JPWO1997047667A1 - New copolymer, its production method and use - Google Patents

Abstract

(57) [Abstract] A copolymer having (I) repeating units derived from a monomer having a fluorine atom and (II) repeating units derived from a monomer that does not contain a fluorine atom, has one or more urethane or urea bonds, and has one carbon-carbon double bond, provides good water and oil repellency, and is soluble in alcohol solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel copolymer, its production method and uses. Related Art Various water and oil repellents have been proposed in the past.

Japanese Patent Application Laid-Open No. 6-507438 discloses a water and oil repellent comprising a polymer or copolymer obtained by polymerization of a reaction product of a diisocyanate adduct with a perfluoro compound or epichlorohydrin and a (meth)acrylic ester of a compound containing three hydroxyl groups. However, the water repellency is insufficient.

Japanese Patent Application Laid-Open Nos. 6-330027 and 6-313166 disclose water- and oil-repellent base materials obtained by polymerizing or copolymerizing polymerizable α,β-monoethylenically unsaturated monomers having a backbone containing at least two monovalent groups having a perfluoroalkyl group, all of which are bonded to the same carbon atom or carbon atoms. However, the water- and oil-repellency is insufficient.

Japanese Patent Application Laid-Open No. 62-132850 discloses a water and oil repellent comprising a polymer of monomers obtained by reacting toluene-2,4-diisocyanate, a compound having a fluoroalkyl group, and an acrylic ester having a hydroxyl group. However, the water repellency is insufficient.

Japanese Patent Application Laid-Open No. 5-214325 discloses a water/oil repellent composition containing a copolymer obtained by copolymerizing at least two monomers, the essential components of which are a polyfluoroalkyl group-containing acrylate or methacrylate and a urethane bond-containing polyacrylate or polymethacrylate, and a blocked polyisocyanate compound. However, this water/oil repellent composition has poor emulsion stability and is insoluble in alcohol solvents.

Conventional water- and oil-repellent polymers have low solubility in alcoholic solvents. Furthermore, fluorine-containing urethane compounds that are relatively soluble in alcoholic solvents have low water-repellent properties. Summary of the Invention An object of the present invention is to provide a copolymer that provides good water- and oil-repellent properties and is soluble in alcoholic solvents.

The present invention provides a copolymer having (I) repeating units derived from a monomer having a fluorine atom, and (II) repeating units derived from a monomer that does not contain a fluorine atom, has one or more urethane or urea bonds, and has one carbon-carbon double bond.

The present invention also provides a treatment agent containing the copolymer and a solvent. Detailed Description of the Invention The fluorine atom-containing monomer (I) may be a (meth)acrylate having a polyfluoroalkyl group having 3 to 21 carbon atoms. The monomer (I) is represented by the formula: [wherein ^R11 is a hydrogen atom or a methyl group, and Rf is a fluoroalkyl group having 3 to 21 carbon atoms (a nitrogen atom, a sulfonyl group, or an amide group may be present between the carbon-carbon bond)]

Examples of the fluorine atom-containing monomer (I) are as follows:

CF₃(CF₂)₄CH₂OCOC(CH₃)＝CH₂ CF₃(CF₂)₇(CH₂)₂OCOC(CH₃)＝CH₂ CF₃(CF₂)₇(CH₂)₂OCOCH=CH₂ (CF₃)₂CF(CF₂)₄(CH₂)₂OCOCH=CH₂ CF₃(CF₂)₇SO₂N(C₃H₇)(CH₂)₂OCOCH=CH₂ CH₃(CF₂)₇(CH₂)₄OCOCH=CH₂ CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(CH₃)＝CH₂ CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOCH=CH₃ CF₃(CF₂)₇CONH(CH₂)₂OCOCH=CH₂ (CF₃)₂CF(CF₂)₆(CH₂)₃OCOCH=CH₂ (CF₃)₂CF(CF₂)₆CH₂CH(OCOCH₃)CH₂OCOC(CH₃)=CH₂ (CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH=CH₂ CF₃(CF₂)₉(CH₂)₂OCOCH=CH₂ CF₃(CF₂)₉(CH₂)₂OCOC(CH₃)＝CH₂ CF₃(CF₂)₉CONH(CH₂)₂OCOC(CH₃)＝CH₂ (CF₂Cl)(CF₃)CF(CF₂)₆CONH(CH₂)₂OCOCH=CH₂ H(CF₂)₁₀CH₂OCOCH=CH₂ CF₂Cl(CF₂)₁₀CH₂OCOC(CH₃)＝CH₂ Monomer (II), which does not contain fluorine atoms and has one or more urethane or urea bonds and one carbon-carbon double bond, can be obtained by reacting (A) a compound having at least two isocyanate groups, (B) a compound having one carbon-carbon double bond and at least one hydroxyl group or amino group, and (C) a compound having one hydroxyl group or amino group.

Examples of compound (A) are as follows:

Compound (A) is preferably a diisocyanate, but triisocyanates and polyisocyanates can also be used in the reaction.

For example, diisocyanate trimers, polymeric MDI (diphenylmethadiisocyanate), and adducts of diisocyanates with polyhydric alcohols such as trimethylolpropane, trimethylolethane, and glycerin can also be used in the reaction.

Examples of triisocyanates and polyisocyanates are as follows:

Compound (B) is, for example, a compound represented by the formula: The compound may be a compound represented by the formula:

In the formula, ^R1 is a hydrogen atom or a methyl group, and X is as follows:

[In the formula, m and n are numbers from 1 to 300.] Compound (C) can be, for example, a compound represented by the formula: R²-OH R²-NH₂or R²-NH-R³ [In the formula, R²and R³are the same or different, C₁~C_{twenty two}and may contain heteroatoms, aromatic compounds, or alicyclic compounds. ] Preferred R²Groups and R³The group is C₈H₁₇, C₁₇ H₃₅, C₄H₉, cyclohexyl.

Examples of compound (C) are butyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexyl alcohol, 2-ethylhexylamine, and stearylamine.

When compounds (A), (B), and (C) are reacted, if (A) is a diisocyanate, 1 mole of each of (B) and (C) may be reacted per mole of (A); if (A) is a triisocyanate, 1 mole of (B) and 2 moles of (C) may be reacted per mole of (A).

In the present invention, in addition to the monomers (I) and (II), other copolymerizable monomers may be used.

Other copolymerizable monomers may be (meth)acrylic acid esters. Examples of (meth)acrylic acid esters include 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, poly(oxyalkylene) (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, isocyanatoethyl (meth)acrylate, aziridinyl (meth)acrylate, (meth)acrylates with polysiloxanes, N,N-dimethylaminoethyl (meth)acrylate, and acetoacetoxyethyl (meth)acrylate. The use of N,N-dimethylaminoethyl (meth)acrylate improves the water repellency of cotton.

Additional examples of other copolymerizable monomers are ethylene, butadiene, isoprene, chloroprene, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol (meth)acrylamide, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, maleic anhydride, N-vinylcarbazole, and acrylonitrile.

In the copolymer of the present invention, the weight ratio of monomer (I) to monomer (II) is 5:95 to 95:5, preferably 20:80 to 95:5. The amount of other copolymerizable monomers is 90% by weight or less, for example, 5 to 90% by weight, of the copolymer. The molecular weight of the copolymer may be 500 to 1,000,000.

The copolymers can be prepared by solution, emulsion or suspension polymerization.

The copolymers of the present invention can be prepared by solution polymerization in an organic solvent. Examples of such organic solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; alcohols such as ethanol, isopropanol, butanol, 1,3-butanediol, and 1,5-pentanediol; halogenated hydrocarbons such as perchloroethylene, trichlene, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,2,2,3,3-pentafluoropropane, and 1,1-dichloro-1-fluoroethane (HCFC-141b); hydrocarbons such as octane, petroleum, toluene, and xylene; dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, triethylene glycol dimethyl ether, propylene glycol, and ethylene glycol.

Preferred organic solvents include ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, and 1,1-dichloro-1-fluoroethane.

The copolymers of the present invention can also be produced in an aqueous emulsion. The monomers are emulsion-polymerized using water, an emulsifier, and, if necessary, an organic solvent. The mixture may also be pre-emulsified using a high-pressure emulsifier or the like before polymerization.

As the emulsifier, various anionic, cationic or nonionic surfactants can be used.

Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, and perfluoroalkyl carboxylates (trade names: Unidyne DS-101 and 102, manufactured by Daikin Industries, Ltd.).

Examples of cationic surfactants include dialkyl ( _C12 to _C22 ) dimethyl ammonium chloride, alkyl (coconut) dimethyl benzyl ammonium chloride, octadecyl amine acetate, tetradecyl amine acetate, tallow alkyl propylene diamine acetate, octadecyl trimethyl ammonium chloride, alkyl (coconut) trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl (coconut) imidazoline quaternary salt, tetradecyl methyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, polyoxyethylene dodecyl monomethyl ammonium chloride, polyoxyethylene alkyl ( _C12 to _C22 ) benzyl ammonium chloride, polyoxyethylene lauryl monomethyl ammonium chloride, 1- Examples include hydroxyethyl-2-alkyl (beef tallow) imidazoline quaternary salt, silicone-based cationic surfactants having a siloxane group as the hydrophobic group, and fluorine-based cationic surfactants having a fluoroalkyl group as the hydrophobic group (trade name: Unidyne DS-202 (manufactured by Daikin Industries, Ltd.)).

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl 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, and polyoxyethylene sorbitan monolaurate. ester, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene polyoxypropylene block polymer, polyglycerin fatty acid ester, polyether-modified silicone oil (trade names: SH3746, SH3748, SH3749, SH3771 (manufactured by Dow Corning Toray Silicone Co., Ltd.)), perfluoroalkyl ethylene oxide adduct (trade name: Unidyne DS-401, DS-403 (manufactured by Daikin Industries, Ltd.)), fluoroalkyl ethylene oxide adduct (trade name: Unidyne DS-406 (manufactured by Daikin Industries, Ltd.)), perfluoroalkyl oligomer (trade name: Unidyne DS-451 (manufactured by Daikin Industries, Ltd.)), etc.

Examples of organic solvents used in emulsion polymerization are the same as those used in solution polymerization.

In the polymerization, a polymerization initiator, ionizing radiation such as gamma rays, or the like is used to initiate the polymerization. Examples of polymerization initiators include organic peroxides, azo compounds, and persulfates.

Examples of organic peroxides include t-butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, and diisopropyl peroxydicarbonate. Examples of azo compounds include 2,2'-azobisisobutyronitrile and 2,2'-azobis(2-methylbutyronitrile).

The copolymer of the present invention can be used as a treatment agent. The treatment agent may be a water- and oil-repellent agent. The treatment agent contains the copolymer and a solvent. The solvent may be water, an alcohol (e.g., an alkanol), a ketone, an ester, an ether (e.g., a glycol ether), or a mixture thereof. The solvent used in the treatment agent and the solvent used in polymerization may be different. When the solvent used in the treatment agent and the solvent used in polymerization are different, the polymerization solvent is removed (by evaporation or the like) before the treatment agent is prepared.

Alcohols used in the treatment agent include lower alkanols having 1 to 4 carbon atoms, such as methanol, ethanol, 2-propanol, and n-butanol. Of these lower alkanols, ethanol and 2-propanol are preferred from a safety standpoint. Alkanols with 5 or more carbon atoms are not preferred because they have poor drying properties. These lower alkanols can be used alone or in combination.

Solvents such as isoparaffin, n-heptane, n-hexane, mineral turpentine, ethyl acetate, toluene, methyl ethyl ketone, and methyl isobutyl ketone can also be added as long as they are not too dangerous. Alternative fluorocarbons, such as CFC 141b, may also be used. Adding small amounts of glycol ethers, such as dipropylene glycol monomethyl ether, is also effective in preventing whitening.

In the aerosol concentrate, the weight ratio of copolymer to solvent may be from 0.05:99.95 to 5.0:95.0, preferably from 0.1:99.9 to 3.0:97.0.

The treatment agent of the present invention can be blended with various additives as needed. Among these, organopolysiloxane is important because it can enhance water repellency. As organopolysiloxane, silicone oil, silicone dispersion, or a mixture thereof can be used. Silicone oil is most commonly represented by the following formula: These dimethylpolysiloxanes are available with various degrees of polymerization and have viscosities at 25°C ranging from 0.65 to 300,000 cs.

In addition, a small amount of the following group is present in the main chain: Some include:

Other examples include those in which —( _CH3 ) _2SiO— is replaced with —( _CH3CH2 ) _2SiO— , —( _CH3 )HSiO—, —( _C6H5 ) _2SiO— , —( _C6H5 )( _CH3 )SiO—, and mixtures _thereof . There are also those in which the end of the Si _{- O} -Si main chain is substituted with a hydroxyl group. Furthermore, there are those in which the side chains of these are chlorinated, and various modified silicone oils in which amino groups, epoxy groups, polyether groups, carboxyl groups, hydroxyl groups, trifluoroalkyl groups, alcohol ester groups, alkyl groups, etc. are introduced into the side chains. Silicone dispersions are silicone resins or silicone rubbers in an early polymerization state dissolved in a solvent, and when heated, condense to form a coating with a three-dimensional network structure. In addition to the above, various organopolysiloxanes can be used in the present invention. Many types of these organopolysiloxanes are commercially available, including SH 200, PRX413, SH8011, SD8000 (product names of Toray Dow Corning Silicone Co., Ltd.), KP-801M, and KPN-3504 (product names of Shin-Etsu Chemical Co., Ltd.). The amount of organopolysiloxane blended is about 0.05 to about 10% by weight, preferably about 0.5 to 5% by weight, based on the aerosol concentrate.

The treatment agent of the present invention may further contain, as necessary, stain inhibitors, UV inhibitors, surfactants, bactericides, insect repellents, antistatic agents, fragrances, etc., as described in Japanese Patent Publication Nos. 62-6163 and 63-33797. Furthermore, for the purposes of softening the treated fabric, preventing static buildup, improving water and oil repellency, and improving shrink resistance, antistatic agents, aminoplast resins, acrylic polymers, glyoxal resins, melamine resins, natural waxes, silicone resins, etc., may also be incorporated to the extent that the effects of the present invention are not impaired.

The treatment agent of the present invention may be prepared in any desired form, such as an emulsion, a solvent solution, or an aerosol, by conventional methods. For example, an aqueous emulsion composition may be prepared by emulsion polymerization as described above, and a solvent solution composition or an aerosol composition may be prepared by solution polymerization.

The treatment agent of the present invention is preferably used as an aerosol. The treatment agent of the present invention can be easily aerosolized by adding a propellant to the concentrate and filling a container. Propellant sources include liquefied petroleum gas (LPG), propane, butane, dimethyl ether, carbon dioxide, and nitrogen gas. Alternative chlorofluorocarbons, such as HFC-134a and HCFC-141b, can also be used as needed. The weight ratio of concentrate to propellant is 99.5/0.5 to 30/70, preferably 99/1 to 50/50.

The water/oil repellent composition of the present invention can be used to treat a wide variety of substrates, including, but not limited to, textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Examples of textiles include natural fibers of animal and vegetable origin, such as cotton, linen, wool, and silk; various synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fibers and asbestos fibers; and blends of these fibers, as well as yarns and fabrics (woven, nonwoven, and knitted) made from these fibers. The following examples and comparative examples illustrate the present invention in more detail. Unless otherwise specified, all parts are by weight.

The water and oil repellency shown in the following examples and comparative examples are expressed on the following scale: Water repellency is expressed as a water repellency number (see Table 1 below) according to the spray method of JIS L-1092. Oil repellency is expressed as an oil repellency number (AATCC TM118-1992) based on whether a drop (approximately 5 mm in diameter) of the test solution shown in Table 2 below is placed on the sample fabric and left on for 30 seconds. A "+" next to the water repellency number indicates slightly better performance, and a "-" indicates slightly worse performance.

The stain resistance test was carried out in accordance with JIS L 1023-1992. First, a carpet was stained with dry soil having the composition shown in Table 3 in accordance with JIS L 1023-1992.

Thereafter, the excess dry soil on the surface is vacuumed up, and the brightness of the surface is measured using a color difference meter. The soiling rate is calculated using the following formula to evaluate the dry soil antifouling property.

Contamination rate (%) = [(Lo - L) / Lo] x 100 (where Lo is the brightness before contamination, and L is the brightness after contamination). Preparations of monomers containing urethane bonds are shown in Preparation Examples 1 to 4. Preparation Example 1 (Preparation of Product U1) : In a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, 348 g of 2,4-tolylene diisocyanate was dissolved in 348 g of methyl isobutyl ketone (MIBK). The mixture was heated to 80°C with nitrogen purging and stirring. When the temperature reached 80°C, 2 drops of dibutyltin laurate were added, and simultaneously, 260 g of 2-ethylhexyl alcohol was added dropwise, slowly over 2 hours. After the addition, 260 g of 2-hydroxyethyl methacrylate was added dropwise over 2 hours. After the addition, stirring was continued for another 2 hours, maintaining the temperature at 80°C. The MIBK was then distilled off under reduced pressure, yielding 868 g of a pale yellow, transparent, viscous liquid. Complete disappearance of the -NCO group was confirmed by IR, and disappearance of the -OH group, formation of a urethane bond, and presence of a double bond were confirmed by ¹ H-NMR and ¹³ C-NMR. This product is designated U1.

The chemical formula of product U1 is believed to be: Production Example 2 (Production of Product U2) The reaction was carried out in the same manner as in Production Example 1, except that the order in which 2-ethylhexyl alcohol and 2-hydroxyethyl methacrylate were added dropwise was reversed (2-hydroxyethyl methacrylate was added dropwise first). This product is designated as U2.

The chemical formula of product U2 is believed to be: Production Example 3 (Production of Product U3) A reaction was carried out in the same manner as in Production Example 1, except that a solution of 500 g of diphenylmethane diisocyanate (MDI) in 500 g of MIBK was used instead of a solution of 348 g of 2,4-tolylene diisocyanate in 348 g of MIBK. This product is designated as U3.

The chemical formula of product U3 is believed to be: Production Example 4 (Production of Product U4) A reaction was carried out in the same manner as in Production Example 1, except that a solution of 336 g of hexamethylene diisocyanate (HDI) in 336 g of MIBK was used instead of a solution of 348 g of 2,4-tolylene diisocyanate in 348 g of MIBK. This product is designated as U4.

The chemical formula of product U4 is believed to be:

In the following production examples, the monomers shown in Table 4 were used.

Production Example 5: Into a flask equipped with a stirrer, a thermometer, and a reflux condenser, 120 g of Monomer I (fluoroacrylate) shown in Table 4 and 80 g of U1 (urethane bond-containing monomer) synthesized in Production Example 1 were charged and dissolved in 800 g of MIBK. The mixture was heated to 60° C. while stirring and purging with nitrogen.

One hour after the start of nitrogen purging, the internal temperature was confirmed to be 60°C, and 4 g of t-butyl peroxypivalate (trade name: Perbutyl PV, manufactured by NOF Corporation) was added to initiate polymerization.

Eight hours after the start of polymerization, it was confirmed by gas chromatography that 99% of Monomer I had reacted, and a pale yellow liquid with a solid content of 20% was obtained. As a result of GPC measurement, this solid content had a number average molecular weight of 5,000 (polystyrene equivalent). Production Examples 6 to 17 and Comparative Production Examples 1 and 2 : Fluorine-containing acrylates, urethane bond-containing monomers, and other monomers were polymerized in the same manner as in Production Example 5 using the combinations shown in Table 5.

However, in the production examples using monomer IV, AIBN (azobisisobutyronitrile) was used as the polymerization initiator, and the polymerization temperature was 80°C.

Example 1 The solution obtained in Production Example 5 was diluted with isopropyl alcohol (IPA) to a solid content of 1%, and the solubility in IPA at low temperatures was measured. The solution was then used to treat a cloth, and the water and oil repellency was measured.

The test was carried out on polyester tropical fabric (white fabric), nylon taffeta fabric (white fabric), and cotton broadcloth fabric (white fabric).

A cloth was immersed in the diluted solution as described above, squeezed with a mangle so that the wet pick-up was about 40%, and dried at room temperature for 1 hour. Examples 2 to 13: The water and oil repellency was measured in the same manner as in Example 1 using the polymers shown in Table 6. Comparative Examples 1 and 2 : The water and oil repellency was measured in the same manner as in Example 1 using the solutions obtained in Comparative Preparation Examples 1 and 2. Comparative Example 3: A polymer was prepared in the same manner as in Examples 2 and 10 of JP-A-6-507438, and this polymer was diluted with IPA to a solids content of 1%, and the water and oil repellency was measured in the same manner as in Example 1.

○ = Dissolved △ = Slightly cloudy but stable × = Sedimentation occurs Examples 14 to 26 and Comparative Example 4 The products obtained in Examples 1 to 13 and Comparative Example 3 were filled into uncoated tin cans with the following compositions using carbon dioxide gas as a propellant to prepare aerosol products.

- Stock solution composition: Solids 1.0%, MIBK 5.0% , IPA 94.0%, Total 100% - Aerosol composition: Stock solution 96.3% , Carbon dioxide 3.7% , Total 100% Test fabrics (polyester tropical, cotton broadcloth, nylon taffeta) were cut into 20cm x 20cm pieces, sprayed with aerosol for 4 seconds, and dried at room temperature for 1 hour to prepare samples for water and oil repellency tests. The test results are shown in Table 7. Comparative Example 5 : Aerosol was prepared as in Example 1 of JP-A-6-313166, and a water and oil repellency test was conducted. The test results are shown in Table 7. Comparative Example 6 : Aerosol was prepared as in Example 9 of JP-A-6-313166, and a water and oil repellency test was conducted. The test results are shown in Table 7.

Production Example 18: 120 g of Monomer I (fluorine-containing acrylate) shown in Table 4 and 80 g of U1 (urethane bond-containing monomer) synthesized in Production Example 1 were dissolved in 20 g of methyl isobutyl ketone (MIBK), followed by the addition of 12 g of sodium α-olefin sulfonate, 8 g of polyoxyethylene nonylphenyl ether, and 880 g of ion-exchanged water, followed by pre-emulsification using a high-pressure homogenizer. The resulting emulsion was transferred to a flask equipped with a stirrer, thermometer, and reflux condenser, and thoroughly purged with nitrogen at 60°C. Then, 1.1 g of ammonium persulfate was added to initiate polymerization. Ten hours after the start of polymerization, gas chromatography confirmed that 99% of Monomer I had reacted, yielding an emulsion with a solids concentration of 20%. Comparative Production Example 3 : Emulsion polymerization was carried out in the same manner as Production Example 18, except that Monomer VIII was used in place of Monomer U1, to yield an emulsion with a solids concentration of 20%. Production Example 19: 120 g of Monomer I (fluorine-containing acrylate), 20 g of Monomer U1, and 60 g of Monomer VIII shown in Table 4 were charged into a flask equipped with a stirrer, thermometer, and reflux condenser, dissolved in 800 g of n-octane, and the temperature was raised to 60°C while stirring and purging with nitrogen. One hour after the start of nitrogen purging, 4 g of t-butyl peroxypivalate was added to initiate polymerization. Eight hours after the start of polymerization, gas chromatography confirmed that more than 99% of Monomers I and VIII had reacted, yielding a pale yellow liquid with a solids concentration of 20%. Comparative Production Example 4 : Solution polymerization was carried out as in Production Example 19, except that 80 g of Monomer VIII was charged instead of 20 g of Monomer U1 and 60 g of Monomer VIII, yielding a colorless, transparent liquid with a solids concentration of 20%. Example 27 The emulsion obtained in Preparation Example 18 was diluted with water to a solids content of 3%, and the solution was sprayed uniformly onto a nylon loop pile carpet fabric (without a backing) at 100 g/ ^m² . A hand spray was used for spraying. The carpet was then dried at 130°C for 5 minutes. Oil repellency and stain resistance tests were conducted on this treated carpet.

The test results are shown in Table 8. Example 28 The emulsion obtained in Production Example 18 and a polymethyl methacrylate/ethyl methacrylate (MMA/EMA weight ratio = 80/20 wt ratio) emulsion described in JP-A-8-3113 were mixed in a solids weight ratio of 1:1, and then diluted with water to a solids content of 3%, and tested as in Example 27. The results are shown in Table 8. Comparative Example 7 The emulsion obtained in Comparative Production Example 3 was used, and a test was carried out in the same manner as in Example 27.

The results are shown in Table 8. Example 29 The solution of Production Example 19 was diluted with n-octane to a solids concentration of 10 wt %, and 50 g of each was allowed to stand in thermostatic baths at 10°C, 0°C, -5°C, and -10°C for 24 hours, after which the state was observed.

The results are shown in Table 9. Comparative Example 8 The solution of Comparative Production Example 4 was diluted with n-octane to a solids concentration of 10 wt %, and 50 g of each was left in thermostatic baths at 10°C, 0°C, -5°C, and -10°C for 24 hours, after which the state was observed. The results are shown in Table 9.

EFFECTS OF THE INVENTION The copolymer of the present invention has good solubility in alcohol solvents and good water and oil repellency.

─────────────────────────────────────────────────────── Continued from the front page (51) Int.Cl. ⁶ Identification Symbol FI C08L 33/16 C09D 133/16 C09K 3/18 (Note) This publication has been created based on the gazette published internationally by the International Bureau (WIPO). The effect of the international publication of the Japanese language patent application (Japanese language utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act), and is unrelated to this publication.

Claims (5)

[Claims] 1. A copolymer having (I) repeating units derived from a monomer having a fluorine atom, and (II) repeating units derived from a monomer that does not contain a fluorine atom, has one or more urethane or urea bonds, and has one carbon-carbon double bond. 2. The copolymer according to claim 1, wherein monomer (II) is a monomer obtained by reacting (A) a compound having at least two isocyanate groups, (B) a compound having one carbon-carbon double bond and at least one hydroxyl group or amino group, and (C) a compound having one hydroxyl group or amino group. 3. A treating agent comprising the copolymer according to claim 1 and a solvent. 4. The treatment agent according to claim 3, which is in the form of a solution, emulsion or aerosol. 5. A method for producing the copolymer of claim 1, wherein the copolymerization is carried out in an organic solvent solution or in an aqueous emulsion.