JPH09158045A - Treatment of fiber with high friction durability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart excellent water and oil repellent performances and friction durability of the performances to a fiber having a polyamide structure such as wool by treating the fiber with a treating agent containing a specific hydrophilic compound and an aqueous medium and then carrying out the water and oil repellent treatment with a polyfluoroalkyl group-containing compound having >=0ζ potential. SOLUTION: A fiber is treated with a treating agent containing a hydrophilic compound having >=1 anionic residues and >=2 benzene rings and an aqueous medium to adsorb 1.0-15.0 pts.wt. hydrophilic compound based on 100 pts.wt. fiber. The water and oil repellent treatment of the resultant fiber is then carried out with a polyfluoroalkyl group-containing compound as a water and oil repellent. A compound of the formula [(n) is an integer of 2-5; (m) is an integer of 1-5] useful as a fixing agent for nylon is preferred as the hydrophilic compound for pretreatment and the polyfluoroalkyl group-containing compound having >=0ζ potential in an aqueous medium in a particulate state is applied to the fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a fiber having excellent friction durability, and a fiber and a fiber product treated by the method. More specifically, it relates to a method of imparting excellent water / oil repellency and friction durability of the performance to fibers having a polyamide structure such as wool.

[0002]

2. Description of the Related Art Conventionally, a polymer or copolymer of a polymerizable monomer containing a polyfluoroalkyl group (hereinafter referred to as R ^f group), or a compound containing an R ^f group is dissolved in an organic solvent solution or A technique is known in which a textile product or the like is treated as an aqueous dispersion to impart water and oil repellency to the surface thereof.

Conventionally, in order to improve the durability of water and oil repellency against washing and dry cleaning, R ^f
Attempts have been made to copolymerize a monomer monomer having an adhesive group with a group-containing polymerizable monomer, or to blend a polymer having an R ^f group with a polymer having high film strength.

Further, as a water repellent finishing method for textiles,
A method is known in which an aqueous dispersion of a compound containing an R ^f group is first processed, and then an organic solvent solution of a compound containing an R ^f group is treated.

For example, Japanese Patent Laid-Open No. 58-46176 discloses that
As a method for antifouling a carpet, a method has been proposed in which nylon fiber is treated with a polyphenol compound and then the nylon fiber is reacted with a low molecular weight fluorine-containing compound (monomer) that reacts with a phenol group in an organic solvent. There is.
Further, Japanese Patent Application Laid-Open No. 60-110981 proposes a method in which a cellulose-based fiber is processed with a resin and then treated with water repellency. JP-B-5-12469, JP-A-2-259165
Proposes a method in which a polyamide fiber is treated with a sulfonated phenol formaldehyde or a styrene sulfonic acid type treatment agent and then treated with a fluorine type water repellent. Japanese Unexamined Patent Publication (Kokai) No. 3-213572 proposes an antifouling method in which silk fiber is treated with an epoxy compound and then treated with a fluorine-based water repellent.

[0006]

However, in the conventional water repellents and water repellent processing methods, treatment in an organic solvent, water- and oil-repellent washing durability, or dry cleaning durability is satisfactory. Even if you can do it,
The expression of the water-repellent friction durability and the water-repellent durability which are practical durability functions required for actual clothing were insufficient. In particular, when the material is wool, it has a relatively highly hydrophilic polyamide structure and also has a cuticle as a single fiber surface structure. Before doing so, its water-repellent function was significantly reduced due to the effect of friction during wearing, which was a practical problem.

[0007]

Means for Solving the Problems The present inventors have made detailed studies on a water- and oil-repellent durability developing mechanism for polyamide fibers such as wool fibers and a method for strengthening the water-repellent function.

As a result, when the fiber is treated with the R ^f group-containing compound, by treating the fiber product with a specific hydrophilic compound in advance as a pretreatment, there is a practical problem as compared with the treatment with only the water / oil repellent agent. It has been found that the water- and oil-repellent friction durability is significantly improved, and that the friction durability is significantly improved when the amount of the specific hydrophilic compound is set in a specific range. Further, they have found that the use of a compound having a specific structure as the R ^f group-containing compound further improves the effect.

That is, the present invention provides a fiber treatment method characterized in that the fiber is treated in the following treatment step 2 after the following treatment step 1. Treatment step 1: Treatment agent 1 containing a hydrophilic compound having one or more anionic residues and two or more benzene rings and an aqueous medium in an amount of the hydrophilic compound in an amount of 100 parts by weight of the fiber. Step of treating 0 to 15.0 parts by weight. Treatment step 2: a step of treating the fibers with a treatment agent 2 containing fine particles containing a polyfluoroalkyl group-containing compound having a zeta potential of 0 or more in the aqueous medium and the aqueous medium.

In the fiber treating method of the present invention, first, in the treating step 1, the fiber is treated with a treating agent 1 containing a specific hydrophilic compound and an aqueous medium. The specific hydrophilic compound is
It is a hydrophilic compound having at least one anionic residue and at least two benzene rings in the molecule. Examples of the anionic residue include a sulfonic acid group, a carboxyl group and a phosphoric acid group. It is considered that the anionic residue in the hydrophilic compound is a site which exhibits hydrophilicity, and when the fiber is a polyamide fiber, the anionic residue is adsorbed to the amino residue of the polyamide structure. The hydrophilic compound may have one type or two or more types of anionic residues in the same molecule, and a sulfonic acid group is preferable from the viewpoint of water solubility and adsorption to wool fibers. Further, the hydrophilic compound may have a group other than an anionic residue bonded to the benzene ring, and preferably has a hydroxyl group.

The molecular weight of the hydrophilic compound is 500 to 50.
00 is preferable, 1000 to 3000 is particularly preferable,
Further, 1000 to 2000 is preferable. If the molecular weight is too low, the hydrophilicity tends to be too strong, so that the water repellency of the polyfluoroalkyl group-containing compound in the treatment agent 2 in the treatment step 2 may be impaired, while if the molecular weight is too high, It has a drawback that it is difficult to be adsorbed on fibers.

Specific preferred examples of the hydrophilic compound contained in the treatment step 1 include the following compounds. However, in the following formula, n represents an integer of 2 to 5 and m represents an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.

[0013]

Embedded image

The above-mentioned hydrophilic compound is a known compound used as a so-called fixing agent for nylon and is easily available. The treating agent 1 in the treating step 1 contains the above specific hydrophilic compound and an aqueous medium. Examples of the aqueous medium include water or a mixture of water and a water-soluble organic solvent, but water alone is preferable. Examples of the water-soluble organic solvent include water-soluble alcohols and glycols.
The amount of the hydrophilic compound in the aqueous medium is 0.02
It is 0.8% by weight, preferably 0.04 to 0.5% by weight.

The treatment amount of the treating agent 1 is 1.0 to 15.0 parts by weight, and particularly preferably 2.0 to 10 parts by weight, based on 100 parts by weight of the fiber, as the amount of the hydrophilic compound. When less than 1.0 part by weight of the hydrophilic compound is treated, the washing durability is exhibited, but the more rigorous durability against friction is not exhibited. The amount of hydrophilic compound is 100
When the amount is 15.0 parts by weight or more based on parts by weight, there are disadvantages that the development of water repellency is hindered and the texture becomes hard. The above-mentioned hydrophilic compound is known as a fixing agent, but it is usually used for the purpose of improving the fixing property of the dye, and its treatment concentration is low. However, in the present invention, by treating the hydrophilic compound in a concentration range higher than usual, a new function of improving friction durability is found without deteriorating the performance of the water / oil repellent agent.

In the treating agent 1, other than the above hydrophilic compound,
Other additive components can also be blended. As an additional component, an organic acid such as acetic acid or formic acid may be contained for the purpose of adjusting the pH of the processing bath and promoting adsorption on the fiber surface.

As the treatment method in the treatment step 1, an exhaustion method is preferable because adsorption can be surely performed. The treatment temperature is not particularly limited and is preferably about 50 to 80 ° C., and the treatment time is preferably 10 to 30 minutes.

In the present invention, the fibers are treated in the treatment step 1 and then in the treatment step 2, but it is preferable to remove the excessively treated hydrophilic compound after the treatment step 1. As a removing method, a method of washing with water is usually used. Insufficient washing with water causes fine particles in the treating agent 2 to agglomerate, settle, etc., or hinder the water-repellent effect. Moreover, it is preferable to dry the fiber before the treatment with the treatment agent 2, if necessary.

The treatment step 2 is a step of treating the fibers with a treatment agent 2 containing fine particles containing a polyfluoroalkyl group-containing compound having a zeta potential of 0 or more in an aqueous medium and an aqueous medium.

The fine particles contained in the treating agent 2 are fine particles having a surface potential (zeta potential) of 0 or more in an aqueous medium. If the zeta potential is negative, the adsorption of fine particles on the fiber surface, particularly on the wool fiber surface, may be hindered, and water repellency and friction durability may be reduced. The zeta potential is preferably +10 mV to +80 mV. Further, the fine particles contain a compound containing R ^f group. As the compound containing an R ^f group, a known or well-known compound used for ordinary water / oil repellency treatment for fibers is adopted, and a polymer containing a polymerized unit of an R ^f group-containing polymerizable monomer is preferable. .

Here, the R ^f group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. Of the hydrogen atoms of the alkyl group, hydrogen atoms which are not replaced by fluorine atoms may be replaced by chlorine atoms. Further, a hydrogen atom which is not substituted with a fluorine atom may be present at the terminal part in the R ^f group. The proportion of fluorine atoms in the R ^f group is preferably at least (the number of hydrogen atom in the number + ^the R ^f group of fluorine atoms in ^the R ^f group) (R ^f number of fluorine atoms in the group) /] × 100
(%) Is preferably 60% or more, particularly 80%
It is preferable that it is above. The R ^f group may contain a chlorine atom.

The R ^f group preferably has a linear or branched structure, and particularly preferably a linear structure. In the case of a branched structure, it is preferable that the branched portion is present near the end of the R ^f group. The branched portion is preferably a short chain having about 1 to 4 carbon atoms. Further, the R ^f group has 4 to 20 carbon atoms.
Is preferable, and 6 to 16 is particularly preferable. The R ^f group is preferably a R ^f group containing a perfluoroalkyl group or a perfluoroalkyl group moiety in the case where the ratio of the above fluorine atoms is substantially 100%. The perfluoroalkyl group also preferably has a linear structure. As a straight-chain perfluoroalkyl group, CF ₃ (CF ₂ ) _k — [where k is 3
Is an integer from -19. ] The group represented by] is preferable.

A polymerizable monomer containing an R ^f group (hereinafter, R
^{It is referred to as f} group-containing polymerizable monomer. ) Means a compound having the above R ^f group and a polymerizable unsaturated group. ^The R ^f group ^the R ^f group-containing polymerizable monomer, showed the same meaning as ^the R ^f group described above, and their preferred embodiments are also the same. Further, ^the R ^f group-containing polymerizable monomer may be a mixture of two or more different compounds of the carbon number of ^the R ^f group, that case, the average carbon number of the R ^f group is 6 or more.

The R ^f group-containing polymerizable monomer is CF ₃ (CF ₂ ) _k — [where k is an integer of 3 to 19]. ] A polymerizable monomer containing a perfluoroalkyl group represented by and a perfluoroalkyl group having a polymerizable unsaturated group is preferable. The polymerizable monomer containing a perfluoroalkyl group may be a mixture of two or more compounds having different k numbers, but it is preferable that the average of k numbers is 6 or more. When it is less than 6, the water / oil repellency is lowered, and the desired function may not be exhibited. the value of k, or k
The average of 6 to 16 is preferable, 8 to 14 is particularly preferable, and 9 to 12 is more preferable. If the value of k is too large, it is solid at room temperature, has high sublimability, and is difficult to handle.

In the R ^f group-containing polymerizable monomer, the R ^f group and the polymerizable unsaturated group are directly or indirectly bonded via a bonding group, and are indirectly bonded. The case is preferred. The bonding group is a divalent or higher valent bonding group, preferably a divalent bonding group, and is an alkylene bond, ester bond, amide bond, amino bond, urethane bond, ether bond, phenyleneoxy bond, sulfonyl bond, or a combination thereof. Linking groups containing bonds are preferred. These R
^{As the f} group-containing polymerizable monomer, a known or well-known compound can be adopted. The R ^f group-containing polymerizable monomer can be easily synthesized from R ^f group-containing alcohol, R ^f group-containing carboxylic acid, R ^f group-containing sulfonic acid and the like by a known method.

The R ^f group-containing polymerizable monomer is preferably a compound having a structure in which one R ^f group is linked to a polymerizable unsaturated group via a divalent bonding group. For example, R ^f group-containing acrylate, R ^f group-containing methacrylate, R ^f group-containing styrene, R ^f group-containing vinyl ester, and R ^f group-containing fumarate are preferable.

From the viewpoint of versatility, the R ^f group-containing polymerizable monomer is particularly preferably the above R ^f group-containing acrylate or methacrylate. In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate. The R ^f group-containing (meth) acrylate is also advantageous from the viewpoints of polymerizability with other monomers, flexibility of the film formed on the surface of the wool fiber, adhesiveness, solubility, ease of emulsion polymerization, and the like. .

Specific examples of the R ^f group-containing polymerizable monomer are shown below, but the invention is not limited thereto. In the following, R represents a hydrogen atom or a methyl group.

[0029]

[Chemical 2] CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCR = CH ₂ , CF ₂ Cl (CF ₂ ) ₉ (CH ₂ ) ₃ OCOCR = CH ₂ , HCF ₂ (CF ₂ ) ₉ (CH ₂ ) ₂ OC (O) CR = CH ₂ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₁₁ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₉ CONH (CH ₂ ) ₅ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₉ O ( CF ₂ ) ₂ (CH ₂ ) ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ COOCH = CH ₂ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ COOCH = CH ₂ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₃ OCOCR = CH ₂ .

[0030]

Embedded image CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCH = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CF ₂ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ CH = CH ₂ , CF ₃ (CF ₂ ) ₉ CONH (CH ₂ ) ₂ CH = CH ₂ , CF ₃ (CF ₂ ) ₁₃ SO ₂ NH (CH ₂ ) ₂ CH = CH ₂ , CF ₃ (CF ₂ ) ₁₃ (CH ₂ ) ₆ OCOCR = CH ₂ , HCF ₂ (CF ₂ ) ₉ CH = CH ₂ .

The polymer containing polymerized units of ^the R ^f group-containing polymerizable monomer, a polymer containing at least one polymerized units of ^the R ^f group-containing polymerizable monomer, or, ^the R ^f group-containing It may be a polymer containing at least one polymerized unit of a polymerizable monomer and at least one polymerized unit of another polymerizable monomer. However, in order to further develop the desired performance, the fluorine content in the polymer is 50 to 70 in the polymer.
% By weight.

The other polymerizable monomer is not particularly limited as long as it is a compound containing an unsaturated group capable of polymerizing with the R ^f group-containing polymerizable monomer. Further, one or more kinds of other polymerizable monomers can be used, and in the case of two or more kinds, they can be used in an arbitrary ratio. In the following, other polymerizable monomers will be referred to as copolymerizable monomers.

Examples of the copolymerizable monomer include (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters, fumarates and maleates. These copolymerizable monomers preferably have a hydrocarbon group or a benzene ring, and particularly preferably have a hydrocarbon group. Further, the copolymerizable monomer may be vinyl chloride, ethylene, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, styrenes and the like.

The copolymerizable monomer includes an epoxy group, a halogen atom, a hydroxyl group, an amide group, an amino group, an imino group, an alkoxysilyl group, an N-methylol group, an N-alkyloxyalkyl group and a blocked isocyanate group. It may be a copolymerizable monomer containing a reactive group other than the polymerizable unsaturated bond. For example, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth )
Acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, γ-
Trimethoxysilylpropyl (meth) acrylate, glycidyl (meth) acrylate and the like are preferable.

As the copolymerizable monomer having a blocked isocyanate group, at least one of a hydroxyl group-containing (meth) acrylate and a polyisocyanate compound is used.
A blocked product of the reaction product obtained by reacting at a ratio in which one isocyanate group remains, and a polyisocyanate compound having at least one blocked isocyanate group and at least one isocyanate group in a hydroxyl group-containing (meth) acrylate. Reaction products obtained by the reaction are preferable.

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly ( Oxyethylene / oxypropylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate and the like are preferable.

Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, and fats such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate and bis (isocyanatomethyl) cyclohexane. Examples thereof include cyclic polyisocyanates and their nurate modified products, prepolymer modified products, buret modified products, and the like, and aliphatic diisocyanates or alicyclic diisocyanates are preferable.

Examples of the blocking agent include oximes, alkyl ketoxime, phenols, β-diketones, malonic acid esters, lactams, alkanols and the like. Specific examples include cyclohexane oxime, methyl ethyl ketoxime, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butanol, ε-caprolactam, maleic acid imide, sodium bisulfite, and the like, and cyclohexane oxime, methyl ethyl ketookim, etc. Is preferred.

The fine particles in the treating agent 2 (1) fine particles of two or more polymers containing polymerized units of ^the R ^f group-containing polymerizable monomer, or, (2) ^the R ^f group-containing polymerizable monomer It is preferred that the particles are fine particles composed of at least one polymer containing a polymerized unit of a monomer and at least one polymer not containing an R ^f group. When the fine particles of (1) or (2) are adopted, a higher friction durability can be obtained in combination with the treatment agent 1.

[0040] When a particle consisting of fine particles (1) two or more polymers containing polymerized units of ^the R ^f group-containing polymerizable monomer, polymer, respectively, different ^the R ^f group-containing polymerizable It is preferably a polymer containing polymerized units of monomers or a polymer having different fluorine contents.

Further, in the case of fine particles (2), the fine particles are composed of at least one kind of polymer containing polymerized units of R ^f group-containing polymerizable monomer and at least one kind of polymer not containing R ^f group.
Fine particles composed of one type of polymer containing a polymerized unit of an R ^f group-containing polymerizable monomer and one type of polymer not containing an R ^f group are preferred. The polymer containing no R ^f group is preferably a polymer containing a polymerized unit of one or more polymerizable monomers selected from the above-mentioned copolymerizable monomers. As the copolymerization monomer, one or more kinds can be arbitrarily selected from the above-mentioned copolymerization monomers.

The fine particles of (1) or (2) described above are preferably present in the aqueous medium as so-called core-shell type fine particles from the viewpoint of improving friction durability. Core-shell type fine particles include fine particles containing two or more different polymers as described above, and the outer shell of the fine particles has a more hydrophilic polymer site, and the inner shell of the fine particles has a more hydrophobic polymer site. Refers to the morphology of the particles present.

The method for synthesizing the fine particles of the polymer containing the polymerized units of the R ^f group-containing polymerizable monomer is not particularly limited, and known or known polymerization methods can be adopted.
Polymerization by an emulsion polymerization method or a dispersion polymerization method is preferable.
In particular, when producing core-shell type fine particles, it is preferable to employ a multi-step polymerization method such as a so-called seed polymerization method.

When an emulsifier is used at the time of polymerization, one or more kinds selected from known or well-known emulsifiers of nonionic type, cationic type and amphoteric type can be adopted from the viewpoint of zeta potential of dispersed particles. Not preferable.
The amount of the emulsifier is 100 parts by weight of the polymerizable monomer,
The amount is preferably 0.5 to 20 parts by weight, and particularly preferably about 1 to 10 parts by weight from the viewpoint of water / oil repellency and stability of the dispersion liquid.

Examples of the polymerization medium include water or water containing an organic solvent. As the organic solvent, a water-soluble organic solvent is preferable, and an ester-based, ketone-based, or ether-based organic solvent is preferable. As the ester organic solvent, ethyl acetate, butyl acetate, diethyl succinate and the like are preferable, as the ketone organic solvent, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable, and as the ether organic solvent, diethylene glycol, Dipropylene glycol, triethylene glycol, glycol, and their monomethyl ether or dimethyl ether, diethyl ether and the like are preferable. Among these, the organic solvent is preferably an ether type organic solvent from the viewpoint of low flammability. The ratio of water to the organic solvent is not particularly limited and may be any ratio.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and general-purpose initiators such as azo type, peroxide type and redox type initiators can be used depending on the polymerization temperature. The polymerization temperature is not particularly limited, but is 20 ° C to 150 ° C.
Is preferred. In order to make the zeta potential after the completion of the polymerization positive, an azoamidine-type initiator is particularly preferable.

The polymerization reaction is carried out after a mixture of a polymerizable monomer, water and an emulsifier is treated with a homomixer, a high pressure emulsifier or the like and pre-dispersed in advance as a pre-step of starting the polymerization. preferable.

The fine particles in the treating agent 2 are preferably present in the aqueous medium as an emulsion or a dispersion.

In the treating agent 2, the concentration of the R ^f group-containing compound is preferably about 1 to 50 parts by weight with respect to 100 parts by weight of the aqueous medium, and it is preferable to adjust the concentration with water so as to attain the concentration. . The concentration can be appropriately changed depending on the purpose and the form of the composition. The treatment amount of the treating agent 2 is 0.1 in terms of the solid content concentration with respect to 100 parts by weight of the fiber before the treating agent 1 is treated.
It is preferably 10 to 10 parts by weight, preferably 0.2 to 5 parts by weight. If the treatment amount of the treatment agent 2 is small, the friction durability may be reduced.

Further, the treating agent 2 may be blended with an additive component other than the above. For example, other water repellents, oil repellents, cross-linking agents, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents and the like can be appropriately added and used in combination.

The treatment step 2 is preferably carried out by a usual padding method or a treatment method such as an exhaust method, and the padding method is preferable from the viewpoint of simplicity of treatment.

The fiber treatment method of the present invention is particularly effective for various fibers having a polyamide structure, and is a treatment method suitable for wool fibers. For wool fiber,
It may be any of wool fibers and blended fibers of wool fibers and other fibers. Further, the wool fiber may be a fiber product, and examples thereof include outer garments such as suits and sportswear, work clothes, and uniforms. Examples of fibers other than wool include nylon and the like.

According to this treatment method, these fibers can be imparted with water / oil repellency, antifouling property, their washing resistance and dry cleaning resistance. And, moreover, the durability of these performances against friction can be imparted.

[0054]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The various evaluations in the examples were carried out according to the methods and criteria shown below.

[Evaluation method of water repellency] JIS-L-109
The water repellency number by the spray method of No. 2 (see Table 1). Usually, the shower water temperature was 27 ° C. In addition, the evaluation results represented by adding + (-) marks to the following water repellency numbers show that each evaluation is slightly better (worse) than those represented by numbers.

[Dry cleaning method] JIS-L-
1092.3.2. (2) According to the method described.

[Evaluation Method of Rainfall Test After Friction Durability] The sample was rubbed (pressing pressure 450 g) for 5 minutes with a pilling tester equipped with a wet cotton cloth, and then the method described in JIS-L-1092 (C) method (Bundesmann test). ), The rainfall is 1
It was rained under the conditions of 00 cc / min, the temperature of rainfall was 20 ° C., and the rainfall time was 10 minutes, and the wet state of the surface was judged according to the water repellency number in Table 1.

[Evaluation method of oil repellency] Several drops (diameter about 4 mm) of the test solution shown in Table 2 were placed at two places on the test cloth, and the state of permeation after 30 seconds (AATCC-TM118) was determined.
-1966).

[0059]

[Table 1]

[0060]

[Table 2]

Reference Example 1 Production Example of Treatment Agent 2 Perfluoroalkylethyl acrylate [C _k F _{2k + 1}
(CH ₂ ) ₂ OCOCH = CH ₂ : k is 6, 8, 1
A mixture of 0, 12, 14, 16 with an average of 9. ]
(Hereinafter referred to as FA) 3013 g, dodecyl mercaptan 55.8 g, nonionic emulsifier polyoxyethylene secondary alkyl ether 155 g, cationic emulsifier alkyldimethylamine acetate 15.5 g, water 5032 g
Was pre-dispersed with a homogenizer, and then 400 kg using a high-pressure homogenizer (manton-goulin emulsifier).
/ Cm ² to obtain an emulsion.

7,000 g of the emulsion was placed in a 10-liter stainless steel autoclave, 39.8 g of azobisisobutyronitrile was added, and the atmosphere was replaced with nitrogen. After heating to 60 ° C., polymerization was carried out for 8 hours (solid content 38.8% (polymerization yield 97.0%)). Into a 10 liter stainless steel autoclave, the above polymer dispersion (solid content concentration 38.8
%) 5000 g (solid content 1940 g; 100 parts by weight), FA 349 g (60 parts by weight), cyclohexyl methacrylate 175 g (30 parts by weight), glycidyl methacrylate 58.2 parts by weight (10 parts by weight).
Was charged.

Further, 252 g of dipropylene glycol monomethyl ether and 359 g of water were added to give a total solid content of 4
It was adjusted to be 0% by weight. After stirring the mixture,
2,2'-Azobis (2-amidinopropane) dihydrochloride (25.0 g) was added, and after nitrogen substitution, polymerization was carried out at 60 ° C for 15 hours. After cooling, the dispersion was taken out. The solid content concentration was 38.2% by weight. When the emulsion particles were observed by a transmission electron microscope, the obtained particles were fine particles having a core-shell structure and a particle diameter of about 0.2 μm.
Also, the zeta potential of an emulsion of a pH 6 aqueous solution is +1.
It showed 6 mV. The solid content concentration of the obtained dispersion liquid was adjusted to 20% by weight to prepare a treating agent 2 stock solution.

Reference Example 2 Production Example of Water Repellent Latex with Negative Zeta Potential Instead of the cationic emulsifier alkyl dimethylamine acetate used in Reference Example 1, anionic emulsifier sodium polyoxyethylene lauryl sulfate was used. A perfluoroalkyl group-containing aqueous dispersion was obtained in the same manner as in Reference Example 1 except that was used to prepare a water repellent latex. The zeta potential of the obtained emulsion was -6 mV at pH 7.

Reference Example 3 Production Example of Treatment Agent 2 FA 3100 g, stearyl acrylate 1650 g,
165 g of 2-hydroxyethyl methacrylate, 85 g of N-methylol acrylamide, 13 g of dodecyl mercaptan, 30 polyoxyethylene secondary alkyl ether
0 g, alkyldimethylamine acetate 30 g, dipropylene glycol monomethyl ether 2000 g, water 50
After predispersing 00 g at 60 ° C. with a homogenizer, it was treated with a high-pressure homogenizer (Emulsifier manufactured by Manton Goulin Co., Ltd.) at 60 ° C. and 400 kg / cm ² to obtain a white emulsion.

7,000 g of the emulsion was put into a 10-liter stainless steel autoclave, and 25.0 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added, and then the atmosphere was replaced with nitrogen. After heating to 60 ° C., polymerization was carried out for 12 hours (solid content 40.9% (polymerization yield 94%). After cooling, the dispersion liquid was taken out. When the emulsion particles were observed with a transmission electron microscope, it was obtained. The obtained particles have a particle size of about 0.1.
The particles were 5 μm. The zeta potential of the emulsion of pH 6 aqueous solution was +20 mV. The solid content concentration of the obtained dispersion liquid was adjusted to 20% by weight with ion-exchanged water to obtain a processing agent 2 stock solution.

Example 1 (Treatment Step 1) Hydrophilic compound (n in the above formula (1)
Is a mixture of 2 to 5 and m is 1, and the average molecular weight is 180.
0 compound) 0.27 g and ion-exchanged water 300 g 5
A wool tropical cloth (cloth weight 10.0 g) was immersed in a 00 ml beaker, and this was attached to a water bath (the weight of the hydrophilic compound to the cloth weight 100 was 2.7% by weight, and the bath ratio was about 1 :). 30, concentration of hydrophilic compound in processing bath 0.09%). The bath temperature was raised to 70 ° C., and the fabric was taken out after being kept for 15 minutes while slowly stirring, thoroughly washed with ion-exchanged water, and air-dried.

(Treatment Step 2) Treatment Agent 2 stock solution (solid content 20%) 8% produced in Reference Example 1, melamine resin (Sumitex Resin M3 manufactured by Sumitomo Chemical Co., Ltd.) 0.3%, catalyst (Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX).
A processing bath aqueous solution containing 3% of isopropanol and 1.5% of isopropanol was prepared, and the wool tropical cloth of the treatment step 1 was dipped in this, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 60% by weight. (Dip and squeeze were each repeated twice). Then, the treated cloth is dried at 110 ° C. for 90 seconds and further heat treated at 150 ° C. for 60 seconds,
A test cloth was obtained. The water repellency and oil repellency of the obtained test cloth were measured, and the water repellency number was 100 and the oil repellency number was 6.

Further, when the post-rubbing rainfall test was conducted on the water-repellent treated wool obtained above, the water-repellent number was 9
It was 0. Further, this test cloth was repeatedly dry-cleaned 5 times in the same manner, and then dried at 90 ° C. for 60 seconds, and a post-friction rain test was carried out. As a result, the water repellency number was maintained at 80.

Example 2 Treatment Agent 1 as hydrophilic compound
Is the same as in Example 1 except that the amount of the compound is 0.54 g (the weight of the hydrophilic compound is 5.4% by weight relative to the cloth weight of 100, the bath ratio is about 1:30, and the hydrophilic compound in the processing bath is Of 0.18%), and then a treatment cloth 2 was obtained through the treatment step 2. The initial water repellency, oil repellency, and water repellency after the post-friction rain test of the obtained test cloth were 100, 6, 100-, respectively.
Met. Further, after performing 5 times of dry cleaning, it was dried at 90 ° C. for 60 seconds and a post-friction rain test was carried out.

[Example 3] Reference example 3 as a stock solution of treating agent 2
A test cloth was obtained by performing the same processing as in Example 1 except that the stock solution of the treating agent 2 produced in 1. was used. When the water and oil repellency of the obtained test cloth was measured, the water repellency number was 10.
The oil repellency number was 0 and 6.

Further, when the post-rubbing rainfall test was conducted on the water-repellent treated wool obtained above, the water-repellent number was 8
It was 0-. Further, this test cloth was repeatedly dry-cleaned 5 times in the same manner, and then 60 ° C. at 90 ° C.
A water repellency number of 70 was obtained by conducting a rain test after rubbing for 2 seconds after rubbing.

[Example 4] A water repellent cloth was obtained by the same treatment method as in Example 2 except that the treated cloth was changed to nylon taffeta. When the water and oil repellency of the obtained test cloth were measured, the water repellency number was 100 and the oil repellency number was 7.

When the post-friction rain test was conducted on the treated cloth obtained above, the water repellency number was 100. Further, this test cloth was repeatedly washed 10 times by the same method, dried at room temperature and then subjected to a post-friction rain test to find that the water repellency number was 80.

[Comparative Example 1] Example in which treatment step 1 was omitted A test cloth was obtained by the same operation as in Example 1 except that the treatment step 1 was not performed. Initial water repellency number of test cloth is 1
The oil repellency number was 00. The water repellency number was 50 when the rain test after friction was carried out.

Comparative Example 2 Example 1 as a hydrophilic compound
The same as in Example 1 except that 2.0 g of the same compound as in Example 1 was used (the weight of the hydrophilic compound was 20% by weight with respect to 100 of the fabric weight, the bath ratio was about 1:30, and the hydrophilic compound in the processing bath was A density of 0.66%) and then a treatment step 2 to obtain a test cloth. The initial water repellency, the oil repellency, and the water repellency after the post-friction rain test of the obtained test cloth were 80 and 3, respectively.

[Comparative Example 3] Example in which a treating agent having a negative zeta potential was used, except that the water repellent latex produced in Reference Example 2 was used as the undiluted treating agent 2 in the treating step 2 of Example 1. A test cloth was obtained by the same operation as in 1. The initial water repellency number of the test cloth was 70 and the oil repellency number was 4. A water repellency number was 0 when a rain test after rubbing was conducted.

[0078]

According to the treatment method of the present invention, excellent water / oil repellency can be imparted to fibers and textile products. Further, according to the method of the present invention, it is possible to impart excellent friction durability, which is a performance that is practically important, and water repellency against rainfall. The friction durability can be exhibited even after dry cleaning. Further, there is also an advantage that excellent performance can be imparted to polyamide-based fibers such as wool fibers, which have been difficult to impart these properties in the past, and the fiber products. Further, since the treating agents used in the present invention are all aqueous treating agents, they are advantageous in terms of handling and environmental protection.

Claims (11)

[Claims] 1. A fiber treatment method comprising treating a fiber in the following treatment step 2 after the following treatment step 1. Treatment step 1: Treatment agent 1 containing a hydrophilic compound having one or more anionic residues and two or more benzene rings and an aqueous medium in an amount of the hydrophilic compound in an amount of 100 parts by weight of the fiber. Step of treating 0 to 15.0 parts by weight. Treatment step 2: a step of treating the fibers with a treatment agent 2 containing fine particles containing a polyfluoroalkyl group-containing compound having a zeta potential of 0 or more in the aqueous medium and the aqueous medium. 2. The method for treating fibers according to claim 1, wherein the treating agent 1 is a treating agent containing a hydrophilic compound having at least one sulfonic acid group and at least two benzene rings, and an aqueous medium. 3. The hydrophilic compound of the treating agent 1 has a molecular weight of 50.
The fiber treatment method according to claim 1 or 2, which is 0 to 5000. 4. The polyfluoroalkyl group-containing compound in treating agent 2 is a polymer containing a polymerized unit of a polyfluoroalkyl group-containing polymerizable monomer.
3. The fiber treatment method according to any one of 3 above. 5. The content of fluorine in the polymer is 50 to 70% by weight.
The method for treating fibers according to claim 4, wherein 6. The fine particles containing a polyfluoroalkyl group-containing compound of the treating agent 2 are fine particles containing two or more kinds of polymers containing a polymerized unit of a polyfluoroalkyl group-containing polymerizable monomer. Item 6. The fiber treatment method according to any one of Items 1 to 5. 7. A polymer according to claim 1, wherein the fine particles containing a polyfluoroalkyl group-containing compound in the treating agent 2 include a polymerized unit of a polyfluoroalkyl group-containing polymerizable monomer.
The fiber treatment method according to any one of claims 1 to 5, which is a fine particle containing one or more kinds and one or more kinds of polymers not containing a polyfluoroalkyl group. 8. The fiber treatment method according to claim 1, wherein in the treatment step 2, the treatment agent 2 is treated in a solid content of 0.1 to 10 parts by weight with respect to 100 parts by weight of the fiber. 9. The fiber treatment method according to claim 1, wherein the fibers are wool fibers. 10. A fiber treated by the fiber treatment method according to claim 1. 11. A fiber product treated by the fiber treatment method according to claim 1.