JP2023145051A - Polymer for water- and oil-repellents, water- and oil-repellent composition, and product processed with water- and oil-repellent - Google Patents

Abstract

To provide a polymer for water- and oil-repellents that can endow a target material with superior water- and oil-repellency, a water- and oil-repellent composition, and a product processed with water- and oil-repellents.SOLUTION: A polymer for water- and oil-repellents comprises a fluorine-containing copolymer, comprising a constitutional unit derived from a fluorine-containing monomer (a) represented by formula (1) and a constitutional unit derived from a fluorine-free monomer (b1) represented by formula (2), wherein, assuming the total amount of the constitutional units derived from all the monomers to be 100 pts.mass, the mass of the constitutional unit derived from the monomer (a) is 10-90 pts.mass, and the mass of the constitutional unit derived from the monomer (b1) is 10-90 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to polymers for water and oil repellents, water and oil repellent compositions, and water and oil repellent treated products.

Fluororesins can impart water repellency, oil repellency, stain resistance, releasability, etc. to various objects to be treated. For example, by using a fluorine-containing copolymer having a perfluoroalkyl group, water and oil repellency can be imparted to fibers, leather, paper, and the like.

Patent Document 1 discloses a compound containing a structural unit derived from a fluorine-containing monomer having a perfluoroalkyl group and a structural unit derived from a non-fluorine monomer having a long-chain alkyl group and an amide group, urethane group, or urea group. A fluorine copolymer is disclosed.

JP2020-59800A

However, the fluorine-containing copolymer of Patent Document 1 has poor film-forming properties on hydrophilic base materials such as natural fibers and natural leather, and is difficult to impart sufficient water and oil repellency.

In view of the above circumstances, an object of the present invention is to provide a water and oil repellent polymer, a water and oil repellent composition, and a water and oil repellent composition that can impart excellent water and oil repellency to a treated object. Our objective is to provide treated oil products.

That is, the present invention provides a structural unit derived from a fluorine-containing monomer (a) represented by the following formula (1) and a structural unit derived from a non-fluorine monomer (b1) represented by the following formula (2). A fluorine-containing copolymer containing 10 to 90 parts by mass of structural units derived from the monomer (a) when the total amount of structural units derived from all monomers is 100 parts by mass. , relates to a polymer for water and oil repellents, in which the mass of the structural unit derived from the monomer (b1) is 10 to 90 parts by mass.
(In formula (1), R ¹ represents a hydrogen atom or a methyl group, l is an integer of 0 to 4, and m is an integer of 0 to 5.)
(In formula (2), R ² represents a hydrogen atom, a methyl group, or a halogeno group, R ³ represents an alkyl group having 12 to 24 carbon atoms, and A represents an alkylene group having 1 to 10 carbon atoms. , X represents 0 or 1, and Y is a hydroxyurethane structure selected from the group consisting of the following formula (3), formula (4), formula (5), and formula (6).)

The present invention also relates to a water and oil repellent composition containing the water and oil repellent polymer and a liquid medium.

Furthermore, the present invention relates to a water- and oil-repellent-treated product to which the water- and oil-repellent polymer is attached.

According to the present invention, there is provided a polymer for water and oil repellents, a water and oil repellent composition, and an excellent water and oil repellent composition capable of imparting excellent water and oil repellency to base materials such as synthetic fibers, natural fibers, and natural leather. A water/oil repellent treated product having water and oil repellency can be provided.

<Fluorine-containing monomer (a)>
The fluorine-containing monomer (a) is a monomer represented by the following formula (1).
(In formula (1), R ¹ represents a hydrogen atom or a methyl group, l is an integer of 0 to 4, and m is an integer of 0 to 5.) Also, in formula (1), l is 1 Preferably, it is an integer of 2 to 2, and m is preferably an integer of 3 to 5.

Specific examples of the compound represented by the fluorine-containing monomer (a) include 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, and 3-( Examples include perfluorohexyl)propyl (meth)acrylate, 4-(perfluorohexyl)butyl (meth)acrylate, and 2,2,2 trifluoroethyl (meth)acrylate. Preferred are 2-(perfluorohexyl)ethyl (meth)acrylate and 2-(perfluorobutyl)ethyl (meth)acrylate, but 2-(perfluorohexyl)ethyl methacrylate is preferred because of its excellent water and oil repellency. More preferred. The fluorine-containing monomer (a) may be used alone or in combination of two or more.

<Non-fluorine monomer (b1)>
The non-fluorine monomer (b1) is a monomer represented by the following formula (2), and has a hydroxyurethane structure, which can improve the film-forming properties of the polymer on the object to be treated, Can provide excellent water repellency. The non-fluorine monomer (b1) may be used alone or in combination of two or more.
(In formula (2), R ² represents a hydrogen atom, a methyl group, or a halogeno group, R ³ represents an alkyl group having 12 to 24 carbon atoms, and A represents an alkylene group having 1 to 10 carbon atoms. , X represents 0 or 1, and Y is a hydroxyurethane structure selected from the group consisting of the following formula (3), formula (4), formula (5), and formula (6).)

In formula (2), R ² is preferably a hydrogen atom or a methyl group from the viewpoint of facilitating the progress of the polymerization reaction.

In formula (2), R ³ represents an alkyl group having 12 to 24 carbon atoms. Having an alkyl group with 12 to 24 carbon atoms induces crystallization of the side chain, forming a dense film with aligned alkyl groups on the surface of the object to be treated, and exhibiting excellent water repellency. . Examples of the alkyl group having 12 to 24 carbon atoms include linear or branched alkyl groups having 12 to 24 carbon ^atoms . The number is preferably 12 to 22, more preferably 18 to 22. Moreover, it is more preferable that R ³ is a linear alkyl group.

In formula (2), A represents an alkylene group having 1 to 10 carbon atoms, and X represents 0 or 1. The number of carbon atoms in A is preferably 1 or more, and preferably 4 or less.

In formula (2), Y is a hydroxyurethane structure selected from the group consisting of formula (3), formula (4), formula (5), and formula (6) above. In view of superior water repellency, Y has a structure of formula (3) or formula (4).

As the non-fluorine monomer (b1), it is particularly preferable to use a compound having a molecular weight in the range of 355 to 800.

The method for producing the non-fluorine monomer (b1) is not particularly limited, and it can be produced by a known method, but for example, a compound having both a (meth)acryloyl group and a cyclic carbonate group and It can be obtained by addition reaction with an amine compound having 24 alkyl groups.

<Vinyl monomer (b2)>
The vinyl monomer (b2) is a vinyl group-containing monomer that can be copolymerized with the fluorine-containing monomer (a) and the non-fluorine monomer (b1). Examples of the vinyl monomer (b2) include (meth)acrylic ester compounds, (meth)acrylamide compounds, aromatic alkenyl compounds, vinyl halides, and vinyl cyanide compounds. Among these, it is preferable to copolymerize at least one (meth)acrylic acid ester compound or (meth)acrylamide compound. The vinyl monomer (b2) may be used alone or in combination of two or more types.

As the (meth)acrylic acid ester compound or the (meth)acrylamide compound, it is preferable to use a compound having at least one vinyl group and represented by the following formula (7).
(In formula (7), R ⁴ represents a hydrogen atom, a methyl group, or a halogeno group, Z represents an oxygen atom or a nitrogen atom, and R ⁵ represents a hydrogen atom or an optionally substituted carbon number 1 ~22 hydrocarbon groups, n represents 1 when Z is an oxygen atom, and represents 2 when Z is a nitrogen atom.)

In formula (7), the hydrocarbon group of R ⁵ may have a substituent. The compound represented by formula (7) used as the vinyl monomer (b2) includes a compound in which R ⁵ is a hydrocarbon group having a substituent, and a compound in which R ⁵ is a hydrocarbon group without a substituent, respectively. It is preferable to include one or more.

Examples of compounds in which R ⁵ is a hydrogen atom include (meth)acrylic acid, (meth)acrylamide, and the like.

Examples of the unsubstituted hydrocarbon group for R ⁵ include linear, branched, or cyclic alkyl groups having 1 to 22 carbon atoms.

Specific examples of compounds having a linear or branched alkyl group having 1 to 22 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, ( Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate Nonyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylate Examples include docosyl acrylate, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, etc., but (meth)acrylic Preferred are methyl acid, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate. More preferred is stearyl (meth)acrylate.

Examples of the unsubstituted cyclic hydrocarbon group in R ⁵ include monocyclic or polycyclic alkyl groups having 3 to 22 carbon atoms. Examples include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and 1-adamantyl (meth)acrylate, which can improve the durability of water and oil repellency. From this point of view, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are preferred. More preferred is cyclohexyl (meth)acrylate.

When the hydrocarbon group in R ⁵ has a substituent, examples of the substituent include a hydroxyl group, an ether group, an epoxy group, a carbonyl group, an ester group, an amide group, an isocyanate group, a urethane group, a urea group, a vinyl group, and an amino group. , an onium base, a heterocyclic group, an aryl group, an organosiloxy group, and a polydimethylsiloxane group. Among these substituents, R ⁵ is preferably a hydrocarbon group having an aryl group, a polydimethylsiloxane group, a hydroxyl group, or an ether group. The molecular weight of the hydrocarbon group-containing monomer having a polydimethylsiloxane group is preferably 1,000 to 30,000.

Specific examples of compounds in which the hydrocarbon group has a substituent include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and mono(meth)acrylate. ) Glycerol acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate, (meth) Methoxypolyethylene glycol acrylate, methoxypolypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl (meth)acrylate, (meth)acrylic acid 2 - Isocyanatoethyl, dimethylaminoethyl (meth)acrylate, trimethylammoniumethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, "Plaxel FM series" (manufactured by Daicel Corporation, ε-prolactone adduct of 2-hydroxyethyl methacrylate, trade name), 3-(trimethoxysilyl)propyl (meth)acrylate, "Siraplane FM- 0721 (manufactured by JNC Corporation, polydimethylsiloxane group-containing macromonomer (molecular weight 5,000), trade name), Silaprene FM-0725 (manufactured by JNC Corporation, polydimethylsiloxane group-containing macromonomer (molecular weight 10) ,000), trade name), Silaprene FM-7721 (manufactured by JNC Corporation, polydimethylsiloxane group-containing bifunctional macromonomer (molecular weight 5,000), trade name), diacetone (meth)acrylamide, N -Methylol (meth)acrylamide and the like. 2-Hydroxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene (meth)acrylate because of their good water and oil repellency and ease of copolymerization with the non-fluorine monomer (b1). Glycol, benzyl (meth)acrylate, "Siraplane FM-0721 (manufactured by JNC Corporation, polydimethylsiloxane group-containing macromonomer (molecular weight 5,000), trade name)", "Siraplane FM-0725 (manufactured by JNC Corporation, product name)" Polydimethylsiloxane group-containing macromonomer (molecular weight 10,000, trade name) manufactured by Co., Ltd., diacetone (meth)acrylamide, and N-methylol (meth)acrylamide are preferred.

Examples of the aromatic alkenyl compound used as the vinyl monomer (b2) include styrene, α-methylstyrene, and p-methoxystyrene.

Examples of the halogenated vinyl compound used as the vinyl monomer (b2) include vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide.

Examples of the vinyl cyanide compound used as the vinyl monomer (b2) include (meth)acrylonitrile.

<Composition ratio of polymer for water and oil repellent>
The polymer for water and oil repellent agents is a fluorine-containing copolymer containing a constitutional unit derived from a fluorine-containing monomer (a) and a constitutional unit derived from a non-fluorine monomer (b1), or a fluorine-containing copolymer containing a constitutional unit derived from a fluorine-containing monomer (a). ), a structural unit derived from the non-fluorine monomer (b1), and a fluorine-containing copolymer containing a structural unit derived from the vinyl monomer (b2).

In the fluorine-containing copolymer, when the total amount of structural units derived from all monomers is 100 parts by mass, the mass of structural units derived from monomer (a) is 10 to 90 parts by mass, and the monomer The mass of the structural unit derived from (b1) is 10 to 90 parts by mass. In the fluorine-containing copolymer, from the viewpoint of water and oil repellency and solubility, when the total amount of structural units derived from all monomers is 100 parts by mass, the mass of structural units derived from monomer (a) is , is preferably 30 to 80 parts by mass, more preferably 40 to 80 parts by mass, and preferably the mass of the structural unit derived from monomer (b1) is 10 to 70 parts by mass. , more preferably 20 to 60 parts by mass. When the mass of the structural unit derived from monomer (a) is less than 10 parts by mass, water and oil repellency tends to decrease,
If it is more than 90 parts by mass, the solubility of the fluorine-containing copolymer in a hydrocarbon solvent tends to decrease significantly.

In addition, when the fluorine-containing copolymer contains structural units derived from the vinyl monomer (b2), from the viewpoint of water and oil repellency and solubility, the total amount of structural units derived from all monomers is 100 parts by mass. The mass of the structural unit derived from the monomer (b2) is preferably 80 parts by mass or less, more preferably 1 to 50 parts by mass, and even more preferably 5 to 30 parts by mass. preferable.

<Production method of polymer for water and oil repellent>
The water- and oil-repellent polymer can be obtained by radical polymerizing a monomer mixture containing at least a fluorine-containing monomer (a) and a non-fluorine monomer (b1). The polymerization method is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used.

As the polymerization initiator, organic peroxides, azo compounds, persulfates, etc. can be used. Specific examples of the polymerization initiator include tert-butylperoxypivalate, tert-hexylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di-3 ,5,5-trimethylhexanoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropion) (amidine) dihydrochloride, ammonium persulfate, etc. The amount of the polymerization initiator used can be appropriately set depending on the combination of monomers used, reaction conditions, and the like.

In a polymerization method using solution polymerization, various monomers are dissolved in an arbitrary solvent in the presence of a polymerization initiator, and after nitrogen substitution, polymerization can be carried out by heating and stirring.

In the polymerization method using emulsion polymerization, various monomers are emulsified in water or a mixture of an organic solvent and water in the presence of a polymerization initiator and a surfactant, and after nitrogen substitution, polymerization is carried out by heating and stirring. can.

The arrangement of the constituent units of each monomer in the water- and oil-repellent polymer is not particularly limited, and may be random, block, graft, or the like.

<Weight average molecular weight>
The polymer for water and oil repellent agents is a polymer having a weight average molecular weight in the range of 5,000 to 2,000,000 in terms of polystyrene, and from the viewpoint of good water and oil repellency, the weight average molecular weight is 10,000 to 1,000. A range of 900,000 is preferred. More preferably, it is in the range of 30,000 to 1,800,000. If the weight average molecular weight is within this range, the uniformity of the polymer film will be improved and the water and oil repellency will be good.

A chain transfer agent may be used during polymerization of the water- and oil-repellent polymer for the purpose of adjusting the molecular weight. Examples of chain transfer agents include lauryl mercaptan and tert-butyl alcohol. The amount of the chain transfer agent used can be appropriately determined depending on the combination of monomers used, reaction conditions, and the like.

<Water and oil repellent composition>
The water and oil repellent composition can be produced by mixing a water and oil repellent polymer and a liquid medium. By forming the water- and oil-repellent composition, the water- and oil-repellent polymer can be easily attached to the object to be treated.

There are no particular restrictions on the liquid medium as long as it dissolves or disperses the polymer, but examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, ethanol, n-propanol, isopropyl alcohol, propylene glycol, and dipropanol. Propylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, tetrahydrofuran, dimethyl formaldehyde, toluene, xylene, n-hexane, isohexane, n-heptane, cyclopentane, cyclohexane, methylcyclohexane, isoparaffin solvents, etc. can be mentioned. Among these liquid media, aliphatic hydrocarbon solvents are preferred from the viewpoint of preventing texture and deterioration of the object to be treated. Preferred examples include n-hexane, isohexane, n-heptane, cyclopentane, cyclohexane, and methylcyclohexane, with n-hexane, n-heptane, and cyclohexane being particularly preferred. These liquid media may be used alone or in combination of two or more.

When the total amount of the water- and oil-repellent polymer and the liquid medium is 100 parts by mass, the content of the water- and oil-repellent polymer is preferably 0.1 to 10 parts by mass, and more preferably, The amount is 1 to 10 parts by mass.

The water and oil repellent composition may further contain additives within a range that does not impair the effects of the present invention. For example, when the total amount of the polymer and liquid medium is 100 parts by mass, the content of the additive is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Examples of additives include polymers capable of imparting water and oil repellency other than polymers for water and oil repellents, crosslinking agents, antibacterial and deodorizing agents, flame retardants, antistatic agents, softeners, anti-wrinkle agents, and the like. In particular, when treating fabrics, clothing, etc., and when preventing deterioration of water and oil repellency due to washing, it is preferable to add a crosslinking agent. Examples of the crosslinking agent include compounds having at least one of methylolmelamine, isocyanate groups, and blocked isocyanate groups. By attaching a crosslinking agent to the object to be treated and subjecting it to heat treatment, water and oil repellency can be maintained even after washing.

<Water and oil repellent treated product>
The water- and oil-repellent polymer can impart water- and oil-repellency to an object to be treated, resulting in a water- and oil-repellent treated product. Applicable materials to be treated include, for example, natural fibers such as cotton, linen, and silk, recycled fibers such as rayon and cupro, semi-synthetic fibers such as acetate and triacetate, polyamide, polyester, polyacrylonitrile, polypropylene, and polyvinyl chloride. , synthetic fibers such as polyvinyl alcohol, natural leather, synthetic leather, fur, paper, wood, mixed fibers thereof, fabrics made from these, clothing, shoes, etc., glass fibers, glass, bricks, cement, metals, plastics, etc. It will be done. Among them, particularly high effects are expressed on synthetic fibers, natural fibers, and natural leather.

As a treatment method using a water- and oil-repellent treated product, general methods such as spray coating, bar coating, and dip coating can be used. Further, after applying the water- and oil-repellent-treated material to the object to be treated, it is preferable to volatilize the liquid medium by appropriate heat treatment at room temperature and dry the object to be treated. There are no particular restrictions on the temperature conditions during drying, but in consideration of heat-induced deterioration of the object to be treated, it is preferably 20° C. to 200° C., preferably 50° C. to 150° C.

(Example 1)
First, 120 g of cyclohexane was charged into a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the inside of the flask was purged with nitrogen. Next, 30 g of 2-(perfluorohexyl)ethyl methacrylate <FMAC6> (monomer (a)), 70 g of "HUMA-2" (monomer (b1)) listed in Table 1, and 94.7 g of cyclohexane were added. A monomer solution, a polymerization initiator solution consisting of 3.3 g of tert-hexyl peroxyneodecanate and 15 g of cyclohexane were prepared. The temperature inside the reaction vessel was raised to 55°C, and a monomer solution and a polymerization initiator solution were simultaneously added dropwise over a period of 2 hours. After the dropwise addition was completed, the mixture was reacted at 55° C. for 5 hours, then heated to 70° C., and further reacted for 2 hours to obtain a solution containing the polymer.

Table 2 shows the formulation of each component in Example 1. As shown in Table 2, the structural units derived from the fluorine-containing monomer (a), the structural units derived from the non-fluorine monomer (b1), and the vinyl monomer in the polymer obtained in Example 1 The mass ratio ((a)/(b1)/(b2)) of the structural units derived from (b2) was 30/70/0.

(Examples 2 to 19)
In Examples 2 to 19, the types and amounts of monomers were changed as shown in Tables 2 to 5. Each monomer (b1) is as shown in Table 1. Except for this, the water repellent polymers of each example were produced in the same manner as in Example 1.

(Example 20)
First, in a 1L plastic container, 60g of 2-(perfluorohexyl)ethyl methacrylate <FMAC6>, 25g of "HUMA-2" listed in Table 1, 7.0g of stearyl methacrylate <SMA>, and cyclohexyl methacrylate <CHMA>. 7.0g, N-methylolacrylamide (N-MAM) 1.0g, tripropylene glycol 31.7g, water 258g, and a mixture consisting of 2.8g polyoxyethylene lauryl ether, 2.8g polyoxyethylene isodecyl ether, An emulsifier mixture consisting of 3.5 g of octadecyltrimethylammonium chloride was charged, heated to 60° C., mixed and stirred with a homomixer at 2,000 rpm for 1 minute, and then emulsified and dispersed by ultrasonic irradiation. Next, the emulsified dispersion was transferred to a 500 mL four-necked flask equipped with a thermometer, stirrer, and reflux condenser, and after purging with nitrogen, 0.2 g of lauryl mercaptan and 2,2'-azobis(2-methylpropionamidine) were added. 1.0 g of dihydrochloride was added to the dispersion and reacted at 60° C. for 6 hours to obtain an aqueous dispersion containing a polymer.

(Comparative Examples 1 to 4)
In Comparative Examples 1 to 4, the polymers of each Comparative Example were produced in the same manner as in Example 1, except that the types and amounts of monomers were changed to those listed in Table 6.

The weight average molecular weights of the polymers obtained in Examples 1 to 20 and Comparative Examples 1 to 4 were measured. Specifically, a TOSOH HLC-8320GPC was used as the GPC system, two TOSOH TSKgel Super Multipore HZ-M columns and one TOSOH TSKgel Super H-RC column were consecutively installed, the column temperature was set to 40°C, and the standard The substance was polystyrene, the developing solvent was tetrahydrofuran, the developing solvent was flowed at a flow rate of 1 ml/min, and 0.1 ml of a sample solution with a sample concentration of 0.1% by mass was injected, using the EcoSEC-Work Station GPC calculation program. It was measured

(Test piece preparation)
Polyester cloth, cotton cloth, and cowhide were used as evaluation substrates.

The polymers according to Examples 1 to 19 and Comparative Examples 1 to 4 were diluted with cyclohexane as a liquid medium to produce a solution (water and oil repellent composition) with a concentration of 2.0% by mass. Polyester taffeta cloth and cotton cloth were coated by dipping in each solution, and test pieces (water and oil repellent treated products) were prepared by heating and drying at 150° C. for 3 minutes. Regarding cowhide, each solution was applied by spraying using a spray gun, and then dried at room temperature to prepare a test piece (water and oil repellent treated product).

The polymer according to each Example 20 above was diluted with water as a liquid medium to produce a dispersion liquid (water and oil repellent composition) having a concentration of 2.0% by mass. Polyester taffeta cloth and cotton cloth were coated by immersion in each dispersion, and test pieces (water and oil repellent treated products) were prepared by heating and drying at 150° C. for 3 minutes. For cowhide, each dispersion was applied by spraying using a spray gun, and then dried at room temperature to prepare a test piece (water and oil repellent treated material).

(Water repellency test)
The water repellency of each test piece was evaluated based on JIS L 1092. Spray Tester AW-5 (manufactured by Intec Co., Ltd.) was used as the testing machine. The test piece was attached to a testing machine and 250 mL of water was sprayed on it. The wet state of the test piece after spraying was evaluated according to the criteria shown in Table 7. The higher the value, the better the water repellency. The target value of water repellency was 90 or more for polyester cloth, and 80 or more for cotton cloth and cowhide, which are difficult to impart water repellency to.

(Oil repellency test)
An oil repellency test was conducted based on AATCC Test Method 118-1997. 50 μL of hydrocarbon solvent (Table 8) was gently dropped onto the surface of the test piece, and the state of the droplet was evaluated after 30 seconds. The grade of the hydrocarbon solvent with the lowest surface tension that did not penetrate into the substrate was used as the rating point. The higher the value, the better the oil repellency. The target value for oil repellency was 5 or more for polyester fabrics, and 3 or more for cotton fabrics and cowhide leather, which are difficult to impart oil repellency to.

[Evaluation results]
Tables 2 to 5 show the evaluation results of Examples 1 to 20, and Table 6 shows the evaluation results of Comparative Examples 1 to 4.

However, the substituents of formula (8) used in monomer (b2) in Table 1 are as follows.

The abbreviations shown in Tables 2 to 6 are as follows.
FMAC6: 2-(perfluorohexyl)ethyl methacrylate FAC6: 2-(perfluorohexyl)ethyl acrylate SMA: Stearyl methacrylate CHMA: Cyclohexyl methacrylate BzMA: Benzyl methacrylate FM0721: Silaplane FM0721 manufactured by JNC (contains polydimethylsiloxane group) Macromonomer molecular weight 5,000)
FM0725: Silaprene FM0721 manufactured by JNC (polydimethylsiloxane group-containing macromonomer, molecular weight 10,000)
HEMA: 2-hydroxyethyl methacrylate PME400: Methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide: 9)
DAAM: diacetone acrylamide N-MAM: N-methylol acrylamide

As is clear from the results in Tables 2 to 5, Examples 1 to 20 exhibited excellent water and oil repellency on various base materials.

On the other hand, as is clear from Table 6, Comparative Examples 1 to 4 had insufficient water repellency or oil repellency.

Specifically, in Comparative Example 1, the fluorine-containing copolymer did not have a structural unit derived from the fluorine-containing monomer (a), so the oil repellency was poor. In Comparative Example 2, the fluorine-containing copolymer was insoluble in the hydrocarbon solvent because the ratio of the structural units derived from the fluorine-containing monomer (a) was excessive. In Comparative Examples 3 and 4, the fluorine-containing copolymer did not have a structural unit derived from the non-fluorine monomer (b1), so the water and oil repellency against natural fibers and natural leather was poor.

Claims (4)

A fluorine-containing copolymer containing a structural unit derived from a fluorine-containing monomer (a) represented by the following formula (1) and a structural unit derived from a non-fluorine monomer (b1) represented by the following formula (2) And,
When the total amount of structural units derived from all monomers is 100 parts by mass, the mass of the structural units derived from the monomer (a) is 10 to 90 parts by mass, and the mass of the structural units derived from the monomer (b1) is 10 to 90 parts by mass. A polymer for water and oil repellents, characterized in that the mass of the structural unit is 10 to 90 parts by mass.
(In formula (1), R ¹ represents a hydrogen atom or a methyl group, l is an integer of 0 to 4, and m is an integer of 0 to 5.)
(In formula (2), R ² represents a hydrogen atom, a methyl group, or a halogeno group, R ³ represents an alkyl group having 12 to 24 carbon atoms, and A represents an alkylene group having 1 to 10 carbon atoms. , X represents 0 or 1, and Y is a hydroxyurethane structure selected from the group consisting of the following formula (3), formula (4), formula (5), and formula (6).)
Contains a structural unit derived from the vinyl monomer (b2) represented by the following formula (7),
The repellent according to claim 1, characterized in that when the total amount of the structural units derived from all monomers is 100 parts by mass, the mass of the structural units derived from the monomer (b2) is 80 parts by mass or less. Polymer for water and oil repellent.
(In formula (7), R ⁴ represents a hydrogen atom, a methyl group, or a halogeno group, Z represents an oxygen atom or a nitrogen atom, and R ⁵ represents a hydrogen atom or an optionally substituted carbon number 1 ~22 hydrocarbon groups, n represents 1 when Z is an oxygen atom, and represents 2 when Z is a nitrogen atom.) A water/oil repellent composition comprising the water/oil repellent polymer according to claim 1 or 2 and a liquid medium. A water- and oil-repellent treated product, characterized in that the water- and oil-repellent polymer according to claim 1 or 2 is attached thereto.