JP2017186703A - Composition for fiber treatment and fiber product treated with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for fiber treatment that is excellent in the stability of process liquid and contains a water repellent and an antistatic agent.SOLUTION: A composition for fiber treatment contains (A) at least one quaternary ammonium salt having a specific structure, represented by formula (1), (2) and the like, and (B) a water repellent free from fluorine [Ris a C4-9 alkyl or cycloalkyl; R-Rare methyl or ethyl; Ris a C4-9 alkyl, cycloalkyl or aryl; Xis a monovalent anion].SELECTED DRAWING: None

Description

  The present invention relates to a fiber treatment composition containing a water repellent that does not contain fluorine and an antistatic agent in the field of water repellency processing of fiber products, and a fiber product treated with the composition.

  Synthetic fibers such as polyester and nylon used in the field of textiles for clothing, etc. are known to tend to be triboelectrically charged (easily generate static electricity) because of their hydrophobic composition and low official moisture content. It has been. When these fibers are subjected to water-repellent processing with a fluorine-based water-repellent agent, triboelectric charge is more likely to occur, and this tendency is particularly remarkable in polyester. When frictional electrification occurs in textile processing, especially finishing, not only does it interfere with the operator and nearby machines during winding and transportation of the fabric, but also causes dust and dirt to adhere. Problems occur.

  Therefore, in order to suppress the generation of frictional charging, it is known to use a water repellent and an antistatic agent in combination when finishing a fiber, particularly during water repellent processing. The component of the antistatic agent is a highly hygroscopic salt such as guanidine hydrochloride or an alkyl phosphate ester salt, and these salts absorb the moisture in the air to suppress the frictional charging of the fibers.

  For example, Patent Document 1 proposes a method of using various quaternary ammonium salts in addition to guanidine hydrochloride and a zirconium salt of an organic acid as an antistatic agent used in water-repellent processing.

  However, if a highly hydrophilic antistatic agent is treated at the same time as the water repellent process, the water repellency may be adversely affected. In particular, when a water repellent containing no fluorine is used, there is a problem that the water repellent property is inhibited by the antistatic agent. The quaternary ammonium salt proposed in Patent Document 1 can achieve both water repellency and antistatic properties when used in combination with a fluorine-based water repellent, but does not contain fluorine. When used together, the water repellency was insufficient.

  Furthermore, in the combined use of an antistatic agent and a water repellent, the water repellent emulsion is destabilized by the salting-out effect of a salt such as guanidine hydrochloride or an alkyl phosphate ester salt, which is an antistatic agent. There were also concerns that caused trouble.

  Patent Document 2 proposes an antistatic treatment method using an ionic liquid of a specific dialkylsulfosuccinate or dialkylphosphoric acid and a specific quaternary ammonium salt as antistatic water-repellent processing. However, since these salts are insoluble in water, after dissolving in a solvent such as isopropyl alcohol, the fibers are treated by dipping or spraying, followed by water repellency. That is, the method of Patent Document 2 cannot be processed in one step, and it is necessary to use a solvent.

Japanese Patent No. 2583814 Japanese Patent No. 5301142

  As described above, in water repellency processing using a fluorine-based water repellant, it has been conventionally possible to achieve both water repellency and antistatic properties. However, in recent years, water repellent processing using a water repellent that does not contain fluorine has attracted attention as a countermeasure for environmental problems, and there is a tendency to increase. Water-repellents that do not contain fluorine are inferior in water-repellent performance to fluorine-based water-repellents. It was difficult to achieve both antistatic properties.

Accordingly, the present invention can provide antistatic performance without impairing water repellency even when used in combination with a water repellent that does not contain fluorine, and can achieve water repellency and antistatic properties. An object of the present invention is to provide a fiber treatment composition containing a water repellent and an antistatic agent that is excellent in stability during processing.
The fiber treatment composition specifically refers to a treatment liquid prepared for processing fibers by dipping, coating, spraying or other methods.

  The inventors have made extensive studies on the above problems, and among the quaternary ammonium salts, the number of carbon atoms of the substituent (alkyl group, cycloalkyl group or aryl group) having the largest number of carbon atoms is 4-9. If it is limited to a specific range, it is possible to impart antistatic properties without impairing water repellency even when used in combination with water repellents that do not contain fluorine, and excellent stability during processing. The inventors have found that a composition for water-repellent antistatic processing can be obtained, and have reached the present invention. In the present specification, unless otherwise specified, the “alkyl group” means a linear or branched chain alkyl group that does not include a cyclic structure, and does not include a “cycloalkyl group”. .

［式（１）中、Ｒ_１は炭素数４〜９のアルキル基又はシクロアルキル基、Ｒ_２〜Ｒ_４はメチル基又はエチル基、Ｘ⁻は１価のアニオンを示す。］

［式（２）中、Ｒ_５は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_６は水素、メチル基又はエチル基を示す。Ｘ⁻は１価のアニオンを示す］

［式（３）中、Ｒ_７は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_８はメチル基又はエチル基を示す。Ｘ⁻は１価のアニオンを示す］

［式（４）中、Ｒ_９は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_１０はメチル基又はエチル基、Ｙは炭素数３〜９のアルキレン基又は−ＣＨ_２ＣＨ_２ＯＣＨ_２ＣＨ_２−を示す。Ｘ⁻は１価のアニオンを示す］
（Ｂ）フッ素を含まないはっ水剤、
とを含有する繊維処理用組成物に関する。 That is, the present invention
(A) at least one quaternary ammonium salt having a structure of any one of the following formulas (1) to (4);

[In the formula (1), R ₁ represents an alkyl group or cycloalkyl group having 4 to 9 carbon atoms, R _{2 to} R ₄ represent a methyl group or an ethyl group, and X ⁻ represents a monovalent anion. ]

[In Formula (2), R ₅ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₆ represents hydrogen, a methyl group, or an ethyl group. X ⁻ represents a monovalent anion]

[In Formula (3), R ₇ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₈ represents a methyl group or an ethyl group. X ⁻ represents a monovalent anion]

[In the formula (4), R ₉ is an alkyl group having 4 to ₉ carbon atoms, a cycloalkyl group or an aryl group, R ₁₀ is a methyl group or ethyl group, Y is an alkylene group having 3 to 9 carbon atoms, or —CH ₂ CH ₂ OCH ₂ CH ₂ — is shown. X ⁻ represents a monovalent anion]
(B) a water repellent containing no fluorine,
The composition for fiber processing containing these.

In the quaternary ammonium salt (A), it is more preferable that R ₁ , R ₅ , R ₇ and R ₉ have 6 to 8 carbon atoms.

  Further, (B) the water repellent containing no fluorine is an acrylic copolymer containing 60% by weight or more of (meth) acrylate having a long chain alkyl group having 12 or more carbon atoms, paraffin wax, melamine wax, high grade More preferably, it contains at least one selected from the group consisting of fatty acid ester compounds, higher fatty acid amide compounds, alkylene urea compounds, zirconium compounds and silicone resins.

  The (B) fluorine-free water-repellent agent is an acrylic copolymer, paraffin wax, or higher fatty acid ester type containing 60% by weight or more of a (meth) acrylate having a long-chain alkyl group having 12 or more carbon atoms. More preferably, it contains at least one selected from the group consisting of a compound and a silicone resin.

More preferably, the counter ion X ^{− of the} quaternary ammonium salt contains at least one selected from the group consisting of halide ions other than fluorine, methyl sulfate ions, and ethyl sulfate ions.

The present invention also provides
(A) a step of dipping, coating, spraying or other methods for treating the fiber with the fiber treatment composition according to any one of the above,
(B) It is related with the water-repellent processing method of a textile product including the process of heat-processing at the temperature of 100 degreeC or more after the said process.

  Furthermore, the present invention relates to a fiber product to which water repellency is imparted, which is treated with the fiber treatment composition described above.

  The fiber treatment composition according to the present invention can impart good antistatic properties without impairing water repellency even when a synthetic fiber such as polyester is treated. In addition, the fiber treatment composition of the present invention has no problem in stability during processing and is less likely to cause trouble.

(Composition for fiber treatment)
The fiber treatment composition of the present invention includes (A) at least one specific quaternary ammonium salt and (B) a water repellent that does not contain fluorine. The (A) quaternary ammonium salt in the present invention contains at least one quaternary ammonium salt represented by the following formulas (1) to (4).

［式（１）中、Ｒ_１は炭素数４〜９のアルキル基又はシクロアルキル基、Ｒ_２〜Ｒ_４はメチル基又はエチル基、Ｘ⁻は１価のアニオンを示す。］

[In the formula (1), R ₁ represents an alkyl group or cycloalkyl group having 4 to 9 carbon atoms, R _{2 to} R ₄ represent a methyl group or an ethyl group, and X ⁻ represents a monovalent anion. ]

In the quaternary ammonium salt represented by the formula (1), R ₁ is an alkyl group or cycloalkyl group having 4 to 9 carbon atoms, and more preferably 6 to 8 carbon atoms. R ₁ may be linear or branched as long as it has 4 to 9 carbon atoms, and the cycloalkyl group may have a substituent such as a methyl group.
R ₂ , R ₃ and R ₄ are independently selected methyl or ethyl groups, and these three substituents may be the same or different from each other.
X ⁻ is a monovalent anion, and halide ions other than fluorine (Cl ⁻ , Br ⁻ , I ⁻ ), methyl sulfate ions, ethyl sulfate ions and the like can be mentioned.

  Specific examples of the quaternary ammonium salt represented by the formula (1) include n-butyltrimethylammonium salt, n-hexyltrimethylammonium salt, cyclohexyltrimethylammonium salt, n-octyltrimethylammonium salt, 2- Examples thereof include, but are not limited to, ethylhexyltrimethylammonium salt, butyldimethylethylammonium salt, and butyltriethylammonium salt.

［式（２）中、Ｒ_５は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_６は水素、メチル基又はエチル基を示す。Ｘ⁻は１価のアニオンを示す］

[In Formula (2), R ₅ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₆ represents hydrogen, a methyl group, or an ethyl group. X ⁻ represents a monovalent anion]

In the quaternary ammonium salt represented by the formula (2), R ₅ is an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group. The number of carbon atoms in R ₅ is more preferably 6-8. R ₅ may be linear or branched as long as it has 4 to 9 carbon atoms, and the cycloalkyl group may have a substituent such as a methyl group.
R ₆ represents hydrogen, a methyl group or an ethyl group.

  Specific examples of the quaternary ammonium salt represented by the formula (2) include 1-n-butylpyridinium salt, 1-n-octylpyridinium salt, 1-benzylpyridinium salt, 1-n-butyl- Examples thereof include 4-methylpyridinium salt and 1- (1,1-dimethylethyl) pyridinium salt, but are not limited thereto.

［式（３）中、Ｒ_７は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_８はメチル基又はエチル基を示す。Ｘ⁻は１価のアニオンを示す］

[In Formula (3), R ₇ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₈ represents a methyl group or an ethyl group. X ⁻ represents a monovalent anion]

In the quaternary ammonium salt represented by the formula (3), R ₇ is an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group. The number of carbon atoms in R ₇ is more preferably 6-8. R ₇ may be linear or branched as long as it has 4 to 9 carbon atoms, and the cycloalkyl group may have a substituent such as a methyl group.
R ₈ represents hydrogen, a methyl group or an ethyl group.

  Specific examples of the quaternary ammonium salt represented by the formula (3) include 1-methyl-3-n-butylimidazolium salt, 1-methyl-3-n-hexylimidazolium salt, and 1-methyl. -N-octylimidazolium salt, 1-methyl-3- (1,1-dimethylethyl) imidazolium salt, 1-ethyl-3-n-butylimidazolium salt, and the like, but are not limited thereto. It is not a thing.

［式（４）中、Ｒ_９は炭素数４〜９のアルキル基、シクロアルキル基又はアリール基、Ｒ_１０はメチル基又はエチル基、Ｙは炭素数３〜９のアルキレン基又は−ＣＨ_２ＣＨ_２ＯＣＨ_２ＣＨ_２−を示す。Ｘ⁻は１価のアニオンを示す］

[In the formula (4), R ₉ is an alkyl group having 4 to ₉ carbon atoms, a cycloalkyl group or an aryl group, R ₁₀ is a methyl group or ethyl group, Y is an alkylene group having 3 to 9 carbon atoms, or —CH ₂ CH ₂ OCH ₂ CH ₂ — is shown. X ⁻ represents a monovalent anion]

In the quaternary ammonium salt represented by the formula (4), R ₉ is an alkyl group having 4 to ₉ carbon atoms, a cycloalkyl group, or an aryl group. The number of carbon atoms in R ₉ is more preferably 6-8. R ₉ may be linear or branched as long as it has 4 to ₉ carbon atoms, and the cycloalkyl group may have a substituent such as a methyl group.
R ₁₀ represents hydrogen, a methyl group or an ethyl group.
Y is an alkylene group or _-CH 2 _CH 2 _OCH 2 CH ₂ of 3-9 carbon atoms - is, in the case of an alkylene group, and more preferably 4-6 carbon atoms. Further, the alkylene group may have a substituent such as a methyl group or a hydroxyl group.

  Specific examples of the quaternary ammonium salt represented by the formula (4) include 1-methyl-1-n-butylpiperazinium salt, 1-methyl-1-n-hexylpiperazinium salt, 1- Examples include methyl-1-n-octylpiperazinium salt, 1,2,2,6,6 pentamethyl-1-n-butylpiperazinium salt, 1-methyl-1-n-hexylmorpholinium salt, and the like. However, it is not limited to this.

  What is common to the quaternary ammonium salts shown in the formulas (1) to (4) is that the alkyl group, cycloalkyl group or aryl group having the largest number of carbon atoms has 4 to 9 carbon atoms. Quaternary ammonium salts having 3 or less carbon atoms in all alkyl groups, cycloalkyl groups, or aryl groups have little effect on water repellency, but have insufficient antistatic properties. On the other hand, a quaternary ammonium salt having an alkyl group having 10 or more carbon atoms, a cycloalkyl group or an aryl group has good antistatic properties, but has a large adverse effect on water repellency. Not suitable.

The alkyl group, cycloalkyl group and aryl group of R _{1 to} R ₁₀ and the alkylene group of Y have functional groups such as a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, an ether group, an amide group, and an amino group. You may have.

  The quaternary ammonium salt may contain only one type in the fiber treatment composition, or may contain two or more types. In addition, a known antistatic agent such as a quaternary ammonium salt, guanidine hydrochloride, or alkyl phosphoric acid other than the above can be used in combination as long as it does not adversely affect water repellency.

  The quaternary ammonium salts of the above formulas (1) to (4) can be obtained by mixing and reacting an appropriate tertiary amine and quaternizing agent by a known method.

The counter ion of the quaternary ammonium salt used in the present invention is not particularly limited as long as it is a monovalent anion. From the viewpoint of production, chloride ion, bromide ion, methyl sulfate ion, and ethyl sulfate ion are suitable. Is not limited to this. Other than the above, for example, inorganic ions such as iodide ion, sulfate ion, nitrate ion, phosphate ion, carbonate ion, formate ion, acetate ion, malate ion, citrate ion, n-propyl sulfate ion, benzene Organic acid ions such as sulfonic acid ions, p-toluenesulfonic acid ions, methyl phosphate ions, and ethyl phosphate ions may be used.
Further, only one kind of anion may be used, or a plurality of anions may be used in combination.

  The concentration of the quaternary ammonium salt contained in the fiber treatment composition is such that the quaternary ammonium salt used and the type of water repellent containing no fluorine, the type of fiber to be processed, the woven structure, Although depending on the basis weight and the like, a 0.1 to 2% by weight solution is preferable and a 0.2 to 1% by weight solution is more preferable with respect to the fiber treatment composition. If it is less than 0.1% by weight, sufficient antistatic properties cannot be obtained, and if it is 2% by weight or more, water repellency may be adversely affected.

The fiber treatment composition of the present invention contains a water repellent that does not contain fluorine together with at least one of the quaternary ammonium salts.
The water repellent containing no fluorine is not particularly limited as long as it does not contain a fluorine atom in the molecular structure and exhibits water repellency when applied to fibers. Specifically, an acrylic copolymer containing 60% by weight or more of a (meth) acrylate having a long-chain alkyl group such as a stearyl group, paraffin wax, melamine wax, higher fatty acid ester compound, higher fatty acid amide compound, In addition to alkylene urea compounds, alkyl ketene dimers, zirconium compounds, silicone resins such as dimethyl silicone, methyl hydrogen silicone, and amino-modified silicone can be used. Among these, an acrylic copolymer containing 60% by weight or more of a (meth) acrylic acid ester having a long chain alkyl group, paraffin wax, a higher fatty acid ester compound, and a silicone resin are more preferable, but are not limited thereto. It is not a thing. Moreover, only 1 type may be used for the water repellent which does not contain a fluorine, and 2 or more types may be used together.

The acrylic copolymer means a polymer obtained by copolymerizing an acrylic ester or methacrylic ester with an appropriate polymerizable monomer. In the acrylic copolymer, an acrylic ester and / or a methacrylic ester having an alkyl group having 12 or more carbon atoms is copolymerized in an amount of 60% by weight or more, preferably 70% by weight or more based on the acrylic copolymer. Those are preferred.
The alkyl group having 12 or more carbon atoms may be a chain alkyl group or a cyclic alkyl group, and the chain alkyl group may be linear or branched, but is preferably linear and linear. . For example, lauryl group, myristyl group, stearyl group, isostearyl group, nonylphenyl group and the like can be mentioned.
Examples of the polymerizable monomer copolymerized with an acrylate ester or a methacrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Examples include, but are not limited to, 2-ethylhexyl methacrylate, vinyl acetate, styrene, vinyl chloride, 2-hydroxyethyl methacrylate, acrylamide, N-methylolacrylamide, acrylonitrile, glycidyl methacrylate, N-vinylpyrrolidone, etc. Absent.

  The acrylic copolymer used in the present invention can be usually obtained by a known emulsion polymerization method. For example, the above-mentioned various polymerizable monomers, surfactant and water are charged into a predetermined reaction vessel and emulsified by a known method, and then a polymerization initiator is added and heated in a nitrogen atmosphere while stirring. Is obtained.

  Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides such as hydrogen peroxide, t-butyl hydroxide, and t-butyl peroxybenzoate, and 2,2-azo. Azo compounds such as bisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), azobis (isobutylamidine) dihydrochloride It is done. If acceleration of polymerization rate or low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt is combined with the radical polymerization initiator (redox polymerization initiation). Agent).

  The acrylic copolymer used in the present invention is obtained by an emulsion polymerization method in an aqueous medium as described above, and the solid content concentration of the acrylic copolymer emulsion is preferably 10 to 60% by mass, and 20 to 50% by mass. % Is more preferable. The polymerization reaction may be carried out at a reaction temperature of usually 40 to 90 ° C., preferably about 50 to 85 ° C. for 1 to 10 hours, preferably about 4 to 8 hours in the case of starting single polymerization. In the case of a redox polymerization initiator, the reaction temperature is lower, usually 50 to 80 ° C, preferably about 20 to 70 ° C. As a method for adding the polymerizable monomer, a batch addition method, a divided addition method, a continuous addition method, or the like, such as a monomer tap method or a monomer pre-emulsification tap method can be used. The monomer pre-emulsification tapping method is preferred by the continuous addition method.

  The paraffin wax is mainly composed of linear hydrocarbons (normal paraffin) obtained by separating and extracting hydrocarbons with good crystallinity from a portion of crude oil distilled under reduced pressure. Some paraffin waxes have a melting point of about 40 to 70 ° C., but those having a relatively high melting point are preferable.

  The higher fatty acid ester-based compound is an ester of a fatty acid having 12 or more carbon atoms and various alcohols, and preferably has a melting point of 30 ° C. or higher. As the alcohol, in addition to monohydric higher alcohols such as lauryl alcohol and stearyl alcohol, polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol and sorbitol can be used.

  Silicone resin refers to a polymer mainly composed of dimethylpolysiloxane and methylhydrogenpolysiloxane. Modified silicones having functional groups such as amino groups, epoxy groups, carboxyl groups, hydroxyl groups, silanols, alkyl groups, phenyl groups, and alkylene oxides at the terminals or side chains of the polymer can also be used. Two or more kinds of modified silicones may be used.

  These fluorine-free water repellents are acrylic copolymers or polymerizable monomers, paraffin wax, melamine wax, higher fatty acid ester compounds, higher fatty acid amide compounds, alkylene urea compounds, alkyl ketene dimers. It is preferable to form a water-based dispersion in which water-repellent components such as zirconium compounds and silicone resins are emulsified or dispersed in water using an appropriate surfactant.

  The surfactant used in the aqueous dispersion is not particularly limited, and is an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a polymer surfactant, a reactive interface. Examples include activators.

  Anionic surfactants include fatty acid salts such as potassium oleate, alkyl sulfates such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfonates such as sodium alkyl naphthalene sulfonate, dialkyl Examples include sodium sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl allyl ether phosphate ester, and the counter ion is sodium. , Potassium, calcium, ammonium, triethanolamine and the like, but are not limited thereto.

  Nonionic surfactants include polyoxyethylene alkyl (lauryl, hexadecyl, etc.) ether, polyoxypropylene alkyl (lauryl, etc.) ether, polyoxyethylene alkyl allyl ether, polyoxyethylene / polyoxypropylene block copolymer, polyethylene glycol Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid esters such as various higher fatty acid glycerols, fatty acid alkanolamides, alkyl glucosides, higher alcohols, and alkyldimethylamine-N-oxides.

  Examples of the cationic surfactant include various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, polyoxyethylene alkylamine quaternized products, monoalkylamines, An amine salt obtained by neutralizing an amine such as alkyldimethylamine or polyoxyethylene alkylamine with a suitable acid can be used. Examples of counter ions include, but are not limited to, chlorine ions, bromine ions, sulfate ions, formate ions, acetate ions, methyl sulfate ions, ethyl sulfate ions, and the like.

  Examples of reactive surfactants include polyethylene glycol mono (meth) acrylate, polyoxyethylene alkylphenol ether (meth) acrylate, 2- (meth) acryloyloxyethyl sulfonate, polyethylene glycol monomaleate and its derivatives, ( And (meth) acryloyl polyoxyalkylene alkyl ether phosphate ester salts.

  Examples of amphoteric surfactants include betaine acetate type surfactants such as lauryldimethylaminoacetic acid betaine, amine oxide type surfactants such as lauryldimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazo. Examples thereof include imidazolinium betaine type surfactants such as linium betaine, amide betaine type surfactants such as amidopropyl betaine laurate, and sulfobetaine type surfactants such as lauryl hydroxysulfobetaine.

  Examples of the polymer surfactant include polyvinyl pyrrolidone (PVP), polystyrene sulfonate (PSS), polypyrrole, polythiophene, polyethyleneimine, polyvinyl alcohol (PVA), polyvinyl ether, and polyacrylic acid synthetic polymer surfactant. It is done.

  The method for producing the aqueous dispersion is not particularly limited, and for example, a phase inversion emulsification method, a line mixer, a colloid mill, an ultrasonic wave, a homomixer, a forced emulsification method using a high-pressure homogenizer, or a media disperser such as a bead mill is used. A known method such as a method or an emulsion polymerization method can be used.

  In the present invention, the amount of the surfactant used in the aqueous dispersion is usually about 0.5 to 15 parts by mass with respect to 100 parts by mass of the water repellent component such as the acrylic copolymer. Preferably it is 1-10 mass parts. When the amount of the surfactant used is within this range, an aqueous dispersion having an appropriate average particle diameter can be obtained without producing a coagulated product.

  The water-based water-repellent dispersion containing no fluorine used in the present invention preferably has a solid content of 10 to 60% by mass, more preferably about 20 to 50% by mass.

  As described above, the surfactant used in the aqueous dispersion is not limited, but only the cationic surfactant, or the nonionic surfactant, or the cationic surfactant and the nonionic surfactant are used in combination. It is particularly preferable to treat the textile product.

  In addition, a known solvent may be used in combination for stabilizing the emulsification of the aqueous dispersion and improving the solubility of the water repellent component such as the acrylic copolymer. As the solvent, glycols such as ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether are preferable.

  The concentration of these fluorine-free water repellents contained in the fiber treatment composition is the kind of the water-free water repellent and quaternary ammonium salt used, the type of fiber to be processed, Although it varies depending on the woven structure, basis weight, etc., a 0.5 to 3% by weight solution is preferable and a 0.6 to 2% by weight solution is more preferable with respect to the fiber treatment composition. If it is less than 0.5% by weight, sufficient water repellency cannot be obtained, and even if it is used in an amount of 3% by weight or more, water repellency is not improved and is wasted.

  In addition to the above water-free water repellent and quaternary ammonium salt, the fiber treatment composition of the present invention improves water-repellent washing durability, adjusts the texture, prevents slipping, For stabilization and the like, a crosslinking agent, a softening agent, an anti-slip agent, a penetrating agent, an emulsifier, and the like can be used in combination.

  The fiber processed by the composition of the present invention is not limited to a woven fabric, a knitted fabric, a nonwoven fabric or the like. There are no restrictions on the material, and any of natural fibers, synthetic fibers, and mixed fibers thereof may be used. However, in view of the likelihood of triboelectric charging and the antistatic effect, polyesters such as polyethylene terephthalate are typical. It is preferably used for polyamide-based and polypropylene-based fibers such as those represented by the type 6,6,6 nylon or 6 nylon.

  The method for treating the fiber product with the composition of the present invention is not particularly limited as long as a predetermined amount can be uniformly attached to the fiber product, but the fiber treatment composition may be treated by a continuous method. preferable.

  In the continuous method, for example, after preparing the fiber treatment composition of the present invention, the object to be treated (fiber) is continuously fed into an impregnation apparatus filled with the fiber treatment composition, and the fiber treatment is performed on the object to be treated. After impregnating the agent composition, unnecessary liquid is removed. The impregnation apparatus is not particularly limited, and a padder type, a spray type, a foam type, a coating type, etc. can be used, and a padder type is particularly preferable. The amount of the fiber treatment composition applied to the fiber varies depending on the treatment method, fiber structure, basis weight, concentration of the agent, etc., but the fiber treatment composition may be 20 to 200 wt% with respect to the fiber weight. preferable.

After the immersion step, a heat treatment step is performed at a temperature of 100 ° C. or higher. Examples of the apparatus that performs the heat treatment step include an apparatus such as a pin tenter, a cylinder dryer, and a non-touch dryer. In the heat treatment step, water is removed by treatment at 90 ° C. to 120 ° C. for 1 to 5 minutes in the first stage, and then a water repellant is formed on the fiber surface in the second stage to improve washing durability. In order to perform the crosslinking reaction, it is preferable to perform a heat treatment at 130 ° C. to 180 ° C. for 1 to 3 minutes. When the temperature is low, sufficient water repellency and washing durability are not obtained, and when the temperature is too high, the water repellent may be decomposed or the texture may be cured.
The first and second stage heat treatments usually use the same mechanism, but may use different mechanisms.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these Examples. In addition, the quaternary ammonium salt was synthesized and used as follows without a commercially available product or reagent. When a commercially available product or reagent was present, it was obtained and used.

The quaternary ammonium salt and water repellent used in each Example and Comparative Example were produced as follows.
<Production of quaternary ammonium salt>
Production Example 1: Synthesis of n-butyltrimethylammonium bromide 100 g of toluene, 101 g of n-butyldimethylamine and 95 g of bromomethane were mixed and sealed in an autoclave, and the inside was purged with nitrogen, followed by reaction at 60 ° C. for 24 hours with stirring. After insoluble matter was taken out, washed with normal hexane and dried to obtain 180 g of the desired product.

Production Example 2 Synthesis of n-Hexyltrimethylammonium Chloride 100 g of tetrahydrofuran and 120 g of 1 -chlorohexane were put in an autoclave and sealed. After reducing the pressure to less than 100 mmHg, 200 g of 30% trimethylamine aqueous solution was added at 100 ° C. with stirring. React while dropping. After the reaction, tetrahydrofuran and trimethylamine were distilled off under reduced pressure, and 100 g of normal hexane was added to extract unreacted substances. The aqueous layer was collected and dried to obtain 140 g of the desired product.

Production Example 3: Synthesis of n-octyldimethylethylammonium = ethyl sulfate Into an autoclave, 100 g of normal hexane and 157 g of n-octyldimethylamine were put and sealed, and the inside was purged with nitrogen, and then 160 g of diethyl sulfate was added dropwise with stirring. And react at 30 to 40 ° C. for 24 hours. After the reaction, insoluble matter was taken out, washed with normal hexane, and dried to obtain 300 g of the desired product.

Production Example 4: Synthesis of 1-n-octylpyridinium bromide 100 g of toluene, 193 g of 1-bromooctane and 79 g of pyridine were sealed in an autoclave, the inside was reduced to less than 100 mmHg, and then stirred at 100 ° C. for 24 hours. React. After the reaction, insoluble matter was taken out, washed with normal hexane, and dried to obtain 250 g of the desired product.

Production Example 5: Synthesis of 1-benzylpyridinium chloride = 100 g of toluene, 126 g of benzyl chloride and 79 g of pyridine are sealed in an autoclave, and the inside is purged with nitrogen, followed by reaction at 60 ° C for 24 hours with stirring. After the reaction, insoluble matter was taken out, washed with normal hexane and dried to obtain 170 g of the desired product.

Production Example 6: Synthesis of 1-methyl-3- (2-ethylhexyl) imidazolium bromide 100 g of toluene, 82 g of 1-methylimidazole and 193 g of 2-ethyl-1-bromohexane were put in an autoclave and sealed, and the inside was nitrogen. After the substitution, the mixture is reacted at 80 ° C. for 24 hours with stirring. After the reaction, insoluble matter was taken out, washed with normal hexane, and dried to obtain 250 g of the desired product.

Production Example 7: Synthesis of 1-methyl-1-n-hexylpiperazinium = iodide The autoclave was sealed with 100 g of toluene, 99 g of 1-methylpiperazine, and 211 g of 1 -iodohexane, and the inside was purged with nitrogen. The reaction is allowed to proceed for 24 hours at 60 ° C. with stirring. After the reaction, insoluble matter was taken out, washed with normal hexane and dried to obtain 280 g of the desired product.

Production Example 8: Synthesis of cyclohexyltrimethylammonium = methylsulfate 100 g of normal hexane and 127 g of N, N-dimethylcyclohexylamine were put in an autoclave and sealed, and the inside was purged with nitrogen, and then 126 g of dimethyl sulfate was added dropwise at 40 ° C. with stirring. While reacting. After the reaction, insoluble matter was taken out, washed with normal hexane, and dried to obtain 230 g of the desired product.

Production Example 9 Synthesis of n-octyldimethylbenzylammonium chloride Tetrahydrofuran 100 g, benzyl chloride 126 g, n-octyldimethylamine 157 g were put in an autoclave and sealed, and the inside was purged with nitrogen, and then stirred at 50 ° C. for 24 hours. React. After the reaction, the solvent was removed by drying, and the dried product was washed with normal hexane and dried to obtain 250 g of the desired product.

Production Example 10: Synthesis of 1-decyl-3-methylimidazolium chloride chloride 100 g of toluene, 176 g of 1-chlorodecane, 82 g of 1-methylimidazole were put in an autoclave and sealed, and the interior was purged with nitrogen, and then stirred at 100 ° C. For 24 hours. After the reaction, the solvent was removed by drying, and the dried product was washed with normal hexane and dried to obtain 290 g of the desired product.

Production Example 11: Synthesis of 1,1-dimethylmorpholinium methyl sulfate Into an autoclave, 100 g of tetrahydrofuran and 101 g of 4-methylmorpholine were put and sealed, and the inside was purged with nitrogen. Then, while stirring, 126 g of dimethyl sulfate was added dropwise. React at ℃. After the reaction, the solvent was removed by drying, and the dried product was washed with normal hexane and dried to obtain 200 g of the desired product.

Production Example 12 Synthesis of Potassium Ethylphosphate In a 500 ml flask soaked in ice water, 206 g of water was dissolved while stirring, 56 g of potassium hydroxide was dissolved, and then 109 g of JP-502 (ethyl acid phosphate manufactured by Johoku Chemical Industry Co., Ltd.) was added. The solution was added dropwise so that the internal temperature was 50 ° C. or less, and 370 g of a target product having an active ingredient of 40% was obtained.

<Manufacture of water repellent containing no fluorine>
1. Non-fluorinated water repellant B-1 (acrylic copolymer with long chain alkyl group)
In a 500 mL flask, octadecyl acrylate 70 g, styrene 28 g, N-methylol acrylamide 2 g, stearyltrimethylammonium chloride 1 g, polyoxyethylene (7 mol) lauryl ether 6 g, polyoxyethylene (21 mol) lauryl ether 2 g, dodecyl mercaptan 0.1 g After adding 30 g of dipropylene glycol, heating to 50 ° C. and stirring uniformly, the mixture was emulsified and dispersed by high-speed stirring at 50 ° C. while dropping 224.7 g of ion-exchanged water to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of product containing a polymer concentration of 30% by weight were obtained.

2. Non-fluorinated water repellent B-2 (paraffin wax type)
Add 100 g of 140F paraffin, 20 g of low melting polyethylene oxide, 2 g of stearyltrimethylammonium chloride, 12 g of polyoxyethylene (10 mol) hexadecyl ether, and 0.6 g of potassium hydroxide to a 300 ml flask, heat and melt at 80 ° C., and stir uniformly. Then, the melt is added to 350 g of water heated to 80 ° C. in a 1000 ml beaker while stirring with a homomixer at 5000 rpm and emulsified. After cooling to 40 ° C., 20 g of zirconyl acetate was added to obtain 500 g of an emulsion having a solid content of 30%.

3. Non-fluorinated water repellent B-3 (paraffin wax / fatty acid ester compound)
Add 140F paraffin 104g, behenic acid diglyceride 30g, stearyltrimethylammonium chloride 2g, polyoxyethylene (7 mol) hexadecyl ether 8 g, polyoxyethylene (12 mol) hexadecyl ether 6 g, potassium hydroxide 0.6 g to a 300 ml flask. After heating and melting at 80 ° C. and stirring uniformly, the melt is added to a 1000 ml beaker with stirring at 5000 rpm with a homomixer in 350 g of water heated to 80 ° C. and emulsified. The mixture was cooled to 40 ° C. to obtain 500 g of an emulsion having a solid content of 30%.

4). Non-fluorinated water repellent B-4 (silicone resin)
A 500 ml flask is charged with 150 g of methyl hydrogen polysiloxane, 1 g of cocoalkyltrimethylammonium chloride, 5 g of polyoxyethylene (7 mol) lauryl ether, 5 g of polyoxyethylene (15 mol) lauryl ether, and 340 g of ion-exchanged water at 50 ° C. The mixture was emulsified and dispersed by high-speed stirring to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained 500 g of emulsion liquid with a solid content of 30%.

<Creation of compositions of Examples 1-8 and Comparative Examples 1-10>
Non-fluorinated water repellant (B-1) 50 g / L, Meikanate FM-1 (Blocked isocyanate cross-linking agent manufactured by Meisei Chemical Co., Ltd.) 10 g / L, quaternary ammonium salts of Production Examples 1-12, etc. Water-repellent working fluid (composition for fiber treatment) diluted with water so that the active ingredient becomes 3 g / L is prepared, and the water-repellent working fluids of Examples 1 to 8 and Comparative Examples 1 to 10 are prepared. Obtained. The composition is shown in Table 2.

<Evaluation of water repellency and water repellency>
Each water repellant processing solution is put on a polyester taffeta cloth, niped with two rubber rollers (35% pickup), dried at 110 ° C for 1 minute, and then heat treated at 170 ° C for 1 minute. An evaluation cloth was created. Water repellency was evaluated by the spray method of JIS L 1092.2009.97.2 using the obtained evaluation cloth. In any case, the evaluation fabric was naturally dried after washing. In addition, the water repellency is expressed by a numerical value of 5 levels from 1 to 5 shown in Table 1, and when + (−) is attached to a number, it indicates that it is slightly better (bad) than the evaluation of the number. . The evaluation results are shown in Table 2.

<Evaluation of water-repellent washing durability>
The created evaluation cloth was washed 0 times (HL-0) and washed 10 times (HL-10) according to the washing method described in JIS L 1092.98.55.2a) 3) c). After drying and drying, the water repellency was similarly evaluated. The results are shown in Table 2.

<Evaluation of antistatic properties>
A polyester taffeta cloth processed in the same manner as the evaluation of water repellency was measured in accordance with the method described in JIS L 1094.99.7.2, in the vertical direction, the cloth to be rubbed: cotton, and the friction band voltage was RH = 40%. It was measured. The results are shown in Table 2.

<Evaluation of emulsion stability>
Add 300 ml of the liquid used for water repellency processing to a 500 ml beaker and heat to 35 ° C., and then add 0.03 g of Disper TL (anionic dye dispersant manufactured by Meisei Chemical Co., Ltd.). The test solution was stirred at 2500 rpm × 5 minutes, filtered with a polyester dark cloth, and the filter cloth was air-dried. Stability was evaluated by the amount of scum remaining on the fabric. The evaluation criteria were a five-step evaluation, with grade 1 indicating a large amount of scum and grade 5 indicating almost no scum. The results are shown in Table 2.

As shown in Table 2, when each example was compared with Comparative Example 10 (an example in which no antistatic agent was used), the compositions of the examples maintained excellent water repellency. In addition, good results were obtained with respect to water-repellent washing durability, antistatic properties, and stability of the processing liquid.
In contrast to the examples, the examples using the quaternary ammonium salt having an alkyl group having a small carbon number or an aromatic ring (Comparative Examples 1 to 4 and 7) did not have sufficient antistatic properties. Examples using the quaternary ammonium salt having an alkyl group having a large carbon number (Comparative Examples 5 and 6) significantly inhibited water repellency. The examples using the antistatic agents other than the quaternary ammonium salts (Comparative Examples 8 and 9) had insufficient water repellency, and the stability of the processing liquid was poor.

<Creation of compositions of Examples 9 to 12 and Comparative Examples 11 to 16>
Non-fluorinated water repellent (B-2) 50g / L, Meikanate FM-1 (Blocked isocyanate cross-linking agent manufactured by Meisei Chemical Co., Ltd.) 10g / L, and each quaternary ammonium shown in Table 3 The water-repellent working fluid diluted with water so that the salt and others are 3 g / L of the active ingredient was prepared, and the water-repellent working fluids of Examples 9 to 12 and Comparative Examples 11 to 16 (composition for fiber treatment) ) The composition is shown in Table 3.

<Evaluation>
Using each water repellent fluid, polyester woolly taffeta was processed in the same manner as for water repellent B-1, and water repellency, frictional voltage and stability were evaluated. The results are shown in Table 3.

As shown in Table 3, when each example was compared with Comparative Example 16 (an example in which no antistatic agent was used), the compositions of the examples retained excellent water repellency. In addition, good results were obtained with respect to antistatic properties and stability of the processing liquid.
In contrast to the examples, the examples using the quaternary ammonium salts having an alkyl group having a small carbon number or an aromatic ring (Comparative Examples 11 to 13) did not have sufficient antistatic properties. The example using the quaternary ammonium salt having an alkyl group having a large carbon number (Comparative Example 14) significantly inhibited water repellency. In the example using the antistatic agent other than the quaternary ammonium salt (Comparative Example 15), the water repellency was not sufficient and the stability of the processing liquid was poor.

<Creation of compositions of Examples 13 to 16 and Comparative Examples 17 to 22>
Non-fluorinated water-repellent agent (B-3) 50 g / L, Meikanate FM-1 (Madesei Chemical Industries, Ltd. Blocked isocyanate cross-linking agent) 10 g / L, and each quaternary ammonium shown in Table 4 The water-repellent working fluid diluted with water so that the salt and others are 3 g / L of the active ingredient is prepared, and the water-repellent working fluids of Examples 13 to 16 and Comparative Examples 17 to 22 (composition for fiber treatment) ) The composition is shown in Table 4.

<Evaluation>
Using each water repellent fluid, polyester woolly taffeta was processed in the same manner as for water repellent B-1, and water repellency, frictional voltage and stability were evaluated. The results are shown in Table 4.

As shown in Table 4, when each example was compared with Comparative Example 22 (an example in which no antistatic agent was used), the compositions of the examples retained excellent water repellency. In addition, good results were obtained with respect to antistatic properties and stability of the processing liquid.
In contrast to the examples, the examples using the quaternary ammonium salts having an alkyl group having a small carbon number or an aromatic ring (Comparative Examples 17 to 19) did not have sufficient antistatic properties. The example using the quaternary ammonium salt having an alkyl group having a large carbon number (Comparative Example 20) significantly inhibited water repellency. The example using the antistatic agent other than the quaternary ammonium salt (Comparative Example 21) had insufficient water repellency, and the stability of the processing liquid was low.

<Creation of compositions of Examples 17 to 20 and Comparative Examples 23 to 28>
Use 50g / L of non-fluorinated water repellent (B-4), 5g / L of zinc catalyst, and dilute each quaternary ammonium salt shown in Table 5 with water so that the active ingredient is 3g / L. The water-repellent working fluid was adjusted to obtain water-repellent working fluids (compositions for fiber treatment) of Examples 17 to 20 and Comparative Examples 23 to 28. The composition is shown in Table 5.

<Evaluation>
Using each water repellent fluid, polyester woolly taffeta was processed in the same manner as for water repellent B-1, and water repellency, frictional voltage and stability were evaluated. The results are shown in Table 5.

As shown in Table 5, when each example was compared with Comparative Example 28 (an example in which no antistatic agent was used), the compositions of the examples maintained excellent water repellency. In addition, good results were obtained with respect to antistatic properties and stability of the processing liquid.
In contrast to the examples, an example using a quaternary ammonium salt having four alkyl groups having 4 carbon atoms (Comparative Example 23) and an example using a quaternary ammonium salt having an aromatic ring (Comparative Example 24) The antistatic property was not sufficient. The example using the quaternary ammonium salt having an alkyl group having a large carbon number (Comparative Example 25) significantly inhibited water repellency. The example using the quaternary ammonium salt having a low carbon number (Comparative Example 26) did not have sufficient antistatic properties. The example using the antistatic agent other than the quaternary ammonium salt (Comparative Example 27) was inferior in water repellency and stability of the processing liquid.

Claims (7)

(A) at least one quaternary ammonium salt having a structure of any one of the following formulas (1) to (4);

[In the formula (1), R ₁ represents an alkyl group or cycloalkyl group having 4 to 9 carbon atoms, R _{2 to} R ₄ represent a methyl group or an ethyl group, and X ⁻ represents a monovalent anion. ]

[In Formula (2), R ₅ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₆ represents hydrogen, a methyl group, or an ethyl group. X ⁻ represents a monovalent anion]

[In Formula (3), R ₇ represents an alkyl group having 4 to 9 carbon atoms, a cycloalkyl group, or an aryl group, and R ₈ represents a methyl group or an ethyl group. X ⁻ represents a monovalent anion]

[In the formula (4), R ₉ is an alkyl group having 4 to ₉ carbon atoms, a cycloalkyl group or an aryl group, R ₁₀ is a methyl group or ethyl group, Y is an alkylene group having 3 to 9 carbon atoms, or —CH ₂ CH ₂ OCH ₂ CH ₂ — is shown. X ⁻ represents a monovalent anion]
(B) A composition for fiber treatment containing a water repellent containing no fluorine. The composition for fiber treatment according to claim ₁ , wherein R ₁ , R ₅ , R ₇ and R ₉ have 6 to 8 carbon atoms. (B) An acrylic copolymer, paraffin wax, melamine wax, higher fatty acid ester containing 60 wt% or more of (meth) acrylate having a long-chain alkyl group having 12 or more carbon atoms, wherein the water repellent containing no fluorine The composition for fiber treatment according to claim 1 or 2, comprising at least one selected from the group consisting of a series compound, a higher fatty acid amide series compound, an alkylene urea series compound, a zirconium series compound, and a silicone resin. The (B) fluorine-free water repellent is an acrylic copolymer containing 60% by weight or more of a (meth) acrylate having a long-chain alkyl group having 12 or more carbon atoms, paraffin wax, a higher fatty acid ester compound, and The composition for fiber treatment according to claim 1 or 2, comprising at least one selected from the group consisting of silicone resins. Wherein wherein X ^-, fluorine other than halide ions, fiber treatment composition according to any one of claims 1 to 4 is a methyl sulfate ion, ethyl sulfate ion. (A) The process of processing a fiber with the composition for fiber processing of any one of Claims 1-5,
(B) A water-repellent processing method for a textile product, comprising a step of heat-treating at a temperature of 100 ° C. or higher after the step. A fiber product to which water repellency is imparted, which is treated with the fiber treatment composition according to any one of claims 1 to 5.