluidity than a polymer mainly composed of a monomer, it moves by capillary action in the process of treating a cloth with a water / oil repellent, especially during heat treatment, and (a) In contrast, high T-containing F monomers are mainly used.

 g

 Polymers that are essential constituents have low fluidity, so it is considered that most of them remain in the region (b). That is, a polymer mainly composed of a high T-containing F monomer and a low T-containing F

 g g When a polymer is mixed with a monomer as the main constituent and the fabric is treated, low T is present in the (a) region of the fiber surface where the oil repellency is more likely to be affected by appropriate heat treatment.

 g Polymers containing F-containing monomers as main constituents seem to have a more important impact on water repellency. (b) Many polymers with high T-containing F monomers as main constituents will be present in the region.

 g

 available. This is because blending the polymers has the effect of exceeding the usual expectation that it is possible to significantly improve the performance compared to the case where each is used alone or copolymerized. It is believed that there is.

[0021] As described above, the conventional technology using a combination of different polymers in the water / oil repellent is based on the concept of role sharing at the interface between the outermost surface and the substrate in the water / oil repellent polymer film. While many cases can be explained, this is difficult to explain in the present invention, and can only be understood by assuming a completely new principle as described above.

[0022] T in the homopolymer of the F-containing monomer constituting the polymer is water- and oil-repellent in the polymer chain.

 g

This is an appropriate measure of molecular motion in a continuous domain of F-containing monomers that are thought to contribute greatly to the sex. However, because the mobility of the polymer molecules at the interface is different from the Balta state, the micro-Brownian motion of the domain with the continuous F-containing monomers present on the outermost surface. In order for the homopolymer to be frozen at room temperature, the T of the homopolymer must be above room temperature.

 g

 The temperature of 50 ° C, which separates the high Tg monomer from the low Tg monomer, is considered reasonable in that respect.

 [0023] The expression model of water and oil repellency based on the above considerations rationally explains the improvement of water and oil repellency by the polymer blend in the present invention, but is only for explaining the phenomenon at the present time. It is only a simplified model and may be modified or changed in the future. However, it goes without saying that this does not affect the present invention.

 The invention's effect

[0024] The water / oil repellent composition according to the present invention is conventionally required to obtain sufficient water / oil repellent performance, and does not have a long-chain ^RF group. There is no concern about a decrease in texture due to chain crystallinity, 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 textile products.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0025] 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 thermosetting agent (F), other poly 7 (G) (for example, non-fluorine polymer), an additive and the like.

[0026] 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 It may be 10-90% by weight, especially 20-80% by weight. In the following, “parts” or “%” means “parts by mass” or “mass%” unless otherwise specified. The polymer (A) and the polymer (B) need not be a single polymer, but 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, a polymer containing a fluorine atom in the molecule, and a monomer (b) as necessary. The proportion of the monomer (b) is less than 40 mass _^0/0, such as less than 20 wt%. The proportion of monomer (b) in polymer (A) may be 0% by mass. The lower limit of the proportion of the polymer monomers in (A) (b) is 0.1 mass _^0/0, may 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. The proportion of the monomer (b) is 70%. Less than, for example, less than 50% by weight, especially less than 30% by weight. The proportion of monomer (b) in 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.

The monomer (a) contained in the polymer (A) has a high T-containing F monomer (a ¹ ) and, if necessary, a low T gg-containing F monomer (a ² ) force. The proportion of monomer (a ² ) in the monomer (a) constituting the polymer (A) is less than 50% by mass, for example less than 35% by mass, in particular less than 20% by mass. The proportion of the polymer (A) monomer to total monomers constituting (a) the (a ²⁾ is 0 mass% or more, for example 5 wt% or more, it may be in particular 10 mass _^0/0 above. The monomer (a) contained in the polymer (B) comprises a low T-containing F g monomer (a ² ) and, if necessary, a high T-containing F monomer (a ¹ ). Construct polymer (B)

 g

The proportion of monomer (a ¹ ) in monomer (a) is less than 50% by weight, for example less than 35% by weight, in particular less than 20% by weight. 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 in the polymer (A) or polymer (B) are each composed of two or more types of monomer forces even if they are a single monomer. Also good. The monomer (a ¹ ), monomer (a ² ), and monomer (b) used for the polymer (B) may be the same as, or partially the same as, those used for the polymer (A). It doesn't matter.

[0028] When the polymer (A) and the polymer (B) are copolymers, they are not limited to random copolymers, and may be blocks, graft copolymers, and the like. In this case, the monomer composition is such that the average value of the polymer satisfies the above conditions.

 The homopolymer T is the DSC g described in differential calorimetry tiIS _K_ 7121 _ 1987.

 Measured by the measurement method). The molecular weight of the homopolymer here is about 10,000 or more. This is because if the molecular weight of the homopolymer is 10,000 or more, the T of the homopolymer hardly depends on the molecular weight.

 g

[0029] As the monomer (a ¹ ) and monomer (a ² ), the T-force of the homopolymer from the side chain amorphous fluorine-containing monomer (a ^a ) or the T-force of the homopolymer is 0 ° C or higher. Less than 0 ° C

 g g

One or more monomers can be selected and used Side chain amorphous fluorine-containing monomer (a ^a ) is a direct or bonded bond of monovalent or divalent polymerizable unsaturated group and one or more amorphous R ^f groups (R ^fa groups). The compound is indirectly bonded through a group, and is preferably indirectly bonded. As the polymerizable unsaturated group, an alkylene group, particularly an ethylene group is preferable.

[0030] The amorphous R ^f group (R ^fa group) as used herein is generally a perfluoroalkyl group having 6 or less carbon atoms, or 30 or less carbon atoms, such as 20 or less carbon atoms, particularly 10 carbon atoms. The following perfluoro (poly) ether groups or 20 of the total number of fluorine atoms contained in these structures. / A structure in which fluorine atoms are replaced with hydrogen atoms within a range not exceeding ₀ . 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). FR ^fPFPE- [CF (CF)]-(CF)-(2)

 3 e 2 f

[In the formula, e represents an integer of 0 to 1, and f represents an integer of 1 to 2. R ^fPFPE represents the perfluoropolyether chain structure, [CF (CF) CF〇] [CF CFCF〇] [CF CF O] [CF O]. However

 3 2 a 2 2 2 b 2 2 c 2 d

 A, b, c, and d each represent an integer of 0-6. Moreover, a + b + c + d = 1-6, and the appearance order of each repeating unit is arbitrary. ].

A preferred side chain amorphous fluorine-containing monomer (a ^a ) can be represented by the following general formula (3).

(R ^fa -Y-) X (3)

[Wherein n is 1 or 2, X is a polymerizable unsaturated group, and n is 1, — CR ^a = CH,

 2

-Q-COCR ^a = CH, -Q- (CH)-φ— CR ^a = CH, -Q-CR ^a = CH or

 2 2 m 2 2

— C〇— Q— If CR ^a = CH and n is 2, then — Q— C〇R ^a = CR ^a CO— Q— or

 2

 -Q-COC (CH 2 CO— Q—) = CH (where m is an integer from 0 to 3. Q is —〇—

 twenty two

, _S— or _NR ^b _. (Ί represents a substituted or unsubstituted phenylene group. Is a hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 6 carbon atoms, halogen-substituted alkyl group having carbon atoms:! To 6 or phenyl group. or represents a base Njinore group R ^b is a hydrogen atom, the number of carbon atoms:.! represents an alkyl group or phenylene Le group 1-6).. R ^fa is the above-mentioned amorphous R ^f group, and Y is a divalent organic group or a single bond. ]

[0032] A preferred structure of Y which is a divalent organic group can be represented by the following formula (4). -(CH) T (CH) (CHR ^a )-(4)

 2 p 2 q r

[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 NR ^b -,-SO one, one NHCONH-, -CH (OH)-

twenty two

, _CH (〇COR ^a ) ―, _〇C〇0_, _CO〇_, _OCO_, _〇_, _S-, _C HR ^a- , one CHC1--, one CHBr-, one CHI-, cyclohexenylene group, Represents a phenylene group, a biphenylene group, or —CH [(CH 3) R ^fa ] —. However, s is an integer of 0-2. ]

 2 s

[0033] In general, among side chain amorphous fluorine-containing monomers (a ^a ), ^a compound in which the side chain mobility is limited due to short side chains or branching, particularly its metatalylate and α Rogen-substituted attalylates have a homopolymer wrinkle of 50 ° C or higher. In addition, side chain amorphous g

Among the functional fluorine-containing monomers (a ^a ), compounds containing a perfluoro (poly) ether structure having a large molecular mobility as a side chain, in particular, attalylates thereof, have a T force of homopolymer less than S50 ° C.

 If the polymer has a melting point (T), the glass transition temperature T is lower than T.

 It can be said that the soot of homopolymers with T below 50 ° C is also below 50 ° C. Furthermore, room temperature mg

 For polymers with obvious fluidity, T can be considered to be 50 ° C or less even when no clear transition point is found by the above DSC measurement method.

 g

[0034] T force 5 of monomer (a ¹ ). C or more, for example 60 to: 160. Be C. T of the monomer (a ² ) is gg

45 ° C or less, for example, a monomer (a ² ) homopolymer may be in a molten state at room temperature. The T of the monomer (a ² ) is, for example, _100. C ~ +45. C, especially _80. C ~ + 40. G in C

 It may be.

[0035] As a specific example of the monomer (a ¹ ),

 F (CF) (CH) OCOCCl = CH (T: 65. C),

 2 4 2 2 2 g

 F (CF) CH OCOC (CH) = CH (T: 77

 2 2 2 3 2 g. C),

 (CF) CHOCOC (CH) = CH (T: 91

 3 2 3 2 g. C) and

 C (CH) (CF) CH OCOCH = CH (T: 133 ° C) and the like.

 3 3 2 2 2 g

As a specific example of a monomer (a ² ),

F (CF) (CH) OCOCCl = CH (T: 45 ° C), F (CF) (CH) OCOCH = CH (T: 42 ° C),

 2 4 2 2 2 m

 F (CF) (CH) OCOCH = CH (T: _30.C),

 2 6 2 2 2 g

 (CF) CHOCOCH = CH (T: 15 ° C),

 3 2 2 g

 F (CF) (CH) OCOC (CH) = CH (T: 37 ° C),

 2 4 2 2 3 2 g

 CF CF CF OCFCF CF OCFCF CH OCOC (CH) = CH (T:-34 ° C)

3 2 2 3 2 3 2 3 2 g

 Can be mentioned.

 [0036] The polymer (A) and the polymer (B) may be a copolymer containing a monomer containing a fluorine atom other than the monomer (a) or a copolymerizable monomer (b) singly or in combination. A polymer can also be used.

[0037] Examples of the copolymerizable monomer (b) include the following (hereinafter, acrylate, methacrylate and α-halogen (for example, black mouth) substituted acrylate are generically named. This is also referred to as attalylate analog, and the same applies to acrylamide analog, acrylic acid analog, etc.) That is, an acrylate analog; an acrylamide analog (b ¹ ); an acrylonitrile analog; a 2-alkyl ether (halogenated alkyl) vinyl ether; an ethylene, propylene, isoprene, butene, dodecylethylene, heter Olefins and gens such as xene and butadiene; halogen-substituted ethylenes such as vinyl chloride, vinyl bromide, vinylidene chloride and black-opened plane; 2-chloro-1,3-butane, 2,3-dichloro-opened 1,3 _Halogen-substituted butadienes such as butadiene; styrene and monomethylstyrene, styrenes such as p-methylstyrene; acetic acid bull, propionic acid bull, strong prillic acid bull, lauric acid bull, octanoic acid bull, dodecanoic acid bull, Bull esters of fatty acids such as bull stearate Aliphatic arylenoesters such as heptanoic acid aryl, caplinoleic acid aryl, strong promonic acid aryl, octanoic acid aryl, hexanoic acid aryl; butyl alkyl ketones such as butyl methyl ketone and butyl ethyl ketone; N-alkylmaleimides such as N_methylmaleimide; (di) alkylesters such as maleic acid, fumaric acid, crotonic acid, citraconic acid, and mesaconic acid.

[0038] Further, specific examples of the attalylate analog include an acrylate arylate having a benzene ring such as phenyl acrylate, benzyl acrylate, and the like. Compounds in which a methyl group, a methoxy group, a chlorine atom, etc. are bonded to the zen ring; Cyclohexenorea tallylate analogues, Cyclododecyl attalate analogues, Dicyclopentyl acrylate derivatives such as dicyclopentyl acrylate analogues; Methyl acrylate derivatives , Ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 3,3-dimethyl_2-butyl acrylate C1-C12 saturated alkyl such as analog, hexyl acrylate, octyl acrylate, 2_ethyl hexyl acrylate, decyl acrylate, lauryl acrylate Alkyl acrylate derivatives having a group; Silatalylate analog, cetyl (meth) acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, icosyl acrylate , Acrylate derivatives having a saturated alkyl group having 13 to 25 carbon atoms such as docosyl acrylate, tetracosyl acrylate, analogs of diethylene glycol monoacrylate monomethyl ether, polyethylene glycol monoacrylate monomethyl ether, Polypropylene glycol monoacrylate monomethyl ether analogues, polyethylene glycol Polypropylene glycol monoacrylate monomethyl ether analogues, polyethylene glycol monoacrylate derivatives (2-ethylhexyloxy) ) Atarylate analogs having an ether structure such as ether; isobornyl acrylate, analogs having an alicyclic structure such as an adamantyl acrylate analog; acrylates having a polydimethylsiloxane group Preference is given to analogs; black octyl acrylate; and acrylate derivatives having a urethane bond.

Specific examples of acrylamide analogs (b ¹ ) include acrylamide analogs, N_methyl atrylamide analogs, N-stearyl acrylamide, N-cetyl acrylamide, N, N-dimethyl acrylamide analogs, N, N-J Tylacrylamide analog, N, N-diisopropylacrylamide analog, N-methoxymethylacrylamide analog, N-ethoxymethylacrylamide analog, N-butoxymethylacrylamide analog, N-methylolacrylamide analog, N-butoxymethylol Acrylamide analogs, N-butyrolol athlamide analogs, diacetone acrylamide analogs, methylol-diacetone acrylamide Preferred examples thereof include:

 The monomer (b) may be a monomer having a reactive group other than the polymerizable unsaturated bond, including the above acrylamide analog. Examples of such reactive groups include an epoxy group, a hydroxyxenore group, Carboxyl group, acid anhydride group, amide group, amino group, alkoxysilyl group

, N-methylol group, N-alkyloxy group, isocyanate group, allyloyl group, blocked isocyanate, imino group, cyano group, group and the like. By copolymerizing these reactive group-containing monomers, adhesion to substrates such as fibers is strengthened, and the effects of improving durability, washing resistance, dry cleaning resistance, etc. are seen, and generally There is also a secondary effect of improving the polymerization stability during emulsion polymerization.

Monomers having a reactive group other than the polymerizable unsaturated bond include blocked isocyanate group-containing acrylate (b ² ); 3-chloro-2-hydroxypropyl acrylate, 2-hydroxyethyl Atalylate analogs, 2-hydroxypropyl atallylate analogs, 4-hydroxybutyl atarylate analogs, glycerin monotalylate analogs, trimethylolpropane monoatarylate analogs, glycerin monoatarylate analogs, 2-hydride Atoxylates with hydroxyl groups such as xyloxy-3-phenoxypropyl attalylate analogues; Ataliates with epoxy groups such as glycidyl acrylate, aziridinyl acrylate derivatives, aziridinyl ethyl acrylate derivatives Rate analogs; N, N, N-stearyldimethylammo Nittalylate analogues, N, N, N-cetyldimethylammonium attalylate analogues, attalylate analogues having a quaternary ammonium structure such as hydroxypropyltrimethylammonium chloride methacrylate; diethylene glycol monoacrylate N-stearyl aminoethyl acrylate analogs with ether structures such as analogs, polyethylene glycol monoacrylate derivatives, polypropylene glycol monoacrylate derivatives, polyethylene glycol polypropylene glycol monoacrylate analogs; , N-cetylaminoethyl acrylate, N, N —dimethylaminoethyl acrylate, N, N-jetylaminoethyl acrylate, N, N-stearylmethylaminoethyl Tallate analogs, substituted aminoalkyl acrylate derivatives such as N, N-cetylmethylaminoethyl acrylate, analogs having a straight-chain unsaturated alkyl group having 3 or more carbon atoms such as aryl acrylate Rate analogs; 2-Atariloy oral chechetylhexahydrophthalic acid, 2-Atarileurooxyethyl phthalic acid, 2-Atarileuroxetyl _ 2-hydroxyethyl phthalic acid, β-Acryloyloxetyl hydrogen Succinates, acrylate derivatives with carboxylic acid groups such as β-methacryloyloxychetyl hydrodiphthalate; _Ί — _acrylate derivatives with reactive silyl groups such as trimethysilylpropyl acrylate derivatives Ethylene glycol ditalylate analogs, diethylene glycol ditalylate analogs, neopentyl glycol ditalylate analogs, 1,4_butanediol ditalylate analogs, 1,6-hexanediol ditalylate analogs , Glycerin dichlorate analog, 2 hydroxy 3 Such as chloroxypropyl metatalylate, neopentylglycol bis-atarylate analog, neopentylglycol diatalylate analog of hydroxybivalate, polyoxyethylene diatalylate analog, polypropylene diatalylate analog Polyatalylate analogs; acrylic acid analogs, unsaturated carboxylic acids and anhydrides such as itaconic acid, maleic acid, crotonic acid, maleic anhydride; other, acetatetoxetyl acrylate analogs, 2- (meta ) Atariloy Loxochetyl Acid Phosphate, 2 Acrylamide 2-Methylpropanesulfonic acid, 4 Cyanophenyl Atylate Analogue, Amidimide Group (—CO—NNI ^ I ^ R ³ ) Atalylate Analogue , N vinylcarbazole, triarylcyanurate, allylglycidyl a Tell, Bierpyrrolidone, etc.

In addition, the blocked isocyanate group-containing acrylate ester (b ² ) includes 2_isocyanate acetylate analogue, or an acrylate derivative having a functional group capable of binding to the isocyanate group and a polyisocyanate. A reaction product obtained by reacting cyanate (b ³ ) in a ratio in which at least one isocyanate group remains is preferred.

As the attalylate analog having a functional group capable of binding to an isocyanate group, a mono- or diester of an acrylic acid analog and a polyhydric alcohol, which is preferable to an acrylate arylate analog, is particularly preferable. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerol, trimethylolpropane monoalkylene oxide adduct, pentaerythritol and the like. [0042] Examples of the polyisocyanates (b ³ ) include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate, hexamethylene diisocyanate. , Aliphatic polyisocyanates such as lysine diisocyanate, isophorone diisocyanate

And alicyclic polyisocyanates such as bis (isocyanatemethyl) cyclohexane and norbornene diisocyanate, and modified products such as nurate modified products, prepolymer modified products and burette modified products. Particularly preferred are aliphatic isocyanates, alicyclic isocyanates, and their nurate modified products, prepolymer modified products, and burette modified products.

[0043] Preferred blocking agents for the isocyanate group (b ⁴ ) include oximes, alkyl ketoximes, phenols, alkanols, β-diketones, malonic esters, ratatas and the like. Specific examples include pyrazole, 3-methylbiazole, 3,5-dimethylbiazole, indazole, methyl ethyl ketoxime, cyclohexanone oxime, ε-force prolatatam, acetoacetate ethyl, acetylacetone, phenol, cresol, and methanol. , Jetyl malonate, maleic imide, bisulfite 2-butanone oxime, jetyl malonate, isopropyl alcohol, t-butyl alcohol, maleimide, sodium bisulfite and the like. In particular, 2 butanone oxime, 3-methyl virazole, 3, 5 dimethylpyrazole, cyclohexane oxime, methyl ketyl ketoxime, ethyl acetoacetate, _ε -force prolatatam, jetyl Malonate and pyrazole are preferred.

[0044] Specific examples of the blocked isocyanate group-containing attalylate analogs include the following. 2_ Compound that isocyanate group of isocyanate acetyl acrylate is blocked with methyl ketyl oxime, 2_ Isocyanate group of isocyanate acetyl acrylate is blocked with _ε -force prolatatam, A compound in which the isocyanate group of the 1: 1 reaction (molar ratio) of isophorone dicyanoate and 2-hydroxyethyl acrylate is blocked with methyl ethyl ketoxime, isophorone diisocyanate and 2-hydroxypropyl alicyclic 1: 1 (molar ratio) to the rate analog 1: 1 Molar ratio of norbornene diisocyanate and 2-hydroxyethyl atylate analog, the isocyanate group of the reactant blocked with methyl ethyl ketoxime 1 (Molar ratio) A compound blocked with luketoxime.

 [0045] In the water / oil repellent composition of the present invention, the method for preparing the polymer (A) and the polymer (B) as the active ingredients is not particularly limited, and for example, a solution polymerization method using an organic solvent, a non-aqueous method, or the like. Conventional polymerization techniques such as dispersion polymerization, dispersion polymerization using water as a dispersion medium, emulsion polymerization, suspension polymerization, and bulk polymerization can be employed.

 [0046] 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 polymerization after sufficiently emulsifying the monomer using a high-pressure emulsifier or the like. For example, a mixture of a monomer, a surfactant, and an aqueous medium is mixed and dispersed in advance with a homomixer or a high-pressure emulsion machine before the polymerization is started, thereby improving the yield of the finally obtained polymer. It is possible.

 [0047] 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 obtained copolymer solution, dispersion, and emulsion can be used as a composition as it is or after dilution. A copolymer obtained by solution polymerization, emulsion polymerization, or other polymerization method may be separated and dissolved, dispersed, or emulsified in a solvent, dispersion medium, or emulsification medium as necessary to obtain a composition.

 [0048] In emulsion polymerization, an aqueous medium (C) is used as a polymerization medium. The aqueous medium (C) is a medium containing water, and may be water alone or an organic solvent as a polymerization auxiliary solvent if 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. As ketones, methyl ether ketone, methyl isobutyl ketone, acetone, etc. are preferred. Monoethers of saturated polyhydric alcohols, dialkyl ethers, monoalkyl ether monoacyl esters, dioxanes, etc. are preferred, and nitrogen compounds are preferred. 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.

[0049] The water-soluble organic solvent (c) can be used alone or in combination. Water in aqueous media The amount of the soluble organic solvent (c) is preferably 10 to 50 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B). If there is too much water-soluble organic solvent (c), the durability of water and oil repellency against washing may be reduced. Further, the amount of the aqueous medium may be 10 to 5000 parts by mass, for example 100 to 1000 parts by mass, with respect to 100 parts by mass of the polymer to be polymerized.

 [0050] Specific examples of the monohydric alcohol used in the aqueous medium include ethyl alcohol and isopropyl alcohol.

 As specific examples of the saturated polyhydric alcohol, compounds having 2 to 4 hydroxyl groups are preferable. Examples include tripropylene glycol, tetrapropylene glycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane.

[0051] 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 mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and their acetates; triethylene glycol monomethyl ethere, triethyleneglycol monoethylenoleateol, triethyleneglycol monomonopropylene ether, and their acetates; Propylene glycol monomethyl ether, propylene glycol monomethino ethenore, propylene glycol mono mono propylenoate, And their acetates; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl enoate ethere, dipropylene glycol monomono propinoate ethere, and their acetates; tripropylene glycol monomethyl ether, tripropylene glycol monomole Chill ethers, and their acetates; ethylene glycol dimethyl ether, ethylene glycol eno chineno ethenore, ethylene glycol enores propino eno enore, diethylene glucono lesino methino ree noeno, diethylene glucono lesino eno eno enore, di Ethylene glyconoresin propinoleateol, triethyleneglycoresin methinoreatenore, triethylene glycol jetyl ether, triethylene glycol Over distearate propyl ether, Propylene glyconoresininoatenore, Propyleneglyco-reno-Chinoleatenore, Propyleneglyco-noresi-propenoleatenore, Dipropyleneglyco-noresinino-leinotenole, Dipropyleneglyco-no-resinotinoreatenore, Dipropyleneglyco-no-le Examples thereof include resipropino enoate, tripropylene glycono lesino methino reeenore, and tripropylene glucono lesino enoate.

 [0052] Among them, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether are particularly preferred. As a reaction product of a 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.

 [0053] The polymerization reaction for obtaining the polymer (A) and the polymer (B) can be initiated by heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, etc., but it is water-soluble or oil-soluble. General purpose initiators such as azo-type, peroxide-type, persulfate, redox-type, etc. that are preferably used with radical polymerization initiators can be used depending on the polymerization temperature, especially azo-type compounds and their Salts are preferred.

 [0054] Specific examples of the oil-soluble polymerization initiator include 2, 2'-azobis (2-methylpropionitryl), 2, 2, 1azobis (2-methylbutyronitrile), 2, 2'-azobis ( 2, 4-dimethyl valeronitrile), 2, 2, 1-azobis (2, 4-dimethyl 4-methoxyvaleronitryl), 1, 1 '_ azobis (cyclohexane 1-carbonitryl), dimethinole 2, 2 , Monoazobis (2-methyl propionate), 2, 2, monoazobis (2-isobutyronitrile), benzoyl peroxide, di-tertiary monobutyl peroxide, lauryl peroxide, tamenhydro Preferred examples include peroxide, t_butyl peroxybivalate, diisopropyl peroxydicarbonate, t_butyl perpivalate, and the like.

[0055] Specific examples of the water-soluble polymerization initiator include 2, 2'-azobisisobutylamidine dihydrochloride, 2, 2'-azobis (2_methylpropionamidine) hydrochloride, 2, 2 '—Azobis [2 _ (2—imidazoline _ 2_yl) propane] hydrochloride, 2, 2'—Azobis [2— (2—imidazoline _ 2_yl) propane] sulfate hydrate, 2, 2'—azobis [2— (5-methyl_2_imidazoline-2-yl) propane] hydrochloride, 1-hydroxycyclohexyl hydroperoxide, 3_Carboxypropionyl peroxide, acetyl peroxide, sodium peroxide, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, etc. are preferred.

[0056] The polymerization temperature in emulsion polymerization is not particularly limited, but 20 to: 150 ° C is preferred, and 30 to 80 ° C is particularly preferred.

 The molecular weight of the polymer can be determined by a polystyrene conversion value by gel permeation chromatography. The mass average molecular weights of the polymer (A) and the polymer (B) are 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 / oil repellency can be imparted and high durability can be obtained.

 [0057] The molecular weight can be adjusted by using a chain transfer agent, and it is generally desirable to use a chain transfer agent. The chain transfer agent is particularly preferably an alkylthiol which is preferably a mercaptan such as alkylthiol, alkylenedithiol or thiocyanouric acid or an aromatic compound. Specific examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, t-decyl mercaptan, 2-hydroxyethyl mercaptan, lauryl mercaptan, stearyl mercaptan (octadecyl mercaptan) or α-methylstyrene dimer ( CH = CPhCH C (CH) Ph (where Ph is a phenyl group

 2 2 3 2

 And the like are preferred. It is also possible to use SH group-containing silicones.

[0058] The emulsion polymerization is preferably carried out using a surfactant (D). Nonionic surfactants (d ⁿ ), cationic surfactants (d ^c ), anionic surfactants (d ^a ), and amphoteric surfactants (d ^b ) are not particularly limited in the surfactant used. One or more of the known or well-known surfactants may be employed, but nonionic surfactants (d ⁿ ), cationic surfactants (cf) or amphoteric surfactants are particularly preferred. Agent (d ⁿ ) is preferred. When using surfactants with different ionicity, nonionic surfactant (d ⁿ ) and cationic surfactant (d ^c ), or nonionic surfactant (d ⁿ ) and amphoteric surfactant ( A combination of d ^b ) is preferred. It is also possible to use a polymer surfactant. [0059] The amount of the surfactant (D) is preferably from 0.0:! To 30 parts by mass, particularly from 0.5 to 15 parts per 100 parts by mass of the total amount of the polymer (A) and the polymer (B). About mass parts are preferred. If the amount of the surfactant is too small, the stability of the dispersion may be lowered. If the amount is too large, the durability of the water and oil repellency will be reduced, the compatibility of the power bath will be lowered, and the fastness to dyeing. May be damaged. However, when the monomer (b) constituting the polymer contains a self-emulsifying monomer, the amount of the surfactant may be reduced.

[0060] As the nonionic surfactant (d ⁿ ), a polyoxyalkylene monoalkyl ether, a mono-alkenyl ether, a polyoxyalkylene monoalkyl polyenyl ether, a polyoxyethylene mono (substituted phenyl) ether condensate , Polyoxyethylene mono (substituted phenyl) ether, polyoxyethylene polyoxyalkylene, alkylamine polyoxyethylene, alkylamido polyoxyethylene, alkylamine oxide, alkane (C — C) thiol, ethylene oxide and alkyl (C — C) with Amin

 12 18 12 18

 Examples thereof include a combined product, a condensation product of ethylene oxide and oleic acid, and a condensation product of ethylene oxide and sorbitan monofatty acid (C C).

 7 18

[0061] Specific examples of the nonionic surfactant (d ⁿ ) include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene octyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene octyl ether. Enil ether

, Polyoxyethylene isooctyl phenyl ether, polyoxyethylene hexyl phenyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene polyol ether, polyoxyethylene Urphenyl 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, polyoxypolyoxyethylene Sorbitan monostearate, polyoxyethylene sorbitan mono-O-les , Polyoxyethylene polyoxypropylene block polymer, polyglycerin fatty acid ester, polyether-modified silicone oil (trade names: SH3746, SH3748, SH3 749, SH3771 (manufactured by Toray Dow Cowing Silicone)), Perfluo Loalkylene Tylene Oxide Adduct (Product Name: Tunidain DS—401, DS—403 (Daikin Industries, Ltd.), Fluoroalkyl Ethylene Oxide Adduct (Product Name: Tunidain DS_406, Daikin Industries, Ltd.) And perfluoroalkyl oligomer (trade name: Unidyne DS-451 (Daikin Industries Co., Ltd.)).

[0062] As the cationic surfactant (d ^c ), it is preferable to use a cationic surfactant comprising a substituted ammonium salt. As a cationic surfactant comprising a substituted ammonium salt, 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. For example, mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long Amine salts such as alkenyl) 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 (polyoxyethylene) ammonium chloride, di (long chain alkyl) monomethyl Quaternary ammonium salts such as tilmono (polyoxyethylene) ammonium chloride, mono (long-chain alkyl) dibenzyldodecyldi (hydropolyoxyethylene) ammonium chloride, methylamine'ethyl sulfate and the like. The counter ion is preferably a chlorine ion, an ethyl sulfate ion, or an acetate ion. Long chain alkyls and long chain alkenyls may have 8 to 50 carbon atoms, for example 12 to 22 carbon atoms.

[0063] Specific examples of the cationic surfactant (d ^c ) include dimethylmonococonutamine acetate, tetradecylamine acetate, octadecylamine acetate, beef tallow alkylpropylene diamine acetate, N -[2- (Jetylamino) ethyl] oleamide hydrochloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium chloride, trimethylo Kutadecyl ammonium chloride, behenyl trimethyl ammonium chloride, (Dodeci Nium chloride, benzyl tetradecyl dimethyl ammonium chloride, benzyl otadecyl dimethyl ammonium chloride, biphenyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl monoammonium sulfate, Methyldodecyldi (hydropolyoxyethylene) ammonium chloride, dioleyldimethylammonium chloride, alkyl (beef tallow) dimethylbenzyl ammonium chloride, alkyl (beef tallow) trimethylammonium chloride, tetraradecylmethylbenzylammonium Um chloride, polyoxyethylene dodecyl monomethyl ammonium chloride, polyoxyethylene lauryl monomethyl ammonium chloride, Rukyll (beef tallow) imidazoline quaternary salt, 1-hydroxyethyl 2-alkyl (beef tallow) imidazoline quaternary salt, silicone-based cationic surfactant having a siloxane group as a hydrophobic group, fluorine-based cation having a fluoroalkyl group as a hydrophobic group Surfactants (trade name: Unidyne DS-202 (manufactured by Daikin Industries, Ltd.)), etc., among which octadecyltrimethylammonium chloride, octadecyldimethylmonoethylammonium sulfate, Mono (long-chain alkyl) monomethyldi (polyethylene glycol) ammonium chloride, di (tallow alkyl) dimethylammonium chloride, dimethylmonococonutamine acetate and the like are preferable.

[0064] When containing amphoteric surface active agent (d ^b) is Aranin acids, imidazo linear © beam betaines, Ryo Midobetain acids, or amphoteric surface active agent comprising acetic betaine, etc. (d ^b) is preferred. Specific examples of the amphoteric surfactant (d ^b ) include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylaminoacetic acid betaine, fatty acid amidopropyldimethylamino. Examples include betaine acetate.

[0065] Specific examples of the anionic surfactant (d ^a ) include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nouryl phenyl ether sulfate, polyoxyethylene lauryl ether. Triethanolamine sulfate, sodium cocoyl sarcosine, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, diether hexyl Sodium sulfosulfosuccinate, sodium monosulfine sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl sulfonate (trade name: Unidyne DS—101, 102 (Daikin Kogyo Co., Ltd.))).

 [0066] 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 emulsion polymerization medium as 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. The water-soluble organic solvent (c) used in this case may be the same or different or partially different from that used during polymerization. ,. Alternatively, 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 aforementioned emulsion polymerization can be used. It is also possible to add the 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.

[0067] 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 containing a crystalline R ^F group. Even if the amount of the soluble organic solvent (c) is small, a homogeneous polymer can be obtained immediately, and since it does not contain the water-soluble organic solvent (c) at all, a water- and oil-repellent composition having a low environmental impact due to volatile organic substances is obtained. It is also possible.

[0068] 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 size of the fine particles is 10 to: OOOnm force 10 to 300 nm force S, and particularly preferable particle size 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, resulting in decreased water and oil repellency or when processed into dyed fabrics. There is a risk of discoloration. Also, if the particle size is too large, it will be difficult for the dispersed particles to stably exist in the medium and may settle out. Therefore, it 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.

 [0069] In the water- and oil-repellent composition of the present invention, the polymer (A) and the polymer (B) are not present in the same particle even if they are present in the same particle, and separate particles are used. It may be formed or 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 carrying out 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 monomers are added all at once or divided into several stages, followed by polymerization by adding a polymerization initiator, so-called seed polymerization, or a method of polymer (B) emulsified dispersion with polymer (B This can be achieved by a method in which a monomer and an initiator for polymerizing A) are prepared and a multi-stage polymerization such as seed polymerization is performed. When the polymer (A) and the polymer (B) are present in the same particle, they may have a homogeneous structure with no restrictions on the phase structure, or the so-called core-shell type layer separation structure, Phase separation structures such as island type phase separation structure and spinodal type phase separation structure can be freely adopted.

[0070] The repellent and 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, Examples include urethane resin compounds. Blocked isocyanate compounds (f and amino resin compounds (f ² ) are preferred.

Here, the blocked isocyanate compound (f ¹ ) is a compound having no polymerizable unsaturated group, and the isocyanate group of the polyisocyanate (b ³ ) is converted into the blocking agent described above. A compound having a structure completely blocked by (b ⁴ ) is preferred. In addition, as a monomer constituting a polymer (f ³ ) that does not contain a fluorine-containing monomer having a crosslinkable monomer as an essential polymerization unit, an acrylate amide analog (b ¹ ) or a blocked isocyanate group-containing acrylate copolymer. (B ² ) is preferred, especially N-methylol acrylamide and 2-isocyanate ethyl methacrylate block. Preferred are isomers.

[0072] 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, and includes alcohols such as melamine, guanamine, or urea. Furthermore, addition condensates of amines and formaldehyde, and addition condensates of melamine, guanamine, urea and the like with formaldehyde further include alcohols, compounds obtained by addition condensation of amines, and 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 Alkyl melamine resin such as melamine resin, methylated n-butylated melamine resin, i-butylated melamine resin; benzoguanamine resin; n-butylated benzoguanamine resin, i Examples include alkyl benzoamine amine resins, alkyl benzoamine amine resins, petit laur urea melamine resins, and aceto guanamine resins.

[0073] The amino resin compound (f ² ) in the present invention is preferably substantially soluble in water at room temperature. There are many such commercially available amino succinic compounds (f ² ), such as those manufactured by Sumitomo Chemical Co., Ltd. (for example, trade name Sumtex Resin), manufactured by Dainippon Ink Co., Ltd., Mitsui Chemicals, etc. Things are available. The amount of the thermosetting agent (F) is preferably 5 to 100 parts by mass, and more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the polymer (A) + the polymer (B).

[0074] In the water / oil repellent composition of the present invention, the polymer (A), the polymer (B), and the above-mentioned polymer heat are used as a filler extender or to develop various physical properties in the article to be treated. Polymers (G) other than the curing agents (f ² , 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 and organopolysiloxanes. Examples of the water-soluble polymer include polyacrylamide, polybutyl alcohol, and derivatives thereof.

[0075] Examples of organopolysiloxanes include methylnoid diene polysiloxanes typified by silicone water repellents, terminal OH group-blocked dimethylpolysiloxanes, bur group-containing polysiloxanes, and silicone softeners. Amino group, epoxy group, polyether in side chain And various modified silicone oils modified by introducing a group, a carboxyl group, a hydroxyl group, a trifluoroalkyl group, an alcohol ester group, an alkyl group, and the like. Silicone desperation is a solution in which a silicone resin or silicone rubber in an initial polymerization state is dissolved in a solvent, and when heated, it condenses to form a film having a three-dimensional network structure. In the present invention, not only those mentioned above, but also various kinds of onoreganopolysiloxanes can be used. There are many types of commercial products of these onoreganopolysiloxanes. Examples of the line of products sold include SH200, PRX413, SH8011, SD8000 (product names of Toray Industries, Inc., Silicone Co.), KP-801M, KPN-3504 (product names of Shin-Etsu Chemical Co., Ltd.), and the like. The amount of the polymer (G), for example, the amount of the organopolysiloxane is preferably 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. .

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 due to the inclusion of 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 alcohol and derivatives thereof; oleic acid, tall Fats and oils such as oil, mineral oil, stone wall, etc .; surfactants such as sorbitan fatty acid ester, polyethylene glycol fatty acid ester, and plenoronic type nonionic surfactant; silicone surfactants such as siloxane and silicone resin Can be used alone or in combination. Typical commercial antifoam products include Ade forcenate B, Adecanate B1068, etc. B-series (Asahi Denka Kogyo Co., Ltd.); Formaster DL, Nopco NXZ, SN deformers 113, 325, 308, 368 SN Deformer series; Dehydran 129 3, Dehydran 1513 (manufactured by Sannopco); Furonon SB_110N, SB_210, 510, 551, Aqualen 800, 805, Aqualen 1488 (Kyoeisha Chemical Co., Ltd.); Surfynol 104E (Acetylene-based antifoaming agent manufactured by Air Products & Chemical Co., Ltd.); KS-607A (manufactured by Shin-Etsu Chemical Co., Ltd.); FS Antifoam (manufactured by Dowco Jung); BYK_020, 031, 073, W (manufactured by Big Chemi Co., Ltd.) Dehydran 981 (Henkenore Hakusui); Epanichi 410, 710, 720 (Daiichi Pharmaceutical Co., Ltd.); Tego Foamex series (Tego Goldschmidt); Foamlet Tas 747, TY_10, Sakai series (manufactured by Nikka Chemical Co., Ltd.) and the like. The content of the antifoaming agent is preferably 0.01 to 10% by mass, particularly preferably 0.05 to 5% by mass with respect to the water / oil repellent composition (for example, aqueous resin emulsion).

 [0077] In addition, a compound that is considered to have an action of dissolving, swelling, or softening the polymer and forming the polymer with a small amount of heat, a so-called film forming aid may be used. 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 used. Can be used without limitation. These compounds may contain a fluorine atom in the molecule. Specific examples of film forming aids include methyl acetate, ethyl acetate, butyl acetate, dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, acetic acid diethylene glycol monoethyl ether, di-ethylene adipate η-butyl, butyl carbide Examples include tall acetate, otamethyl trisiloxane, decamethylcyclopentane siloxane, dimethyl phthalate, and jetyl succinate. Usually, the amount of the film-forming aid used is in the range of 0.:! To 70 parts by mass per 100 parts by mass of the polymer, and particularly preferably 5 to 60 parts by mass. 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.

 [0078] Furthermore, other additive components can be blended as necessary. For example, other water and oil repellents, stin blockers, softeners, cross-linking promoting catalysts, texture modifiers, penetrants, insect repellents, antibacterial agents, flame retardants, antistatic agents, polishes, antifungal agents In addition, a water absorbing agent, an anti-shrinking agent, a dye, a pigment, a dye stabilizer, an antioxidant, a deoxidizing agent, a wrinkle adjusting agent and the like can be appropriately used in combination.

 [0079] However, if the amount of the non-volatile component contained in the water / oil repellent composition is too large relative to the total amount of the polymers (Α) and (Β), sufficient performance as a water / oil repellent is inhibited. There is a risk. Therefore, in the water / oil repellent composition of the present invention, the total amount of polymer (Α) and polymer (Β) is 50% by mass or more, preferably 75% by mass or more of the total solid content.

[0080] The water / oil repellent composition of the present invention is diluted to an arbitrary concentration according to the purpose and application, and is treated by an arbitrary method according to the type of article to be treated, the preparation form of the composition, and the like. Applicable to goods. For example, dipping, coating, spraying, padding, roll coating, spin coating A method of adhering to the surface of the article to be treated and drying by using a combination of these methods is employed. As a method for processing the article, a method in which the article is immersed in a water / oil repellent treatment liquid containing the polymer (A) and the polymer (B) is preferable, but the article containing the polymer (B) and not containing the polymer (A) is preferable. After immersing the article in the composition, the polymer (A) containing polymer (B), the method of immersing in the water / oil repellent treatment liquid, and the polymer (A) containing polymer (B) It is also preferable to immerse the article in the water / oil repellent treatment solution and then immerse it in the water / oil repellent treatment solution containing the polymer (B) and not containing the polymer (A). When processing textile products, it is immersed in a processing solution prepared so that the total amount of polymer (A) and polymer (B) is 0.01 to 10% by mass, preferably 0.:! To 3% by mass. An effective method is to remove the excess treatment liquid with a roll or the like and then dry it. 0.01-: By setting the content to 10% by mass, it is possible to surely cover and bond the fibers, the performance is sufficient, and the texture of the fibers is good. If necessary, it may be applied together with a suitable crosslinking agent and cured. In addition, it is also possible to impart water and oil repellency to them by mixing with polypropylene, nylon or the like and molding and fiberizing them.

Articles to be treated with the water / oil repellent composition of the present invention are not particularly limited, fiber products such as fibers, fiber woven fabrics, fiber knitted fabrics, and nonwoven fabrics, and ceramics such as glass, gypsum, asbestos, bricks, cement, and concrete. Products, leather products such as fur, wood, paper, pulp products, metals and their oxides, stones, resins, painted surfaces and plasters. 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. Uses of these items include sportswear, coats, blousons, surgical clothes, work clothes, uniforms and other clothing items, dust masks, shoes, bags, umbrellas, Rikiichi, curtains, wallpaper, tents, architecture Materials, filtration materials, electronics or optical system parts and elements, etc. In particular, when processed into textile products, 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 animal and vegetable natural fibers such as cotton, hemp, wool, and silk, polyamides, polyesters, polybulal alcohol, polyacrylonitrile, polysalts, and polypropylene, synthetic fibers such as rayon and acetate. Semi-synthetic fiber, glass fiber, carbon fiber, tuss Preferable examples include inorganic fibers such as the best fiber, and blended fibers thereof, and any form such as fiber, yarn, fabric, and nonwoven fabric may be used.

 Example

[0082] Hereinafter, the present invention will be described in more detail with reference to polymerization examples (1 to 7), examples (1 to 6) and comparative examples (1 to 10). However, the present invention is not limited to these examples. It goes without saying that it is not done. Various evaluations in Examples and Comparative Examples were performed according to the following methods and standards. In the table, the symbols (a ¹ ), (a ² ), and (b) after the monomer names indicate the category of monomers (a ¹ ), (a ² ), and (b) described above. .

[0083] [Evaluation of water repellency]

 The water repellency is shown by the water repellency (see Table 1 below) by the spray method of JIS-L-1092.

[0084] [Table 1]

[0085] [Evaluation of oil repellency]

 Oil repellency is according to AATCC _TM118-1966. Drop the test solution shown in Table 2 below into two places on the test cloth, observe the penetration state after 30 seconds, and give a test solution that does not show immersion. The highest point of oil repellency was shown as an oil repellency pick-up.

[0086] [Table 2] surface tension

 Oil repellency

 Test solution mN / Ίη

 Nampa

 (25 ° C)

 8 n-heptane 20. 0

7 _n — Octane 21. 8

 6 π—Ding can

 5 π—Dodecane 25. 0

 4 n— r

 3 π-Hexadecane 27. 3

 Nugiol 65 咅 13

 2 / hexadecane 35 parts 29, 6

 1 Nugiol ¾J 1, £ ^

 0 Less than 1

[0087] Polymerization Example 1

 In a 200 mL glass four-necked reactor equipped with a thermometer, condenser, and stirring blade (CF CF CH

 3 2 2

○ 16.7 g of COC (CH) = CH) and 100 ml of ethyl acetate are charged, and nitrogen substitution is performed.

 3 2

 I got it. Raise the temperature to 60 ° C in a nitrogen atmosphere, add 1.63 g of t_butyl peroxypivalate (Nippon Yushi Fatty Butyl PV), and stir for 5 hours while maintaining the temperature of the reaction solution at 60 ° C. Continued. After cooling the reaction solution, it was poured into 300 mL of methanol, and the precipitate was filtered and vacuum dried at 60 ° C. for 1 hour to obtain 13.7 g of a polymer (polymer P1). The obtained polymer T was 77 ° C.

 g

 [0088] Polymerization examples 2 to 7

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

[0089] [Table 3]

Polymerization composition (mass ¾)

 Poly

 Example 5F A (a1 HFIP-MA (a1 9FMA (a2 6FOMA1 (a2 t A (

 Ma

 )))) b)

 Polymerization example

 1 P1 100

 Polymerization example

 2 P2 100

 Polymerization example

 3 P3 70 30

 Polymerization example

 4 P4 100

 Polymerization example

 5 P5 100

 Polymerization example

 6 P6 70 30

 Polymerization example

 Hu P Hu 85 15

[0090] The abbreviations in Table 3 represent the following meanings.

 5FMA: CF CF CH OCOC (CH) = CH (T: 77 ° C)

 3 2 2 3 2 g

 HFIP-MA: (CF) CHOCOC (CH) = CH (T: 91 ° C)

 3 2 3 2 g

 9FMA: F (CF) (CH) OCOC (CH) = CH (T: 37.C)

 2 4 2 2 3 2 g

 6FOMAl: CF CF CF OCFCF CF OCFCF CH OCOC (CH) = CH (T:-

3 2 2 3 2 3 2 3 2 g

(34 ° C)

 StA: Stearyl Atarylate

 [0091] Examples:! -6 and comparative examples:! -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 (force Nebo Naturine, nylon 6, amber-dyed cloth) is immersed in the treatment solution, treated at 500 rpm for 18 seconds in a centrifuge, air-dried at room temperature for 1 second, and then heat treated at 150 ° C for 5 minutes. Then, the water and oil repellency of the treated cloth was evaluated. The results are shown in Table 5. The + mark in the table indicates slightly better than the performance shown in each.

[0092] [Table 4] Mixed polymer composition (mass%) Example

 P1 P2 P 3 P4 P5 P6 P7 Example 1 85 15 Example 2 85 15 Example 3 85 15 Example 4 50 50

Example 5 70 30

Example 6 85 15

 Ten

Comparative Example 1 0

 Ten

Comparison 2 0

 10 Comparative Example 3 0

 Ten

Comparative Example 4 0

 10 Comparative Example 5 0

 10 Comparison 6 0

 1 0 Comparison 7 0 Comparison 8 50 50

Comparative Example 9 50 50

Comparative Example 1

 0 50 50 Table 5]

Example Water repellency Oil repellency Example 1 90 + 2

Example 2 90 2

Example 3 90 + 2

Example 4 90 + 4

Example 5 90 + 3

Example 6 1 00 2

Comparative Example 1 90 + 1

Comparative Example 2 90 0

Comparative Example 3 80 + 0

Comparative Example 4 90 4

Comparative Example 5 50 0

Comparative Example 6 80 + 2

Comparative Example 7 90 1

Comparative Example 8 80 + 0

Comparative Example 9 80 10 0

Comparative Example 1 0 80 + 2

Claims

The scope of the claims

[1] (A) a fluorine-containing monomer (a ¹ ) having a glass transition temperature (T) of a homopolymer of 50 ° C or higher, and

 g

Polymerization of existing fluorine-containing monomer (a ² ) if necessary and T of homopolymer is less than 50 ° C

 g

A polymer having as a unit, as well as polymer, is (a ¹⁾ the amount of (a ¹⁾ and (a ²⁾ a total of 50 mass _^0/0 or more with respect to the

(B) a fluorine-containing monomer (a ¹ ) present if necessary because the T of the homopolymer is 50 ° C or higher, and

 g

And a polymer having a fluorinated monomer (a ² ) having a T of less than 50 ° C as a polymerized unit.

 g

A Lima, quantity (a ¹⁾ and (a ²⁾ Total fluorinated water repellent oil repellent composition comprising a polymer in excess of 50 mass _^0/0 for the in (a ^2).

[2] Polymer (A) further contains a fluorine-containing monomer (b) copolymerizable with the fluorine-containing monomer as a polymerization unit, and the mass of monomer (b) in polymer (A) The fluorine-containing water and oil repellent composition according to claim 1, wherein the fraction is less than 40% by mass.

[3] The polymer (B) further contains, as a polymerization unit, a fluorine-free monomer (b) copolymerizable with the fluorine-containing monomer, and the mass fraction of the monomer (b) in the polymer (B). The fluorine-containing water / oil repellent composition according to claim 1, wherein the ratio is less than 70% by mass.

4. 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.

[5] 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.

[6] The fluorinated monomer (a ¹ ) and (a ² ) force formula:

(R ^fa -Y-) X

 [Where

R ^fa : Perfluoroalkyl group having 6 or less carbon atoms, perfluoro (poly) ether group having 30 or less carbon atoms, or fluorine atoms within a range not exceeding 20% of the total fluorine atoms contained in these groups A group replaced by an atom,

 Y: Divalent organic group or single bond,

 n: l or 2,

X: polymerizable unsaturated group, when n is 1 — CR ^a = CH, -Q-COCR ^a = CH , -Q- (CH)-φ -CR ^a = CH, -Q-CR ^a = CH or _C〇_Q_CR ^a = C

2 m 2 2

If H and n is 2, one Q— C〇R ^a = CR ^a C〇1 Q— or one Q— C〇C (CH C

twenty two

O-Q-) = CH. Where m is an integer from 0 to 3. Q is 101, 1 S— or 1 NR

 2

Represents b_. φ represents a substituted or unsubstituted phenylene group. 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. R ^b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ]

 The fluorine-containing water / oil repellent composition according to any one of claims 1 to 5, which is a compound represented by the formula:

[7] The fluorine-containing monomer (a ¹ ) and (a ² ) force S, an talylate or a metatalylate containing a perfluoroalkyl group having 6 or less carbon atoms as a side chain, or an alicyclic in which the _α- position is substituted with a halogen atom The fluorine-containing water repellent composition according to any one of claims 1 to 6, which is a rate.

 [8] The mass ratio of the polymer (Α) to the polymer (Β) is 5: 95-95: 5, and the total proportion of the polymer (Α) and the polymer (Β) in the total solid content is 50% by mass or more. The fluorine-containing water and oil repellent composition according to any one of claims 1 to 7.

[9] The repulsive force of the monomer (a ¹ ) is 5 ° C or more and the T force of the monomer (a ² ) is ¾5 ° C or less.

 The fluorine-containing water / oil repellent composition according to any one of the above.

[10] A method of treating a substrate with the fluorine-containing water / oil repellent composition according to any one of claims:! To 9.

 [11] A treated substrate obtained by the method of claim 10.