JP2017206775A - Aqueous dispersion for water-repellent treatment of fiber product and method for producing the same, water-repellent finishing method and water-repellent fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion for water-repellent finishing of a fiber product that achieves both water repellency and seam slippage prevention by the addition of a component to prevent seam slippage without affecting the water repellency.SOLUTION: An aqueous dispersion for water-repellent finishing of a fiber product contains, as a seam slippage prevention component, a hydrophobic inorganic fine particle containing at least one compound selected from the group consisting of an aluminum compound, a silicon compound and a titanium compound, and contains, as a water-repellent component, at least one selected from the group consisting of a fluorine copolymer, an acrylic copolymer, a urethane copolymer and a silicone copolymer.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous dispersion for imparting water repellency to a textile product, a method for producing the same, a water repellency processing method, and a water-repellent fiber product treated with the aqueous dispersion.

  Water repellent treatment agents used for imparting water repellency to textile products are well known. In the field where durability of water repellency is required, the conventional 55 Fibers of about 11 to 44 dtex (10 to 40 d) that are thinner than ˜110 dtex (50 to 100 d) have been used. On the other hand, in a textile product using such thin fibers, the slipperiness of the stitches is likely to occur due to the water-repellent treatment, which may cause misalignment or misalignment of the sewn portion during sewing or wearing. In particular, it is known that a water-repellent agent that does not contain fluorine has a large tendency to deteriorate the stitch slippage.

  Patent Document 1 discloses a water repellent containing alkyl (meth) acrylate as a main component. Patent Document 2 discloses a water-repellent agent containing an acrylate polymer and paraffin wax. However, these prior literatures do not describe any slippage of the seam, and even if the water repellent disclosed therein is used, both water repellency and prevention of seam slipping are achieved. It was difficult.

  On the other hand, it is known to use inorganic fine particles such as colloidal silica as a measure for preventing the slippage of stitches. However, the method of adding colloidal silica has a problem that the surface of the fabric is easily wetted by the hydrophilic group or the dispersant in the colloidal silica, and the durability of the water repellent process is lowered.

JP 2006-328624 A Special table 2012-522062 gazette

  In recent years, there has been an increasing demand for clothes using thin synthetic fiber fabrics. In clothes such as a down jacket made of such a thin fabric, the breakage of the seams between the fabrics and the loss of feathers are often a problem. Such a problem is considered to occur when the slippage of the used fabric deteriorates. On the other hand, for clothes using many thin synthetic fiber fabrics, water repellency processing is applied using a water repellant containing no fluorine, and this process deteriorates the slippage of the stitches. It is known. In view of this situation, the present invention adds a component that prevents stitch slippage without affecting water repellency, and achieves both water repellency and stitch slippage prevention for water repellency processing of textile products. It is an object to provide a dispersion.

  As a result of intensive studies on the above problems, the present inventors have made water repellency by using an aqueous dispersion containing a specific water repellency component and hydrophobic inorganic fine particles as a stitch slip prevention component. Was found not to be hindered, and it was also possible to improve the slipperiness of the stitches together with the water-repellent washing durability, and the present invention was completed. That is, the present invention includes the following inventions.

(1) As a stitch slip prevention component, comprising hydrophobic inorganic fine particles comprising at least one compound selected from the group consisting of aluminum compounds, silicon compounds and titanium compounds,
As a water-repellent component, at least one selected from the group consisting of a fluorine-based copolymer, an acrylic copolymer, a urethane-based copolymer, and a silicone-based copolymer is included.
Water-based dispersion for water-repellent processing of textile products.
(2) The water-based dispersion for water-repellent processing of a fiber product according to (1), wherein the hydrophobic inorganic fine particles have an average primary particle diameter of 1 to 100 nm.
(3) The water-based dispersion for water-repellent processing of a fiber product according to (1) or (2), wherein the ratio of the hydrophobic inorganic fine particles to the water-repellent component is 0.5 to 50% by mass.
(4) In addition to the aqueous dispersion described in any one of (1) to (3), (a) an aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or ( b) A water-based dispersion for water-repellent processing of textiles, comprising N-methylolmelamine.
(5) A fluorine-containing copolymer obtained by dispersing hydrophobic inorganic fine particles containing at least one compound selected from the group consisting of an aluminum compound, a silicon compound and a titanium compound in a hydrophilic solvent in an amount of 5 times or more in advance. Of an aqueous dispersion for water-repellent processing of textile products, which is blended with an aqueous dispersion containing at least one selected from the group consisting of acrylic copolymers, urethane copolymers and silicone copolymers Method.
(6) Along with the aqueous dispersion according to any one of (1) to (3), (a) an aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or (b) ) Water-repellent processing method for textile products using N-methylolmelamine.
(7) A water-repellent processing method for a textile product, comprising a step of immersing the fiber in a processing liquid containing the aqueous dispersion according to (4) and a step of heat-treating at a temperature of 100 ° C. or higher after the step.
(8) A water-repellent fiber product processed by the method described in (6) or (7).

  The water-based dispersion for water-repellent processing of a textile product according to the present invention can impart excellent water repellency to the textile product, is excellent in water-repellent washing durability, and is used for treated fibers. Sliding can be prevented.

(Aqueous dispersion for water-repellent processing of textile products)
The water-based dispersion for water-repellent processing of the textile product of the present invention is characterized by containing a seam slip-preventing component and a water-repellent component. Hydrophobic inorganic fine particles are used as the stitch slip prevention component. As the material of the hydrophobic inorganic fine particles used in the present invention, aluminum, silicon, titanium and the like can be used. In addition, the hydrophobic inorganic fine particles referred to in the present specification are obtained by treating the surface of the inorganic fine particles used as a material with silicone oil, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and the like to obtain methyl groups and octyl groups. A hydrophobic group is modified on the particle surface.

  As the degree of hydrophobicity, methanol wettability (M value) can be referred to. Methanol wettability is a concept that represents the degree of hydrophobicity of fine particles. The higher the methanol wettability, the lower the hydrophilicity. When the fine particles are uniformly dispersed in a water / methanol mixed solution, the minimum amount of methanol is required. Expressed as a percentage of capacity. The methanol wettability is calculated by the following method as described in JP 2014-214286 A.

<Methanol wettability (M value) calculation method>
0.2 g of a measurement sample (hydrophobic inorganic fine particles) is added to 50 mL of water in a beaker having a capacity of 300 mL, and then methanol is dropped from the burette until the entire amount of the measurement sample is suspended. At this time, the solution in the beaker is constantly stirred with a magnetic stirrer, and the time when the whole amount of the measurement sample is uniformly suspended in the solution is set as the end point. )
The M value of the hydrophobic inorganic fine particles used in the present invention may be larger than 0, but is preferably 30 to 80, more preferably 40 to 70.

  The hydrophobic inorganic fine particles are preferably any one of an aluminum compound, a silicon compound, and a titanium compound. Examples of the aluminum compound include alumina (aluminum oxide) fine particles, examples of the silicon compound include silica fine particles, and examples of the titanium compound include titanium oxide fine particles. Among these, hydrophobic silica fine particles are more preferable in terms of availability and improvement in washing durability.

As products that can be obtained from the market as hydrophobic inorganic fine particles, WACKER HDK H15, H20, H30 (Asahi Kasei Wacker Silicone Co., Ltd., “WACKER HDK” is a registered trademark of Asahi Kasei Wacker Silicone Co., Ltd.), Nipsil SS-10, 15, 115 70, 50 (Tosoh Silica Corporation, “Nipsil” is a registered trademark of Tosoh Silica Corporation), AEROSIL R972, R974, R976S, RX50, RX200, RX300, RA200H, RA200HS, AEROXIDE Alu C805, TiO ₂ T805, TiO ₂ NKT90 (Nippon Aerosil Co., Ltd., “AEROSIL”, “AEROXIDE” is a registered trademark of Nippon Aerosil Co., Ltd.) and the like.

  The particle diameter of the hydrophobic inorganic fine particles is preferably fine particles having an average primary particle diameter of 1 to 100 nm, more preferably fine particles having an average primary particle diameter of 5 to 50 nm, more preferably fine particles having an average primary particle diameter of 5 to 30 nm. It is. It is generally known that the slippage of the seams is improved by attaching fine particles to the fabric surface, and many particles having a smaller particle size can be adhered per unit area of the fabric. It can be expected that the effect of improving seam slipping will be increased. On the other hand, if the average primary particle diameter exceeds 100 nm, the amount of particles per unit area is reduced, so that there is a possibility that a sufficient effect of improving stitch slipping may not be obtained.

  The average primary particle diameter of the inorganic fine particles can be measured by a known method. For example, the average primary particle diameter by number average can be measured and calculated by observation using a transmission electron microscope.

  In addition, when blending the hydrophobic inorganic fine particles with the water-based dispersion for water-repellent processing, a dispersant is used in combination in order to improve the dispersibility after the addition, and it is 5 times or more in advance, preferably 5-20. It is preferable to disperse using a double amount, more preferably 6 to 10 times the amount of hydrophilic solvent. Examples of the hydrophilic solvent used include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and 3-methoxy-3-methyl-1-butanol, ethers and acetals such as tetrahydrofuran, ketones such as acetone and diacetone alcohol, Aldehydes, esters such as methyl lactate, polyhydric alcohol derivatives such as glycerin and ethylene glycol, carboxylic acids and anhydrides such as propionic acid, nitrogen-containing compounds such as N, N-dimethylformamide, dimethyl sulfoxide and the like Preferred examples include sulfur-containing compounds, fluorine compounds such as 2,2,3,3-tetrafluoropropanol, etc., but particularly preferred is excellent uniform dispersion of hydrophobic inorganic fine particles in an aqueous medium and is easy. From the point of being removable, etc. Alcohol, ethyl alcohol, isopropyl alcohol, 3-methoxy-3-methyl-1-butanol.

  As the dispersant, known nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide can be used alone or in combination of two or more.

  An emulsifying and dispersing apparatus for dispersing hydrophobic inorganic fine particles in a hydrophilic medium to form a uniform dispersion is not particularly limited. K. High-speed shear turbine type dispersers such as homomixers (made by Special Machine Industries), high-pressure jet homogenizers such as piston type high-pressure homogenizers (made by Gorin), microfluidizers (made by Microfluidics), and ultrasonic homogenizers Emulsification such as ultrasonic emulsification disperser (Nippon Seiki Seisakusho), medium stirring type disperser such as Attritor (Mitsui Mining Co., Ltd.), forced gap passage type disperser such as colloid mill (Nihon Seiki Seisakusho) It is desirable to perform uniform dispersion processing by using a dispersion device.

  The water-repellent component contained in the aqueous dispersion of the present invention can form a water-repellent film on the fiber surface, and this water-repellent film fixes the aforementioned hydrophobic inorganic fine particles to the fiber surface. Although it will not restrict | limit especially if it functions as a binder, At least 1 sort (s) selected from the group which consists of a fluorine-type copolymer, an acryl-type copolymer, a urethane-type copolymer, and a silicone-type copolymer is included.

  As the fluorine-based copolymer, for example, (A) a specific hydrophobic block polyisocyanate as described in JP-A-2014-17279 is a cationic surfactant in water or a solution containing water as a main component. A hydrophobic block polyisocyanate aqueous dispersion which is forcibly emulsified with a water-repellent and oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms, the hydrophobic block polyisocyanate and the cation A reactant having a surfactant weight ratio of 100: 0.2 to 100: 3, and the cationic surfactant comprises a monoalkyltrimethylammonium salt having 8 to 24 carbon atoms and a monoalkyl having 8 to 24 carbon atoms Although the reaction material etc. of what is selected from the group which consists of an alkylamine salt are mentioned, it does not specifically limit. Specifically, for example, a fluorine-based copolymer composed of 2-perfluorohexylethyl acrylate, n-butyl methacrylate, vinyl chloride, or the like, or other commercially available fluorine-based water repellents can be used.

  As an acrylic copolymer, for example, as described in JP-A-2006-328624, a polymerizable monomer not containing fluorine, and a (meth) acrylic acid ester having an alkyl group having 12 to 24 carbon atoms are polymerized. Examples of the acrylic copolymer are not particularly limited. In the acrylic copolymer, an acrylic acid ester and / or a methacrylic acid ester having an alkyl group having 12 or more carbon atoms is copolymerized in an amount of 60% by mass or more, preferably 70% by mass 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 a linear chain. . 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 methacrylate ester having an alkyl group having 12 or more carbon atoms include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Methyl, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, styrene, vinyl chloride, 2-hydroxyethyl methacrylate, acrylamide, N-methylolacrylamide, acrylonitrile, glycidyl methacrylate, N-vinylpyrrolidone, etc. But not limited to these.

  The acrylic copolymer as described above 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.

  Examples of the urethane copolymer include an active hydrogen component (A) and an organic polyisocyanate component (aromatic polyisocyanate having 8 to 26 carbon atoms) (B) as described in JP-A-2015-52093. A polyurethane resin obtained by reaction, wherein the active hydrogen component (A) is a monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms, based on the mass of the (A). Polyurethane resin containing 0.1 to 20% by mass is not particularly limited.

  Examples of the silicone copolymer include a silicone copolymer prepared by using a reactive silicone oil such as methyl hydrogen polysiloxane, and an organopolysiloxane side as described in JP-A-2004-59609. Examples thereof include, but are not particularly limited to, a silicone copolymer obtained by reacting an amino-modified silicone oil having an amino group bonded to a chain and a polyfunctional isocyanate having two or more isocyanate groups in the molecule.

  A modified silicone having a functional group such as an amino group, an epoxy group, a carboxyl group, a hydroxyl group, or a silanol, an alkyl group, a phenyl group, or an alkylene oxide group at the terminal or side chain of the silicone copolymer can also be used. Two or more kinds of modified silicones may be used.

  The aqueous dispersion of the present invention is obtained by dispersing a dispersion in which hydrophobic inorganic fine particles are dispersed in a hydrophilic solvent into a fluorine-based copolymer, an acrylic copolymer, a urethane copolymer, and a silicone copolymer, which are water-repellent components. It can be obtained by blending in an aqueous dispersion containing at least one selected from the group consisting of polymers. With the aqueous dispersion of the present invention, excellent water repellency can be imparted to the fibers, the washing durability is excellent, and the slip resistance value of the treated fibers can be suppressed. In particular, a water-repellent agent that does not contain fluorine has a large tendency to deteriorate the slipperiness of the stitches, and therefore, the slipperiness prevention effect by adding hydrophobic inorganic fine particles is effectively exhibited.

  The amount of the hydrophobic inorganic fine particles in the aqueous dispersion of the present invention is 0.5 to 50.0% by mass, more preferably 1.0 to 40.0% by mass, and still more preferably based on the water-repellent component. It is 5.0-25.0 mass%. If it is in this range, it is effective in improving washing durability and preventing stitch slippage. If the hydrophobic inorganic fine particles are less than 0.5% by mass, the effect of preventing the slippage of the stitches cannot be sufficiently obtained. If the hydrophobic inorganic fine particles exceed 50.0% by mass, the water repellency may be lowered.

  The aqueous dispersion of the present invention contains optional additives as long as the effects of the present invention are not impaired, in addition to the water-repellent component, the slip-preventing component, and the dispersant for dispersing them. May be. Examples of additives include fiber agents such as anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents, antioxidants, ultraviolet absorbers, pigments, curing accelerators, deodorants, and antibacterial agents. These additives can be used singly or in appropriate combination of two or more.

(Water repellent processing method for textile products)
When the aqueous dispersion of the present invention is processed into a textile product, together with the above aqueous dispersion, (a) an aqueous dispersion or emulsion of a bifunctional or higher blocked isocyanate, (b) N-methylol melamine, etc. It is preferable to use a crosslinking agent in combination.

  (A) A bifunctional or higher functional blocked isocyanate can be obtained by reacting a bifunctional or higher functional isocyanate with an appropriate blocking agent by a known method. Examples of the isocyanate include 4,4'-bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, diisocyanate trimer and trimethylolpropane adduct.

  Examples of the isocyanate blocking agent include secondary or tertiary alcohols, active methylene compounds, phenols, oximes, substituted pyrazoles, and caprolactam. Usually, these blocked isocyanates are emulsified and dispersed using a surfactant by a known method. In addition, after blocking 70 to 95% of all isocyanate groups in advance, by reacting polyalkylene glycol having an appropriate molecular weight, particularly polyethylene glycol, with the remaining isocyanate groups, the blocked isocyanate exhibits self-emulsifying properties and is water repellent. It is effective not only for improving the washing durability of textile products treated with the aqueous dispersion for processing but also for improving the stability of the products.

  (B) Examples of N-methylol melamine include trimethylol melamine and hexamethylol melamine.

The water-based dispersion for water-repellent processing of the present invention is useful for imparting water repellency having excellent washing durability to textiles. For this purpose, the textile product is treated with a working fluid containing the aqueous dispersion of the present invention.
The processing liquid can be obtained by diluting the water-dispersed aqueous dispersion described above, the blocked isocyanate, N-methylol melamine, and the like with water to a predetermined concentration. Further, further chemicals known in the field of textile finishing, for example, softening agents, antistatic agents, flame retardants, and the like may be contained in the processing liquid.

The water-repellent processing method for the textile product is not particularly limited, and various methods can be adopted. And a continuous method or a batch method may be used.
The batch method includes a step of immersing an object to be processed in a working fluid and a step of removing water remaining on the object to be processed after the process. The batch method is preferably employed when the object to be treated is not in the form of a fabric, for example, when it is not suitable for a continuous method such as loose hair, top, yarn and the like. In the soaking step, for example, a cotton dyeing machine, a cheese dyeing machine, a liquid dyeing machine, a beam dyeing machine or the like can be used. In the operation of removing water, a hot air dryer such as a cheese dryer or a tumble dryer, a high-frequency dryer, or the like can be used.

  In either case, the drying (heat treatment) step after immersing the fibers to be treated in the processing liquid can be performed at 80 to 180 ° C., and is preferably heat treated at a temperature of 100 ° C. or higher.

The fiber subjected to the water-repellent treatment is not particularly limited as long as the effect of the present invention is produced. For example, synthetic fibers such as nylon, polyester, acrylic and polyurethane, natural fibers such as cotton, hemp, silk and wool, and those Can be used. In particular, it exhibits a remarkable effect on a thin synthetic fiber fabric, that is, for example, a nylon or polyester fabric having a basis weight of 10 to 100 g / m ² and a used fiber of about 11 to 67 dtex (10 to 60 d).

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by them.

<Example 1>
15 parts of hydrophobic silica fine particles (surface modification with trimethylsilyl group, number average primary particle size of about 12 nm, M value 58) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 700 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
This dispersion is converted into an aqueous dispersion (concentration of water repellency component: 30% by mass) containing an acrylic copolymer composed of stearyl acrylate, 2-ethylhexyl methacrylate, stearyldimethylamine hydrochloride, etc. as a water repellency component. On the other hand, 20% by mass (active ingredient ratio) was added to obtain an aqueous dispersion for water repellent processing of the fiber product of the present invention.

<Example 2>
15 parts of hydrophobic silica fine particles (surface modification with trimethylsilyl group, number average primary particle diameter of about 30 nm, M value 62) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 700 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
20% by mass of this dispersion was added to the aqueous dispersion containing the same acrylic copolymer as in Example 1 to obtain an aqueous dispersion for water-repellent processing of the fiber product of the present invention.

<Example 3>
15 parts of hydrophobic silica fine particles (surface modification with trimethylsilyl group, number average primary particle diameter of about 7 nm, M value of 58) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 700 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
20% by mass of this dispersion was added to the aqueous dispersion containing the same acrylic copolymer as in Example 1 to obtain an aqueous dispersion for water-repellent processing of the fiber product of the present invention.

<Example 4>
In the same manner as in Example 1, 5.0% by mass of the aqueous dispersion of hydrophobic silica was added to the aqueous dispersion of the acrylic copolymer to prepare an aqueous dispersion for water repellency processing.

<Example 5>
In the same manner as in Example 1, 30.0% by mass of an aqueous dispersion of hydrophobic silica was added to the aqueous dispersion of acrylic copolymer to prepare an aqueous dispersion for water repellency processing.

<Example 6>
Hydrophobic titania fine particles (surface modification with octylsilyl group, number average primary particle size of about 21 nm, M value of 65) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 700 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic titania fine particles was obtained.
20% by mass of this dispersion was added to the aqueous dispersion containing the same acrylic copolymer as in Example 1 to obtain an aqueous dispersion for water-repellent processing of the fiber product of the present invention.

<Example 7>
15 parts of hydrophobic alumina fine particles (surface modification with octylsilyl group, number average primary particle size of about 13 nm, M value 60) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 700 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic alumina fine particles was obtained.
20% by mass of this dispersion was added to the aqueous dispersion containing the same acrylic copolymer as in Example 1 to obtain an aqueous dispersion for water-repellent processing of the fiber product of the present invention.

<Example 8>
5 parts of hydrophobic silica fine particles (surface-modified with dimethylsilyl group, number average primary particle diameter of about 7 nm, M value 45) are added to 30 parts of ethyl alcohol together with a dispersant, and stirred at 800 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
10% by mass of this dispersion is added to an aqueous dispersion containing a fluorinated copolymer composed of 2-perfluorohexylethyl acrylate, n-butyl methacrylate, vinyl chloride, etc. An aqueous dispersion for processing was obtained.

<Example 9>
15 parts of hydrophobic silica fine particles (surface-modified with dimethylsilyl group, number average primary particle diameter of about 12 nm, M value 45) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 900 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
10% by mass of this dispersion is added to a urethane copolymer composed of glycerin didodecyl ether, polyoxytetramethylene glycol, 4,4-dicyclohexylmethane diisocyanate, ethylene glycol, etc. An aqueous dispersion for water repellent processing was obtained.

<Example 10>
15 parts of hydrophobic silica fine particles (surface-modified with dimethylsilyl group, number average primary particle diameter of about 16 nm, M value 48) are added to 90 parts of ethyl alcohol together with a dispersant, and stirred at 900 rpm for 10 minutes using a homomixer. As a result, a uniform dispersion of hydrophobic silica fine particles was obtained.
This dispersion was added in an amount of 20% by mass to a silicone copolymer comprising side chain-modified diaminosilicone, hexamethylene diisocyanate, etc. to obtain an aqueous dispersion for water-repellent processing of the textile product of the present invention.

<Comparative Example 1> (Use of hydrophilic inorganic fine particles)
Instead of the hydrophobic silica fine particles of Example 1, commercially available colloidal silica (Snowtex AK (number average primary particle size 10-15 nm, M value 0), manufactured by Nissan Chemical Industries, “Snowtex” is a trademark of the company) Was added to the same water-repellent composition as in Example 1 to obtain an aqueous dispersion for water-repellent processing.

<Comparative Example 2> (No hydrophobic inorganic fine particles)
Using an aqueous dispersion of an acrylic copolymer similar to that in Example 1, an aqueous dispersion for water-repellent processing without adding hydrophobic silica fine particles was prepared.

<Comparative Example 3> (No hydrophobic inorganic fine particles)
Using the same aqueous dispersion of urethane copolymer as that of Example 9, an aqueous dispersion for water repellent processing without adding hydrophobic silica fine particles was prepared.

<Comparative Example 4> (No hydrophobic inorganic fine particles)
Using an aqueous dispersion of a silicone copolymer similar to that in Example 10, an aqueous dispersion for water repellent processing without adding hydrophobic silica fine particles was prepared.

<Comparative Example 5> (No hydrophobic inorganic fine particles)
Using an aqueous dispersion of a wax-based mixture composed of paraffin wax or the like, an aqueous dispersion for water-repellent processing to which no slip-off preventing component was added was prepared.

<Comparative Example 6> (Uses a water-repellent composition that does not provide an anti-slip effect)
A dispersion of hydrophobic silica fine particles similar to that in Example 1 was added in an amount of 20% by mass to the same wax-based mixture as in Comparative Example 5 to obtain an aqueous dispersion.

<Evaluation of water repellency>
Examples 1-10, 50 g / L of aqueous dispersions of Comparative Examples 1-6, Meikanate FM-1 (Blocked isocyanate manufactured by Meisei Chemical Co., Ltd.): 30% active ingredient Processing solution diluted with water to 10 g / L adjust the polyester fabric (basis weight: 60 g / ^{m 2,} using yarn: 56 dtex (50d)) and nylon cloth Padding to (basis weight:: 57.5g / ^{m 2,} using yarn 44 dtex (40d)), 2 pieces of A nip (55% pickup) was made with a rubber roller, dried at 110 ° C. for 2 minutes, and then cured at 170 ° C. for 1 minute to prepare an evaluation fabric. Water repellency was evaluated by the spray method of JIS L 1092 (2009) 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 results are shown in Tables 2 and 3.

<Evaluation of water-repellent washing durability>
After the created evaluation fabric is washed 0 times (HL-0) and washing is performed 10 times (HL-10) and 20 times (HL-20) according to the washing method described in JIS L 1092 (2009) Similarly, water repellency was evaluated. The results are shown in Tables 2 and 3.

<Evaluation of seam slippage>
A polyester taffeta fabric (weight per unit: 60 g / m ² , thread used: 56 dtex (50d)) was processed in the same manner as in the water-repellent processing according to the formulations of Examples 1 to 10 and Comparative Examples 1 to 6, and JIS L 1096-99. 8.21.1 Stitch slip-off method According to the method B, a test was performed with a warp slip at a load of 117.2 N (12 kgw), and the seam slip-off property was evaluated. The slipperiness of the stitches generally requires a performance of a slippage resistance value of 3 mm or less, and a slippage resistance value of 3 mm or less was set as a reference for the stitch slippage prevention property in the present invention. The results are shown in Tables 2 and 3.

  As shown in Table 2, all of Examples 1 to 8 were excellent in initial water repellency and washing durability, and also had good sliding resistance. On the other hand, Comparative Example 1 using hydrophilic inorganic fine particles could not obtain water-repellent washing durability. Further, in Comparative Example 2 where no inorganic fine particles were used, the slip resistance value was large, and there was a tendency that slipping was likely to occur.

  As shown in Table 3, Examples 9 and 10 were both excellent in initial water repellency and washing durability. Further, Example 9 had a good sliding resistance value. Further, when a silicone copolymer is used as the water-repellent component, the slip resistance value becomes extremely large (Comparative Example 4). When hydrophobic inorganic fine particles are added to the silicone copolymer (Example 10), the initial stage is as follows. While maintaining water repellency and washing durability, the slip resistance value was greatly improved. Further, when a wax-based mixture was used as a water-repellent component, the effect of adding inorganic fine particles was not observed (Comparative Example 5 and Comparative Example 6).

Claims (8)

As a stitch slip prevention component, comprising hydrophobic inorganic fine particles containing at least one compound selected from the group consisting of aluminum compounds, silicon compounds and titanium compounds,
As a water-repellent component, at least one selected from the group consisting of a fluorine-based copolymer, an acrylic copolymer, a urethane-based copolymer, and a silicone-based copolymer is included.
Water-based dispersion for water-repellent processing of textile products. The aqueous dispersion according to claim 1, wherein the hydrophobic inorganic fine particles have an average primary particle diameter of 1 to 100 nm. The aqueous dispersion according to claim 1 or 2, wherein a ratio of the hydrophobic inorganic fine particles to the water repellent component is 0.5 to 50% by mass. Furthermore, (a) an aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group, and / or
(B) containing N-methylol melamine,
The aqueous dispersion according to any one of claims 1 to 3. Hydrophobic inorganic fine particles containing at least one compound selected from the group consisting of an aluminum compound, a silicon compound and a titanium compound are previously dispersed in a hydrophilic solvent at least 5 times in amount to obtain a fluorine-based copolymer or an acrylic copolymer. A method for producing an aqueous dispersion for water-repellent processing of a textile product, which is blended with an aqueous dispersion containing at least one selected from the group consisting of a polymer, a urethane copolymer and a silicone copolymer. Along with the aqueous dispersion according to any one of claims 1 to 3,
(A) An aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or (b) a water-repellent processing method for textiles using N-methylolmelamine. A water-repellent processing method for a textile product, comprising: a step of immersing fibers in a processing liquid containing the aqueous dispersion according to claim 4; and a step of heat-treating at a temperature of 100 ° C. or higher after the step. A water-repellent fiber product processed by the method according to claim 6 or 7.