JP2015105287A - Water- and oil-repellent agent composition and method for producing water- and oil-repellent product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water- and oil-repellent composition that has a sufficient stability of a water- and oil-repellent component and a sufficient stability of a treatment liquid and imparts a desired water- and oil-repellency, durability of the water- and oil-repellency, and touch feeling to a fiber product when treated the fiber product with the water- and oil-repellent composition, while the water- and oil-repellent component of the water- and oil-repellent composition has a perfluoroalkyl group having carbon atoms of 6 or less.SOLUTION: A water- and oil-repellent composition includes a copolymer obtained by copolymerizing a monomer composition comprising: a monomer represented by following general formula (1); at least one monomer (B) selected from an alkyl(meth)acrylate (B) having 16 to 22 carbon atoms; at least one monomer (C) selected from the group consisting of vinyl chloride monomer and vinylidene chloride; at least one monomer (D) selected from the group consisting of diglycidyl methacrylate, hydroxyethyl methacrylate, N-methylol methacrylamide, and 3-chloro-2-hydroxypropyl methacrylate. CF(CH)OC(O)C(CH)=CH...(1) [In the formula (1), n represents 2 or 3.].

Description

  The present invention relates to a water / oil repellent composition capable of imparting water / oil repellency to a fiber product and a method for producing a water / oil repellent fiber product.

  Conventionally, a water / oil repellent component having a perfluoroalkyl group having 8 or more carbon atoms has been used for the purpose of imparting water / oil repellency to textiles.

In recent years, a water- and oil-repellent component having a perfluoroalkyl group having 8 carbon atoms is perfluorooctane sulfonic acid (C ₈ H ₁₇ SO _2), which has been concerned about degradation when it is discharged into the environment. F, hereinafter referred to as PFOS) and perfluorooctanoic acid (C ₇ H ₁₅ COOH, hereinafter referred to as PFOA) may be generated. As the carbon number of the perfluoroalkyl group increases, there is a greater concern about the impact on the environment. PFOS, PFOA, perfluoroalkanesulfonic acid having more than 8 carbon atoms and perfluoroalkanoic acid are not generated. Alternatives to water- and oil-repellent components having an alkyl group are being studied.

  As a water / oil repellent component having a perfluoroalkyl group having 6 or less carbon atoms, for example, the following Patent Documents 1 and 2 contain (meth) acrylate having a perfluoroalkyl group having 6 or less carbon atoms as a copolymer component. A water / oil repellent composition comprising a copolymer is disclosed.

Republished 2002-083809 Republished 2004-035708

  A water / oil repellent component having a perfluoroalkyl group having 6 or less carbon atoms tends to be inferior in water / oil repellency and durability compared to those having 8 or more carbon atoms. In Patent Documents 1 and 2, a specific monomer containing a polyfluoroalkyl group and a specific monomer not containing a polyfluoroalkyl group are used in order to improve the durability of the water and oil repellency and the texture of the workpiece. Copolymerization with monomers is described.

  However, when the amount of the monomer having a perfluoroalkyl group in the copolymer is the same, when the carbon number is 6 or less, compared with the case where the carbon number is 8 or more, sufficient results are not obtained, In order to obtain a water / oil repellency equivalent to or close to that of a case where the number of carbon atoms is 8 or more by using a monomer having a perfluoroalkyl group having a number of carbon atoms of 6 or less, perfluoro having a carbon number of 6 or less It is necessary to increase the compounding amount of the monomer having an alkyl group to improve the performance. In this case, in addition to the problem of cost increase, the texture and stability of the composition containing the copolymer (water / oil repellency) The present inventors have found that the stability (component stability) when used as a predetermined treatment liquid (treatment liquid stability) is insufficient, and problems such as processing spots and equipment contamination occur when processing into fiber products. Found. Further, in the conventional copolymer, particularly in the region where the blending amount of the monomer having a perfluoroalkyl group having 6 or less carbon atoms is small, the water and oil repellency and its property are compared with the case where the carbon number is 8 or more. The difference in durability performance was significant, and the texture, water / oil repellency component stability and treatment liquid stability were not sufficiently improved in some cases.

  The present invention has been made in view of the above circumstances, and has sufficient water and oil repellent component stability and treatment liquid stability while being a water and oil repellent component having a perfluoroalkyl group having 6 or less carbon atoms. A water / oil repellent composition capable of providing desired water / oil repellency and durability and texture when the fiber product is treated and a method for producing a water / oil repellent fiber product using the same The purpose is to do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a specific monomer composition containing a specific monomer having a perfluoroalkyl group having 6 carbon atoms as a water / oil repellent component. The water / oil repellent composition containing a copolymer obtained by copolymerizing the product has sufficient water / oil / oil repellent component stability and treatment liquid stability, and when the fiber product is treated, the number of carbon atoms is 8 It has been found that water and oil repellency, durability and texture equivalent to those described above can be provided, and the present invention has been completed based on this finding.

The water / oil repellent composition of the present invention is at least one monomer selected from a monomer (A) represented by the following general formula (1) and an alkyl (meth) acrylate having 16 to 22 carbon atoms. (B), at least one monomer (C) selected from the group consisting of vinyl chloride monomer and vinylidene chloride, glycidyl methacrylate, hydroxyethyl methacrylate, N-methylol methacrylamide and 3-chloro-2-hydroxypropyl It contains a copolymer obtained by copolymerizing a monomer composition containing at least one monomer (D) selected from the group consisting of methacrylates.
_{C 6 F 13 (CH 2)} n OC (O) C (CH 3) = CH 2 ... (1)
[In formula (1), n represents 2 or 3. ]

  According to the water / oil repellent composition of the present invention, it is possible to have sufficient water / oil / oil repellent component stability and treatment liquid stability by containing the copolymer having the above-described structure, and to treat a textile product. In this case, desired water / oil repellency and durability and texture can be provided. Further, according to the water / oil repellent composition of the present invention, sufficient water / oil repellent component stability and treatment liquid stability are obtained even when the proportion of the monomer (A) in the copolymer is reduced. It is also possible to maintain water and oil repellency and durability and texture equivalent to those of 8 or more carbon atoms.

  In the water / oil repellent composition of the present invention, the monomer (B) is stearyl acrylate and / or stearyl methacrylate from the viewpoints of water / oil repellency and durability, texture, treatment liquid stability, etc. The body (C) is preferably a vinyl chloride monomer.

  In addition, the monomer composition is based on the total amount of monomers, the monomer (A) is 1 to 35% by mass, the monomer (B) is 40 to 90% by mass, and the monomer (C) is It is preferable to contain 1-20 mass% and 0.1-5 mass% of monomers (D).

  In a conventional copolymer using a monomer having a perfluoroalkyl group having 6 or less carbon atoms as a copolymer component, the ratio of the monomer having a perfluoroalkyl group having 6 or less carbon atoms is 1 to 35 mass%. %, The difference in performance from the case where the number of carbon atoms is 8 or more, particularly the difference in water and oil repellency and durability, is further increased, and the desired water and water repellency compared to the case where the ratio exceeds 35% by mass. The inventors of the present invention have found that it is difficult to obtain oiliness, durability and texture, and water / oil repellency component stability and treatment liquid stability.

  According to the present invention, even when the ratio of the monomer having a perfluoroalkyl group having 6 or less carbon atoms is 1 to 35% by mass, sufficient water and oil repellency component stability and treatment liquid stability When the textiles are treated, a water / oil repellent composition capable of providing desired water / oil repellency and durability and texture can be provided. According to such a composition, water / oil repellency, durability and texture equivalent to those having 8 or more carbon atoms can be provided.

  The present invention also provides a method for producing a water / oil repellent fiber product comprising a step of treating a fiber product with a treatment liquid containing the water / oil repellent composition according to the present invention.

  According to the present invention, when a fiber product is processed, it has sufficient water and oil repellency component stability and treatment liquid stability while being a water and oil repellency component having a perfluoroalkyl group having 6 or less carbon atoms. Further, it is possible to provide a water / oil repellent composition capable of imparting desired water / oil repellency, durability and texture thereof, and a method for producing a water / oil repellent fiber product using the same.

  Hereinafter, the present invention will be described in detail. In this specification, alkyl (meth) acrylate means both alkyl acrylate and alkyl methacrylate.

The water / oil repellent composition of this embodiment is at least one monomer selected from a monomer (A) represented by the following general formula (1) and an alkyl (meth) acrylate having 16 to 22 carbon atoms. Body (B), at least one monomer (C) selected from the group consisting of vinyl chloride monomer and vinylidene chloride, glycidyl methacrylate, hydroxyethyl methacrylate, N-methylol methacrylamide and 3-chloro-2-hydroxy It contains a copolymer obtained by copolymerizing a monomer composition containing at least one monomer (D) selected from the group consisting of propyl methacrylate.
_{C 6 F 13 (CH 2)} n OC (O) C (CH 3) = CH 2 ... (1)
In formula (1), n represents 2 or 3.

  The monomer (A) preferably has n = 2 from the viewpoints of performance and availability.

  The monomer (A) can be obtained, for example, by an esterification reaction between perfluorohexyl ethyl alcohol and methacrylic acid. Moreover, commercially available products such as Cheminox FAMAC-C (manufactured by Unimatec), 2- (perfluorohexyl) -ethyl methacrylate (manufactured by Daikin Chemicals Sales), 2- (perfluorohexyl) -ethyl methacrylate (manufactured by Aldrich) Product can be used.

  The monomer (B) is an alkyl (meth) acrylate having an alkyl moiety having 16 to 22 carbon atoms, but from the viewpoints of water and oil repellency and its durability, texture, and processing solution stability, stearyl acrylate and Stearyl methacrylate is preferable, and a mixture of stearyl acrylate and stearyl methacrylate is more preferable.

  In the case of using a mixture of stearyl acrylate and stearyl methacrylate, from the viewpoint of texture and processing solution stability, the compounding ratio of stearyl acrylate and stearyl methacrylate is a mass ratio, stearyl acrylate: stearyl methacrylate = 55: 45-90: 10. It is preferable that it is and it is more preferable that it is 60: 40-80: 20.

  The monomer (C) is at least one selected from the group consisting of a vinyl chloride monomer and vinylidene chloride, and is preferably a vinyl chloride monomer from the viewpoint of water and oil repellency and durability.

  The monomer (D) is at least one selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, N-methylol methacrylamide and 3-chloro-2-hydroxypropyl methacrylate. Among these, at least one selected from the group consisting of N-methylol methacrylamide and 3-chloro-2-hydroxypropyl methacrylate is preferable from the viewpoint of water / oil repellency and durability.

  N-methylol methacrylamide can be suitably used when a melamine compound is used in combination to develop durable water and oil repellency. Glycidyl methacrylate, hydroxyethyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate can be suitably used when an isocyanate compound is used in combination to develop durable water and oil repellency.

  In this embodiment, the monomer composition has a monomer (A) of 1 to 35% by mass, a monomer (B) of 40 to 90% by mass, and a monomer (A It is preferable to contain 1 to 20% by mass of C) and 0.1 to 5% by mass of monomer (D).

  In this case, when the blending amount of the monomer (A) is less than 1% by mass, it tends to be difficult to develop good water / oil repellency. From the viewpoint of obtaining desired water and oil repellency, in particular, water repellency equivalent to that having 8 or more carbon atoms and durability thereof, the blending amount of the monomer (A) is more preferably 10 to 35% by mass. preferable.

  When the blending amount of the monomer (B) is less than 40% by mass, the texture tends to be hardened, and when it exceeds 90% by mass, it tends to be difficult to develop good water / oil repellency.

  When the blending amount of the monomer (C) is less than 1% by mass, the water repellency and its durability tend to decrease. When it exceeds 20% by mass, the texture is hardened and the stability of the water / oil repellency component decreases. There is a tendency for the stability of the processing solution to decrease. From the viewpoints of water / oil repellency and durability, texture, water / oil repellency component stability, and processing solution stability, the blending amount of the monomer (C) is more preferably 5 to 15% by mass.

  When the blending amount of the monomer (D) is less than 0.1% by mass, the water repellency and its durability tend to decrease. When it exceeds 5% by mass, the water / oil repellency and its durability decrease There is a tendency for the texture to harden, the water / oil repellency component stability to decrease, and the treatment liquid stability to decrease. From the viewpoints of water / oil repellency and durability, texture, water / oil repellency component stability, and processing solution stability, the blending amount of the monomer (D) is more preferably 0.1 to 3% by mass. Still more preferably, it is 0.3-1 mass%.

  The copolymer according to the present embodiment is water and oil repellency and its durability, texture, water / oil repellency component stability, and the above-mentioned monomers (A) to Other copolymerizable monomers other than (D) may be used.

Other monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, ethylene, vinylidene halides other than vinylidene chloride, alkyls other than styrene, stearyl and behenyl (C ₁ -C _{21) (meth)} acrylate, benzyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, butadiene, polyoxyethylene di (meth) acrylate, trimethoxysilyl (meth) acrylate, blocked isocyanate group-containing (Meth) acrylate etc. which have silicones, such as (meth) acrylate, vinylsilane, and trimethoxysilyl (meth) acrylate, in a side chain are mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types.

  In the copolymer according to the present embodiment, the content of other monomers contained in the monomer composition to be copolymerized is water / oil repellency and its durability, texture, water / oil repellency component stability, From the viewpoint of processing solution stability, it is preferably 15% by mass or less, more preferably 5% by mass or less, based on the total amount of monomers.

  In the copolymer according to this embodiment, the arrangement of monomers (structural units) is not particularly limited, and may be a random copolymer, a block copolymer, or an alternating copolymer.

  The copolymer according to this embodiment preferably has a melt viscosity at 105 ° C. of 5 to 20000 Pa · s, and more preferably 10 to 10,000 Pa · s. When the melt viscosity is less than 5 Pa · s, there is a tendency to decrease water repellency and its durability, and when it exceeds 20000 Pa · s, there is a tendency to decrease water repellency and its durability, texture hardening, and stability of processing liquid. .

  The melt viscosity can be measured at a measurement temperature of 105 ° C. using a flow tester CFT-500D (manufactured by SHIMADZU).

  The copolymer according to this embodiment can be obtained by applying a conventionally known copolymerization method. Examples thereof include a solution polymerization method using an organic solvent as a solvent, and an emulsion polymerization method using water as a solvent and containing an organic solvent and various surfactants.

  Examples of organic solvents include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, 2-ethylhexanol, glycerin; ethylene glycol, diethylene glycol , Glycols such as triethylene glycol, propylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, diethylene glycol monobutyl ether, triethylene glycol Glycol ethers such as monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; n- Hydrocarbons such as hexane, isohexane, cyclohexane, methylcyclohexane, n-heptane, isooctane, n-decane, mineral terpene, turpentine oil, isoparaffin, toluene, xylene, solvent naphtha; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, Ketones such as cyclohexanone and diacetone alcohol; ethyl acetate, methyl acetate, butyl acetate, Esters such as methyl acid and ethyl lactate; ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbitol, tetrahydrofuran; acetonitrile, n-methylpyrrolidone, dimethylformamide , DMSO, propylene carbonate, dimethyl carbonate, halogen compounds, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, etc. Among them, water / oil repellency, water / oil repellency component stability, treatment liquid stability And at least one selected from the group consisting of glycols and glycol ethers from the viewpoint of the property and permeability of the treatment liquid into the fiber product. Tripropylene glycol and polypropylene glycol (average molecular weight 200 to 4000) are more preferable from the viewpoint of water / oil repellency component stability, and diethylene glycol monobutyl ether is more preferable from the viewpoint of treatment liquid stability.

  Such a solvent can be used individually by 1 type or in combination of 2 or more types. When using in combination of 2 or more types, it is preferable to mix and use with water. Use of a mixed solvent is preferable because the solubility and emulsification dispersibility of the copolymer can be easily controlled, and the permeability to the fiber product can be easily controlled during processing.

  As the surfactant, it is preferable to use a nonionic surfactant, a cationic surfactant, an amphoteric surfactant or the like.

  Nonionic surfactants include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and polypropylene glycol.

  Examples of alcohols include linear or branched alcohols having 8 to 24 carbon atoms or alkenols. Examples of the polycyclic phenols include monovalent phenols such as phenol and naphthol, which may have a hydrocarbon group having 1 to 12 carbon atoms, or styrenes thereof (for example, styrene, α-methylstyrene, vinyltoluene). Etc.) adducts or their benzyl chloride reactants. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms. Examples of amides include linear or branched fatty acid amides having 8 to 44 carbon atoms. Examples of fatty acids include linear or branched fatty acids having 8 to 24 carbon atoms. Examples of the polyhydric alcohol fatty acid esters include a condensation reaction product of a polyhydric alcohol and a linear or branched fatty acid having 8 to 24 carbon atoms. Examples of the oils and fats include vegetable oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, hydrogenated oils, and the like. Among these, from the viewpoints of little influence on water and oil repellency, little influence on light resistance, and good emulsifiability of the copolymer, linear or branched alcohol having 8 to 24 carbon atoms or alkenol. Are preferred, and linear or branched alcohols having 8 to 24 carbon atoms are more preferred.

  Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin and the like. From the viewpoints of little influence on water and oil repellency and good emulsifiability of the copolymer, the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, more preferably ethylene oxide.

  The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the added mole number of alkylene oxide is less than 1 mole, product stability and water / oil repellency tend to be lowered, and when it exceeds 200 moles, water / oil repellency tends to be lowered.

  In the copolymer according to this embodiment, when a nonionic surfactant having an HLB of 8 to 16 is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, HLB is based on HLB of Griffin, and the hydrophilic group refers to an ethylene oxide group.

  These nonionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type. When using 2 or more types in combination, a better aqueous dispersion can be obtained when a nonionic surfactant is used so that the weighted average HLB is 8-16.

  Examples of the cationic surfactant include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, and dialkylamines having 8 to 24 carbon atoms. Examples thereof include acetates and alkyl imidazoline quaternary salts having 8 to 24 carbon atoms.

  These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  The above-mentioned various surfactants may be used alone or in combination of two or more, but the emulsifying dispersibility of the monomer during copolymerization, the emulsifying dispersibility of the copolymer From the viewpoint of the stability of the treatment liquid and water / oil repellency, it is preferable to use a nonionic active agent or a nonionic active agent in combination with a cationic active agent, and it is more preferable to use a nonionic active agent in combination with a cationic active agent.

  Such a surfactant is preferably contained in an amount of 3 to 20% by mass based on the copolymer, and preferably 6 to 16% by mass based on the copolymer. When it is less than 3% by mass, the stability of the water / oil repellent component tends to be lowered. When it exceeds 20 mass%, there exists a tendency for water and oil repellency and its durability to fall.

  In this embodiment, it is preferable to produce a copolymer by emulsion polymerization in a solvent containing water. The copolymer solution and emulsion dispersion thus obtained may be used as they are, or may be used after dilution. Further, after separating the copolymer, it may be used after being dissolved or emulsified and dispersed in a solvent. It is preferable to pre-emulsify using a high-pressure emulsifier before starting the polymerization reaction. For example, it is preferable to mix and disperse a mixture comprising a monomer, a surfactant, an organic solvent, water and the like with a homomixer or a high-pressure emulsifier. It is preferable to mix and disperse the raw material mixture in advance before the start of polymerization because the water / oil / oil repellent component stability of the finally obtained water / oil repellent composition is improved.

  At the start of the polymerization reaction, heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, or the like is preferably used. In particular, a water-soluble or oil-soluble radical polymerization initiator is preferable, and general-purpose initiators such as an azo polymerization initiator, a peroxide polymerization initiator, and a redox initiator can be used depending on the polymerization temperature. As the polymerization initiator, an azo compound is particularly preferable, and when polymerization is performed in a solvent using water, a salt of an azo compound is more preferable. Although polymerization temperature is not specifically limited, 20-150 degreeC is preferable and 50-70 degreeC is more preferable.

  In the polymerization reaction, a molecular weight modifier may be used. As the molecular weight modifier, aromatic compounds or mercaptans are preferable, and alkyl mercaptans are more preferable.

  When the monomer remains, it can be removed by a method such as distillation under reduced pressure as necessary.

  In the water / oil repellent composition of the present embodiment, the copolymer is preferably dispersed as particles in a solvent. In this case, the average particle diameter is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and even more preferably 10 to 200 nm, from the viewpoints of water / oil repellency and water / oil repellency component stability.

  The average particle size was measured by using a laser diffraction type / scattering type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), and the percentage integrated value of the particle size of the ultraviolet absorber for fibers was 50% from the small particle size side. It can be measured by setting the diameter to the average particle diameter.

  The water / oil repellent composition of the present embodiment preferably contains a solvent from the viewpoint of easy handling. As such a solvent, a solvent equivalent to the solvent that can be used to obtain the above copolymer can be used.

  Of these, it is preferable to use the same solvent as described above from the same viewpoint as in the case of the copolymer.

  The content of the solvent in the water / oil repellent composition is preferably from 50 to 90 mass%, more preferably from 55 to 75 mass%, based on the total amount of the composition.

  When the water / oil repellent composition contains an organic solvent, the content of the organic solvent is preferably from 1 to 20 mass%, more preferably from 5 to 15 mass%, based on the total amount of the composition.

  In the present embodiment, a water / oil repellent fiber product can be obtained by treating the fiber product with a treatment liquid containing the water / oil repellent composition of the present embodiment. The water / oil repellent composition of the present embodiment can be used as a treatment liquid as it is, or can be diluted with water or an organic solvent to obtain a treatment liquid.

  The treatment liquid according to the present embodiment contains 0.3 to 5% by mass of the water / oil repellent composition of the present embodiment from the viewpoint that the amount of the water / oil repellent composition applied to the fiber product is easily controlled. It is preferable that

  The treatment liquid according to this embodiment preferably contains an organic solvent. As such an organic solvent, the organic solvent equivalent to the organic solvent which can be used in order to obtain the said copolymer can be used. Among these, diethylene glycol monobutyl ether can be preferably used from the viewpoint of the stability of the treatment liquid and the permeability to the fiber product.

  Such an organic solvent is preferably contained in the treatment liquid in an amount of 0.3 to 3% by mass, more preferably 0.5 to 1.5% by mass, based on the total amount of the treatment liquid. .

  The water / oil repellent composition of this embodiment preferably has a pH of 2.0 to 6.0 from the viewpoint of water / oil repellency, texture, and water / oil repellency component stability. In addition, the treatment liquid according to the present embodiment preferably has a pH of 3.0 to 7.0, and preferably 3.0 to 6.0, from the viewpoint of water / oil repellency, texture, and stability of the treatment liquid. It is more preferable.

  The pH adjustment of the water / oil repellent composition of the present embodiment and the treatment liquid according to the present embodiment can be adjusted to an arbitrary pH by using a pH adjuster. As such a pH adjuster, acids such as formic acid, acetic acid, malic acid and citric acid; alkalis such as caustic soda, sodium carbonate and aqueous ammonia can be used. Among these, it is preferable to adjust pH using acetic acid and malic acid.

  When treating a textile product with the treatment liquid according to the present embodiment, a penetrant, an antifoaming agent, an antistatic agent, a texture adjusting agent, a melamine resin, an isocyanate compound, a glyoxal resin, a catalyst, and the like are contained in the treatment liquid. You may use together.

  The treatment liquid according to the present embodiment can be produced, for example, by mixing water, an organic solvent, and the water / oil repellent composition of the present embodiment. In this case, the mixing order is not particularly limited, but from the viewpoint of processing solution stability, a method of mixing the organic solvent diluted with water and the water / oil repellent composition of the present embodiment diluted with water, or A method of diluting one of the organic solvent or the water / oil repellent composition of the present embodiment with water and then mixing the other is preferred.

  The method for producing a water / oil repellent fiber product of the present embodiment includes a step of treating the fiber product with a treatment liquid containing the water / oil repellent composition of the present embodiment.

  As a method for treating a textile product with the treatment liquid, a conventionally performed method can be used without limitation. For example, the fiber product is treated with the treatment liquid by a pad method, a dipping method, a spraying method, a foaming method, a coating method, and the like, and then dried. Further, after drying, a curing (heat treatment) step may be incorporated as necessary. As a drying method, a conventionally used method can be used without limitation, and either a dry heat method or a wet heat method may be used.

  The material of the textile product to which the manufacturing method according to this embodiment can be applied is not particularly limited, and natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, nylon, polyester, polyurethane, and polypropylene. And synthetic fibers such as these, composite fibers of these, and blended fibers. In addition, the form of the textile product may be any form such as a woven fabric, a knitted fabric, a yarn, a nonwoven fabric, and paper.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
[Preparation of water / oil repellent composition]
In a 500 ml flask, 16.8 g of C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (hereinafter abbreviated as C6FMA) as monomer (A) and stearyl acrylate (hereinafter referred to as C6FMA) 44.1 g and stearyl methacrylate (hereinafter abbreviated as SMA) 19.8 g, 0.3 g of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) as the monomer (D), and polyoxyethylene alkyl ether 9.0 g (hereinafter abbreviated as POA), 1.5 g of stearyltrimethylammonium chloride (hereinafter abbreviated as STMAC), 30 g of tripropylene glycol (hereinafter abbreviated as TPG), and 169 g of ion-exchanged water were added. Stir and mix at ° C. This was emulsified and dispersed with an ultrasonic emulsifier, cooled to 30 ° C. or lower, and transferred to a 300 ml stainless steel autoclave container. To this, 0.3 g of dodecyl mercaptan was added and nitrogen substitution was performed for 10 minutes. To this was added 0.3 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.), and 9.0 g of vinyl chloride monomer (hereinafter abbreviated as VCM) was added as monomer (C). Reaction was performed at 60 ° C. for 4 hours to obtain a water / oil repellent composition. The obtained water / oil repellent composition had a non-volatile content of 30.5%. Moreover, the melt viscosity at 105 ° C. of the copolymer contained in the water / oil repellent composition was about 110 Pa · s. In addition, the melt viscosity of the copolymer is determined by using a flow tester CFT- for a sample obtained by adding an organic solvent such as methanol or acetone to a water / oil repellent composition and drying the solid content that has been emulsified and separated. 500D (manufactured by SHIMADZU) was used and measured at a measurement temperature of 105 ° C.

[1. Preparation of treatment liquid A and production of water and oil repellent fiber product A]
The water / oil repellent composition obtained above was diluted with ion-exchanged water to prepare treatment solutions A containing the water / oil repellent composition at concentrations of 4 g / l, 6 g / l, and 8 g / l, respectively. . In this treatment liquid A, a dyed polyester woven fabric (120 g / m ² ) is immersed, and the wet pick-up rate is reduced to 60% with a mangle, followed by drying at 120 ° C. for 60 seconds and further at 180 ° C. for 30 seconds. A water / oil repellent fiber product A was obtained. The water repellency of this water / oil repellent fiber product A was evaluated by the method described later. The results are shown in Table 6.

[2. Preparation of treatment liquid B and production of water / oil repellent fiber product B]
The water / oil repellent composition obtained above and NK Assist FU (trade name, manufactured by Nikka Chemical Co., Ltd., blocked isocyanate cross-linking agent) are diluted with ion-exchanged water to obtain a water / oil repellent composition. A treatment liquid B containing 30 g / l and NK assist FU 5 g / l was prepared. In this treatment liquid B, a dyed polyester woven fabric (120 g / m ² ) is immersed, and the wet pick-up rate is reduced to 60% with a mangle, followed by drying at 120 ° C. for 60 seconds and further at 180 ° C. for 30 seconds. A water / oil repellent fiber product B was obtained. The durable water repellency of this water / oil repellent fiber product B was evaluated by the method described below. The results are shown in Table 6.

[3. Preparation of treatment liquid C and production of water / oil repellent fiber product C]
The water / oil repellent composition obtained above was diluted with ion-exchanged water to prepare a treatment liquid C containing 30 g / l of the water / oil repellent composition. In this treatment liquid C, a dyed polyester fabric cloth (120 g / m ² ) is immersed, and the wet pick-up rate is reduced to 60% with a mangle, followed by drying at 120 ° C. for 60 seconds and further at 180 ° C. for 30 seconds. A water / oil repellent fiber product C was obtained. The oil repellency and texture of this water / oil repellent fiber product C were evaluated by the methods described below. The results are shown in Table 6.

[Evaluation of water repellency]
As shown in Table 1 below, the water-repellent No. 1 by the spray method of JIS L-1092. The water repellency of the water / oil repellent fiber product A was expressed.

  Water repellent No. Those marked with + indicate slightly better performance and those marked with-indicate slightly inferior.

[Evaluation of durable water repellency]
In accordance with JIS L 0217 (1995), the water repellency of the water / oil repellent fiber product B was evaluated at the initial stage, after 3 times of washing, and after 5 times of washing.

[Evaluation of oil repellency]
In accordance with AATCC_TM-118 (1966), five test solutions shown in Table 2 below were placed on a test cloth (water / oil repellent fiber product C), and the oil repellency was determined by the penetration state after 30 seconds.

[Evaluation of texture]
The tactile sensation of the water / oil repellent fiber product C was determined according to the criteria shown in Table 3 below, and the texture was evaluated.

[Stability of water and oil repellent components]
The water / oil repellent composition obtained above was stored at 45 ° C. for 7 days, and the state at that time was determined by visual observation according to the criteria of Table 4 below, and the stability was evaluated.

[Processing liquid stability]
300 g of a test solution was prepared by diluting the water / oil repellent composition obtained above with ion-exchanged water so that the concentration of the water / oil repellent composition was 10 g / L. The test liquid heated to 40 ± 3 ° C. was stirred with a homomixer at 6000 rpm for 10 minutes and filtered with a black cotton cloth. The amount of the residue remaining on the cotton cloth was visually determined according to the criteria shown in Table 5 below, and the stability was evaluated.

(Examples 2-22, Comparative Examples 1-21)
Example except that monomer (A), monomer (B), monomer (C), monomer (D) and other monomers were changed to the compositions shown in Tables 6-9. The same operation as in Example 1 was performed to obtain water / oil repellent compositions and water / oil repellent fiber products A to C of Examples 1 to 22 and Comparative Examples 1 to 21, respectively.

  In the same manner as in Example 1, the water / oil repellent composition and the water / oil repellent fiber products A to C were evaluated. The results are shown in Tables 6-9.

The symbols in the table indicate the following compounds.
_{C6FMA: C 6 F 13 CH 2} CH 2 OCOC (CH 3) = CH 2
SA: stearyl acrylate SMA: stearyl methacrylate VA: behenyl acrylate VMA: behenyl methacrylate VCM: vinyl chloride monomer VDC: vinylidene chloride HEMA: hydroxyethyl methacrylate GMA: glycidyl methacrylate NMAM: N-methylol methacrylamide 3C2HPMA: 3-chloro-2-hydroxy methacrylate PEGM: polyethylene glycol methacrylate LA: lauryl acrylate 2EHMA: 2-ethylhexyl methacrylate BzMA: benzyl methacrylate _{C8FA: C 8 F 17 CH 2} CH 2 OCOCH = CH 2
_{C6FA: C 6 F 13 CH 2} CH 2 OCOCH = CH 2
_{C4FMA: C 4 F 9 CH 2} CH 2 OCOC (CH 3) = CH 2
HEA: hydroxyethyl acrylate 35DPBI: 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate EGDM: ethylene glycol dimethacrylate

The water / oil repellent compositions of Examples 1 to 22 containing a copolymer of the monomer (A), the monomer (B), the monomer (C) and the monomer (D) have sufficient repellent properties. It has water / oil repellency component stability and treatment liquid stability, and can give desired water / oil repellency and its durability and texture when textile products are treated.

Claims (4)

Monomer (A) represented by the following general formula (1), at least one monomer (B) selected from alkyl (meth) acrylates having 16 to 22 carbon atoms, vinyl chloride monomer and vinylidene chloride And at least one monomer (C) selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, N-methylol methacrylamide and 3-chloro-2-hydroxypropyl methacrylate. A water / oil repellent composition comprising a copolymer obtained by copolymerizing a monomer composition containing the monomer (D).
_{C 6 F 13 (CH 2)} n OC (O) C (CH 3) = CH 2 ... (1)
[In formula (1), n represents 2 or 3. ] The water / oil repellent composition according to claim 1, wherein the monomer (B) is stearyl acrylate and / or stearyl methacrylate, and the monomer (C) is a vinyl chloride monomer. The monomer composition comprises 1 to 35% by mass of the monomer (A), 40 to 90% by mass of the monomer (B), and the monomer (C The water / oil repellent composition according to claim 1 or 2, which contains 1 to 20% by mass of) and 0.1 to 5% by mass of the monomer (D). A method for producing a water / oil repellent fiber product comprising a step of treating a fiber product with a treatment liquid containing the water / oil repellent composition according to any one of claims 1 to 3.