JP2012180323A - Method for producing antimicrobial agent for fiber, antimicrobial agent for fiber obtained by the production method, and antimicrobial fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method with which an antimicrobial agent for fiber with a specific sharp particle size distribution, excellent product stability, and excellent stability of a treatment bath, is obtainable within a short period of time and without admixture of any abraded matter by using a metal-based antimicrobial agent.SOLUTION: The metal-based antimicrobial agent is subjected to a finely pulverizing and dispersing treatment in an aqueous medium under high pressure of 50 MPa or more by using, as a dispersant, at least one kind selected from a group consisting of an anionic surfactant induced from a compound with a specific structure and a nonionic surfactant with a specific structure.

Description

  In the present invention, a metal antibacterial agent is treated with an antibacterial agent obtained by treating the metal antibacterial agent under high pressure using a dispersant in an aqueous medium, the antibacterial agent obtained by the method, and the antibacterial agent. It is related with the antibacterial fiber product obtained by this.

  Metal antibacterial agents are known as antibacterial agents with a broad antibacterial spectrum, and a method has been proposed in which finely divided water is dispersed using a media-type wet disperser such as a bead mill or ball mill and processed into fibers. Yes.

  For example, a method using a dispersion in which the content of iron and copper is 0.1% by weight or less based on pyrithione zinc (Patent Document 1), and a pyrithione zinc dispersion adjusted between pH 4 and 10 are used. Method (Patent Document 2), Method using a dispersion liquid pulverized such that pyrithione zinc having an average particle diameter of 0.1 to 1 μm and a particle diameter of 2 μm or more is 5% by weight or less based on total pyrithione zinc (patent) Document 3) has been proposed. In addition, a method has been proposed in which a pyridine antibacterial agent dispersed in fine particles is used in combination during dyeing (Patent Document 4).

  However, in the method of Patent Document 1, it is necessary to use a non-metallic medium in order to make the content of iron and copper 0.1 wt% or less with respect to pyrithione zinc. Furthermore, even when non-metallic media are used, metal contamination cannot be completely prevented due to wear on the inner wall of the disperser, causing problems such as decomposition of pyrithione zinc and coloring of the pyrithione zinc aqueous dispersion. .

  In the method of Patent Document 2, the decomposition of pyrithione zinc and the decrease in the antibacterial property due to the shift in pH caused by the metal mixing are prevented by adjusting the pH, but the trouble of adjusting the pH during or after the atomization treatment is required. Furthermore, there is a problem that the treatment of the pyrithione zinc aqueous dispersion on the fibers is limited to treatment in the vicinity of neutrality.

  In the method of Patent Document 3, a long time treatment is required to make the average particle size of pyrithione zinc 0.1 to 1 μm, and the particle size distribution hardly remains narrow even after a long time treatment and remains. There is a problem that fine particles of 2 μm or more adversely affect product stability and processing bath stability.

  When a pyridine-based antibacterial aqueous dispersion is used in combination during the dyeing treatment as in the method of Patent Document 4, the dispersibility of the dye is deteriorated, which causes dyeing spots. This is a problem caused by the use of a media-type wet disperser and a problem caused by a surfactant used as a dispersant.

  Further, silver antibacterial agents have a problem that silver is oxidized by long-time treatment and the aqueous dispersion is colored. Furthermore, the metal oxide antibacterial agent has a problem that it is difficult to make fine particles due to its large specific gravity and the dispersion stability is poor, and a surfactant must be used in order to improve the stability. There's a problem.

  As described above, metal antibacterial agents have many problems in order to obtain an aqueous dispersion that can be used as a fiber treating agent.

JP 2001-288014 A JP 2001-288015 A JP 2001-288017 A JP 2000-8275 A

  The present invention has been made in view of the above circumstances, and problems when a metal antibacterial agent is dispersed into fine particles using a media type wet disperser (problem contamination problem, long-time treatment problem) The purpose is to solve the problems caused by surfactants such as the improvement of product stability and treatment bath stability in a short time. The object of the present invention is to provide a production method capable of obtaining an antibacterial agent for fibers having a specific sharp particle size distribution without wear and contamination, good product stability and treatment bath stability. is there.

  Furthermore, it aims at providing the antibacterial agent for textiles manufactured by this manufacturing method, and the antibacterial fiber product with the washing-proof durability which provided it.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have carried out a media type wet process by subjecting a metal antibacterial agent to a fine particle dispersion treatment using a specific surfactant under a specific high pressure. It has been found that an antibacterial agent for fibers having a specific sharp particle size distribution can be obtained in a short time, with a low wear (low metal content), compared to the case of using a disperser. Furthermore, the obtained antibacterial agent for fibers was found to be excellent in product stability and treatment bath stability, and the present invention was completed based on these findings.

Therefore, the present invention comprises the following items 1) to 5).
1) A metal-based antibacterial agent is selected from the group of an anionic surfactant derived from a compound represented by the following general formula [1] and a nonionic surfactant represented by the following general formula [2] under a high pressure of 50 MPa or more. A method for producing an antibacterial agent for fibers, which comprises subjecting at least one selected to a dispersing agent to a fine particle dispersion treatment in an aqueous medium.

R- ^[O- (R 1 _-O) a -H] _m ··· [1]

(In the formula, m represents an integer of 1 or more, R represents a residue obtained by removing m hydroxy groups from an aromatic hydroxy compound having m hydroxy groups, and R ¹ represents an alkylene having 2 to 4 carbon atoms. A represents an integer of 0 or 1 or more)

R- ^[O- (R 1 _-O) b -H] _m · · · [2]

(In the formula, m represents an integer of 1 or more, R represents a residue obtained by removing m hydroxy groups from an aromatic hydroxy compound having m hydroxy groups, and R ¹ represents an alkylene having 2 to 4 carbon atoms. Represents a group, and b represents an integer of 3 or more)

  2) The method for producing an antibacterial agent for fibers according to 1), wherein the high pressure is 100 MPa or more and the dispersant is an anionic surfactant derived from the compound represented by the general formula [1].

  3) An aromatic hydroxy compound having m hydroxy groups represented by R is a (3 to 8 mol) styrene adduct of phenol, 4-cumylphenol, 4-phenylphenol or 2-naphthol, (3- The method for producing an antibacterial agent for fibers according to 1) or 2), which is 8 mol) an α-methylstyrene adduct or (3 to 8 mol) a benzyl chloride reactant.

4) An antibacterial agent for fibers obtained by the production method according to any one of 1) to 3).
5) An antibacterial fiber product obtained by treating with the fiber antibacterial agent described in 4).

  According to the method for producing an antibacterial agent for fibers according to the present invention, a problem arises when a metal antibacterial agent is subjected to fine particle dispersion using a conventional media-type wet disperser (problem mixing problem, long time The problem of processing and the problem of wide particle size distribution) can be solved all at once, and also the problems caused by surfactants such as improvement of product stability and processing bath stability can be solved.

  According to the present invention, there is also provided a production method capable of obtaining an antibacterial agent for fibers having a specific sharp particle size distribution and having good product stability and treatment bath stability in a short period of time without contamination of wear. It becomes possible to provide. Furthermore, it becomes possible to provide an antibacterial agent for fibers obtained by the production method and a functional fiber product having antibacterial properties having anti-washing durability imparted with the antibacterial agent.

Below, the preferable form for implementing this invention is demonstrated.
In the present invention, a metal antibacterial agent is microparticulated and dispersed using a specific surfactant under a specific high pressure, thereby reducing the amount of low wear (low metal content) in a short time compared to the conventional method. ) Provides a method for producing a fiber antibacterial agent adjusted to a specific sharp particle size distribution. Furthermore, the antibacterial agent for fibers excellent in product stability and treatment bath stability obtained by the production method and a functional fiber product obtained by treating with the antibacterial agent are provided.

  Examples of the metal antibacterial agent useful in the present invention include a zinc antibacterial agent, a silver antibacterial agent, and a metal oxide antibacterial agent. Examples of zinc-based antibacterial agents include 2-pyridinethiol zinc-1-oxide. Examples of the silver antibacterial agent include silver-supported zeolite, silver glass, silver-supported zirconium phosphate, silver-supported calcium phosphate, and silver-supported aluminum tripolyphosphate. Examples of the metal oxide antibacterial agent include silver oxide, zinc oxide and titanium oxide. These metal antibacterial agents can be used alone or in combination of two or more.

  These metal antibacterial agents are available as commercial products, such as zinc omazine (zinc pyrithione) (manufactured by Arch Chemicals), Zeomic HD-10N (silver zeolite) (manufactured by Sinanen Zeomic), zinc oxide. (Manufactured by Hakusui Tech Co., Ltd.), Silver Ace (silver-supported calcium phosphate) (manufactured by Taihei Chemical Sangyo Co., Ltd.), Rasap AN-600 (Silver-supported poorly soluble phosphate) (manufactured by Rasa Industrial Co., Ltd.), Novalon AG- 300 (silver-supported zirconium phosphate) (manufactured by Toagosei Co., Ltd.), JA-1 (titanium oxide) (manufactured by Ishihara Sangyo Co., Ltd.), Ion Pure (silver glass) (manufactured by Ishizuka Glass Co., Ltd.), etc. It is done.

  In the present invention, these metal antibacterial agents are preferably contained in the fiber antibacterial agent in an amount of 1 to 80% by mass, and from the viewpoint of fine particle dispersibility and antibacterial properties, it is 1 to 70% by mass. Is more preferable. If it is less than 1% by mass, the antibacterial property of the antibacterial fiber product tends to be hardly exhibited. If it exceeds 80% by mass, the viscosity of the antibacterial agent for fibers tends to be high, and the fine particle dispersion treatment tends to be difficult.

  Examples of the method for carrying out the fine particle dispersion treatment at a high pressure of 50 MPa or more include, for example, (i): a method in which the dispersion liquid is collided from two or more directions and fine particle dispersion, and (ii): the dispersion liquid is passed through the gap (slit). There is a method in which fine particles are dispersed using a shearing force at the time of forming. Specifically, as the method (i), an emulsifying dispersion machine such as Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), Ultimizer (manufactured by Sugino Machine Co., Ltd.), Starburst (manufactured by Sugino Machine Co., Ltd.) or the like is used. Process. Examples of the method (ii) include treatment using an emulsifier / disperser such as a homogenizer (manufactured by NIRO SOAVI) or (manufactured by APV GAULIN). These fine particle dispersion processing methods are non-media methods. The non-media method is a method that does not use media. With the high-pressure distributed processing in the present invention, non-media distributed processing is possible.

  In the present invention, the metal-based antibacterial agent is processed in a shorter time than the conventional method using a media-type wet disperser such as a bead mill or a ball mill by the method of finely dispersing and dispersing at a high pressure of 50 MPa or more. Thus, the fine particles can be dispersed in a sharp particle size distribution without causing the problem of contamination of the metal components such as the above or other wear from the disperser.

  In the present invention, the high pressure is 50 MPa or more, more preferably 100 MPa or more, and even more preferably 150 MPa or more. When it is less than 50 Mpa, it becomes difficult to obtain a target antibacterial agent for fibers having a specific sharp particle size distribution in a short time.

  An anionic surfactant useful in the present invention is an anionic surfactant derived from the compound represented by the general formula [1]. The nonionic surfactant useful in the present invention is a nonionic surfactant represented by the general formula [2].

  In the compound represented by the general formula [1], examples of the aromatic hydroxy compound having m hydroxy groups represented by R include phenol, 2-cumylphenol, 3-cumylphenol, and 4-cumyl. Monovalent aromatic hydroxy compounds such as phenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 1-naphthol, 2-naphthol, cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol; catechol, resorcinol, hydroquinone Divalent aromatic hydroxy compounds such as bisphenol A, bisphenol F and bisphenol S; pyrogallol (1,2,3-trihydroxybenzene), 1,2,4-trihydroxybenzene, phloroglucinol (1,3,3) Trivalent aromatic hydroxy compounds such as -trihydroxybenzene); tetravalent aromatic hydroxy compounds such as tetrahydroxybenzene; or their styrenes (styrene, α-methylstyrene, vinyltoluene) adducts, or (3 -8 mol) aromatic hydroxy compounds such as benzyl chloride reactants.

  Among them, from the viewpoint of particle size distribution, product stability, and treatment bath stability of the obtained antibacterial agent for fibers, (3 to 8 mol) styrene of phenol, 4-cumylphenol, 4-phenylphenol or 2-naphthol. Adducts, (3-8 mol) α-methylstyrene adducts or (3-8 mol) benzyl chloride reactants are preferred.

  Addition of styrenes to an aromatic hydroxy compound can be obtained, for example, by reacting styrenes with an aromatic hydroxy compound at 120 to 150 ° C. for 1 to 10 hours. The molar ratio of aromatic hydroxy compound to styrenes may be 1: 1 to 10, preferably 1: 3 to 8.

In the general formula [1], R ¹ is an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. From the viewpoint of particle size distribution, product stability, and treatment bath stability of the antibacterial agent for fibers, the alkylene group is preferably an ethylene group or a propylene group, and more preferably an ethylene group.

a is the number of added moles of the alkyleneoxy group represented by (R ¹ —O), and is 0 or an integer of 1 or more. a is preferably from 0 to 200, more preferably from 3 to 100. Even more preferably, it is 10-50. When a exceeds 200 mol, the effect of narrowing the particle size distribution of the antibacterial agent for fibers and the effect of improving the product stability and the treatment bath stability tend to decrease.

  The anionic surfactant derived from the compound represented by the general formula [1] is a sulfate ester salt, a phosphate ester salt, a carboxylate type anionic surfactant and a sulfosuccinic acid of the compound represented by the general formula [1]. It is a salt type anionic surfactant.

  The sulfate ester salt of the compound represented by the general formula [1] can be sulfated by reacting the compound represented by the general formula [1] with a sulfating agent according to a conventional method, and then neutralized appropriately with an alkaline compound. Or can be obtained by reacting the compound represented by the general formula [1] with sulfamic acid.

  The phosphate ester salt can be obtained by reacting the compound represented by the general formula [1] with phosphoric anhydride to form a phosphate ester according to a conventional method, and then neutralizing with an alkaline compound as appropriate.

  The carboxylate-type anionic surfactant can be obtained by reacting the compound represented by the general formula [1] with chlorocarboxylic acids in the presence of an alkaline compound as appropriate according to a conventional method.

  The sulfosuccinate type anionic surfactant can be obtained by reacting the compound represented by the general formula [1] with succinic anhydride and then reacting with anhydrous sodium bisulfite or anhydrous sodium sulfite according to a conventional method. .

  In the anionic surfactant derived from the compound represented by the general formula [1], when the compound represented by the general formula [1] has two or more hydroxy groups, 50% of the hydroxy groups It is preferable to anionize the above, more preferably 80% or more, and most preferably 100%.

  These anionic surfactants derived from the compound represented by the general formula [1] can be used alone or in combination of two or more.

  Among these anionic surfactants, from the viewpoint of particle size distribution, product stability, and treatment bath stability of the antibacterial agent for fibers, it is a sulfate ester salt, phosphate ester salt, sulfosuccinate salt type anionic surfactant. Preferably, it is a sulfate ester salt represented by the following general formula [3].

R- ^[O- (R 1 _-O) a -A] _m · · · [3]

(In the formula, m represents an integer of 1 or more, R represents a residue obtained by removing m hydroxy groups from an aromatic hydroxy compound having m hydroxy groups, and R ¹ represents an alkylene having 2 to 4 carbon atoms. A represents 0 or an integer of 1 or more, A represents —SO 3 X or H, and X represents H, Na, K, or an ammonium ion which may have a substituent.

In the nonionic surfactant represented by the general formula [2], R and R ¹ may be the same as those in the general formula [1]. b is the number of added moles of the alkyleneoxy group represented by (R ¹ —O), and is an integer of 3 or more. b is preferably 3 to 200, more preferably 5 to 100. Even more preferably, it is 10-50. If b is less than 3, the dispersibility of the antibacterial agent for fibers tends to deteriorate, and if it exceeds 200, the effect of narrowing the particle size distribution of the antibacterial agent for fibers and the stability of the product and the treatment bath are improved. It tends to be less effective.

  The nonionic surfactant represented by the general formula [2] is preferably a nonionic surfactant of HLB11 or more from the viewpoint of the particle size distribution, product stability, and treatment bath stability of the obtained fiber antibacterial agent. , HLB is more preferably 12 or more. In this case, one kind of nonionic surfactant having an HLB of 11 or more may be used, or two or more kinds of activators may be combined to make the HLB 11 or more. When the HLB of the nonionic surfactant represented by the general formula [2] is less than 11, the effect of finely dispersing the metal antibacterial agent by the heat generated during high-pressure treatment tends to be reduced. Here, HLB is based on HLB of Griffin, and a hydrophilic group refers to an ethyleneoxy group.

  In the present invention, only the anionic surfactant derived from the compound represented by the general formula [1] or the nonionic surfactant represented by the general formula [2] is used for the fine particle formation of the metal antibacterial agent. Or a combination of the anionic surfactant and the nonionic surfactant can be used. From the viewpoint of the product stability of the antibacterial agent for fibers and the adsorptivity of the antibacterial agent to the fiber product, it is preferable to use an anionic surfactant.

  These surfactants are preferably blended in the fiber antibacterial agent in an amount of 0.05 to 10% by mass, and from the viewpoint of fine particle dispersibility and fastness, 0.05 to 5% by mass. More preferably. When the amount is less than 0.05% by mass, it is difficult to obtain a target particle size, and the obtained antibacterial agent for fibers may cause separation, sedimentation, solidification, etc. in a short time. When it exceeds 10 mass%, various fastnesses of the antibacterial fiber product obtained by processing with the obtained antibacterial agent for fibers may be reduced.

  The antibacterial agent for fibers of the present invention is, for example, pre-dispersed a metal antibacterial agent in an aqueous medium using a specific surfactant, and then micronized and dispersed at high pressure using the above-mentioned non-media type wet disperser. Or obtained by subjecting a metal antibacterial agent, a specific surfactant and an aqueous medium to micronized dispersion treatment at high pressure continuously using a non-media type wet disperser. Can do.

  In the antibacterial agent for fibers obtained by the production method of the present invention, the content of iron and copper is preferably 2 ppm or less, more preferably 1 ppm or less. When it exceeds 2 ppm, the product stability of the fiber antibacterial agent and the treatment bath stability tend to decrease, and the aqueous dispersion of pyrithione zinc antibacterial agent and silver antibacterial agent tends to be colored.

  In the aqueous medium used in the production method of the present invention, in order to reduce the influence of iron and copper derived from water, the divalent metal such as iron or copper can be removed by treatment with ion exchange resin or activated carbon. preferable. The content of iron and copper can be measured with an Optima 5300 DV (Perkin Elmer) which is an ICP emission spectroscopic analyzer after decomposing an antibacterial agent for fibers with nitric acid.

  The fiber antibacterial agent obtained by the production method of the present invention has a specific particle size distribution in which the 50% cumulative particle size is 0.1 to 0.5 μm and the 90% cumulative particle size is 1.0 μm or less. Is preferred. The 50% cumulative particle size and the 90% cumulative particle size can be measured with a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.). When the 50% cumulative particle size is out of the range of 0.1 to 0.5 μm, the adsorption rate of the metal antibacterial agent to the fiber product is lowered, and the antibacterial property having washing resistance tends not to be exhibited. When the 90% cumulative particle diameter exceeds 1 μm, the product stability and the treatment bath stability of the antibacterial agent for fibers tend to be poor.

  As an aqueous medium used in the production method of the present invention, water or a solution comprising a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol, hexylene glycol, glycerin, sorbitol, butyl glycol, and solfit and water is used. Can be mentioned.

  In some cases, the antibacterial agent for fibers obtained by the production method of the present invention includes an alkylene oxide (carbon number 1 to 2) adduct of a higher alcohol having 10 to 22 carbon atoms, a polyoxyethylene sorbitan fatty acid ester, and the like. Various nonionic active agents, various anionic active agents, various cationic active agents, antibacterial agents, softeners, smoothing agents, penetrating agents, leveling agents, antistatic agents, chelating agents, antioxidants, antifoaming agents, solvents, synthesis A resin, a crosslinking agent, a thickener (such as xanthan gum, sodium polyacrylate, CMC, PVA) and the like may be added as long as the antibacterial performance is not impaired.

  Application of the obtained antibacterial agent for fibers to fibers includes fiber dyeing processing encyclopedia (published in 1965, published by Nikkan Kogyo Shimbun), pages 396 to 397 and color dye chemistry III (1975, published by Jikkyo Publishing Co., Ltd.) 256. ~ Pading process described on page 260, dyeing and finishing equipment overview (published in 1986, published by Textile Co., Ltd.) 196-247, immersion treatment using a batch type dyeing machine described in pages 196 to 247, and dyeing and finishing equipment overview described on pages 473 to 477 It can be performed by a known method such as coating using a special finishing apparatus.

  In the case of padding treatment, the concentration of the metal antibacterial agent in the treatment bath is preferably in the range of 0.01 to 10% by mass, for example. When applying by immersion treatment, the concentration of the metal antibacterial agent in the treatment bath is, for example, 0.01 to 10% o.d. w. f. It is preferable that it is the range of these. In the case of coating, for example, the antibacterial agent aqueous dispersion of the present invention mixed with a binder can be used. In this case, the concentration of the metal antibacterial agent in the binder is, for example, 0.1 to 10% by mass. A range is preferable.

  The amount of the antibacterial agent for fibers of the present invention applied to the fiber is preferably such that the metal antibacterial agent contained therein is 0.001 to 5% by mass relative to the fiber product. If this amount is less than 0.001% by mass, the antibacterial effect with sufficient washing resistance is hardly exhibited, and even if it exceeds 5% by mass, the effect of further improving the antibacterial property with washing resistance is small and economical. is not.

  In addition, when the fiber antibacterial component alone has insufficient durability for washing, urethane resin, melamine resin, glyoxy resin, silicone compound, acrylic compound, and the like can be used in a timely manner.

  The material of the fiber product to which the antibacterial agent for fibers of the present invention can be applied is not particularly limited. For example, natural fibers such as cotton, hemp, wool, and silk, regenerated cellulose fibers such as rayon, cupra, and Tencel (trademark), Used for various materials such as semi-synthetic fibers such as acetate and promix, polyamide fibers, polyester fibers, acrylic fibers, polyolefin fibers, polyvinyl chloride fibers, polyimide fibers, polyurethane fibers, and composite fibers of these fibers be able to. The form of the fiber product is not particularly limited, and examples thereof include short fiber, long fiber, yarn, woven fabric, knitted fabric, non-woven fabric, cotton, sliver, top, and paper.

  In the present invention, the metal antibacterial agent is a fiber antibacterial agent having a specific sharp particle size distribution with a small amount of metal, for the first time by using a specific surfactant and carrying out fine particle dispersion treatment at a specific high pressure. Can be obtained in a shorter time than the conventional method.

  When a specific surfactant is used and dispersion treatment is performed using a conventional media-type wet disperser, the effect of atomization is small, and the metal antibacterial agent cannot be atomized to the target particle size. Or, even if it can be atomized to the target particle size, it takes a long time and is industrially disadvantageous. Further, during the long-term micronization process, wear from the disperser (such as metal) is mixed, causing problems such as changes in appearance, a decrease in stability, and a decrease in adsorption rate.

  When a dispersion treatment is performed at a specific high pressure without using a specific surfactant, the metal antibacterial agent can be dispersed into fine particles, but the effect of stabilizing this dispersion is inferior. Problems such as a decrease in product stability, a decrease in treatment bath stability, and a decrease in adsorption rate occur.

  Only when a specific surfactant as specified in the present invention is combined with a specific high pressure, it is possible to obtain a low metal fiber antibacterial agent having a specific sharp particle size distribution in a short time. An aqueous dispersion having good product stability, treatment bath stability, and adsorption rate can be obtained. By treating the fiber product with this aqueous dispersion, it is possible to obtain a high-quality, antibacterial fiber product having wash resistance.

  Further, the pH of the treatment bath at the time of application of the antibacterial agent for fibers of the present invention to the fiber product may be in the range of 2 to 12, for example, the dyeing bath pH 2 to 5 at the acid dyeing of the polyester fiber or the polyester fiber Even if the dyeing bath pH is 10 to 12 at the time of alkali dyeing, antibacterial processing can be performed simultaneously with dyeing, and the process can be shortened.

  EXAMPLES Hereinafter, although an Example is given and this invention is further demonstrated, this invention is not restrict | limited at all by these Examples.

Antibacterial component Antibacterial agent 1: Zinc omazine (zinc pyrithione), manufactured by Arch Chemicals Co., Ltd. Antibacterial agent 2: Zeomic HD-10N (silver zeolite), manufactured by Sinanen Zeomic Co., Ltd. Antibacterial agent 3: Zinc oxide, manufactured by Hux Itec Corp.

Synthesis of Dispersant Synthesis Example 1: Ethylene oxide 20 mol adduct of tristyrenated phenol, HLB = 13.7 (hereinafter referred to as “TP20E”)
A reaction vessel was charged with 94 parts by mass (1.0 mol) of phenol and 0.1 part by mass of sulfuric acid, heated with heating in a nitrogen gas stream while stirring, and 312 parts by mass (3 mols) of styrene monomer at 110 to 130 ° C. ) Was added dropwise and allowed to undergo an addition reaction at 125 to 135 ° C. for about 3 hours, followed by cooling to obtain a brown transparent viscous liquid tristyrenated phenol.

  403 parts by mass (1 mol) of the obtained tristyrenated phenol and 4.5 parts by mass of caustic soda were charged in an autoclave and heated to about 130 ° C., and then 880 parts by mass (20 mol) of ethylene oxide was added at a temperature of 150 ° C. The reaction was carried out at ˜160 ° C. and a pressure of 0.39 MPa or less. After completion of the ethylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a nonionic surfactant as a slightly yellow soft solid.

Synthesis example 2: Ethylene oxide 10 mol adduct of tristyrenated phenol, HLB = 10.4 (hereinafter referred to as “TP10E”)
Except for changing the number of moles of ethylene oxide added to 10 moles, the same operation as in Synthesis Example 1 was performed to obtain a slightly yellow turbid liquid nonionic surfactant.

Synthesis Example 3: TP20E sulfate (hereinafter referred to as “TP20E-S”)
TP20E (1286 parts by mass) (1 mol) was charged into a reaction vessel, and 116.5 parts by mass (1 mol) of chlorosulfonic acid was added dropwise at 30 to 40 ° C. and a reduced pressure of 200 mmHg, and the reaction was performed at 30 to 40 ° C. for about 2 hours. Dehydrochlorination (sulfation reaction) was performed. A neutralized kettle in which isopropyl alcohol and aqueous ammonia were previously mixed was added with a sulfate at 50 ° C. or lower, and neutralized to pH 8 to obtain a pale yellow transparent liquid composition containing 30% by mass of an anionic surfactant.

Synthesis Example 4: Ammonia neutralized product (hereinafter referred to as “TP20E-P”) of soprophor 3D33 (polyoxyethylene arylphenyl ether phosphate, Rhodia Nikka Co., Ltd.)
Soprophor 3D33 (500 parts by mass) was added to a neutralization kettle in which 50% isopropyl alcohol aqueous solution and 25% ammonia aqueous solution had been mixed in advance, and the mixture was stirred for about 1 hour to make it uniform and neutralized to pH 8 to obtain an anionic interface. A yellow transparent liquid composition containing 50% by mass of the activator was obtained.

Synthesis Example 5: Sulfosuccinate of TP20E (hereinafter referred to as “TP20E-SS”)
24.5 parts by mass (0.25 mol) of maleic anhydride, TP20E (643 parts by mass) (0.5 mol), and 2 parts by mass of paratoluenesulfonic acid were charged into a reaction vessel, and the temperature was raised under a nitrogen gas stream. Then, dehydration reaction was performed at 170 to 180 ° C. for about 4 hours to obtain a diesterified product.

  663 parts by mass of the resulting diesterified product and 127.5 parts by mass of hexylene glycol were charged into a reaction vessel, heated to 80 ° C., heated to 23.8 parts by weight of anhydrous sodium bisulfite, 3.5 parts by mass of caustic soda, and water 244. .2 parts by mass of a neutralized solution was added and sulfonated at 90 to 100 ° C. to obtain a slightly yellow liquid composition containing 65% by mass of an anionic surfactant having a pH of 8.

Synthesis Example 6: Carboxymethylated product of TP20E (hereinafter referred to as “TP20E-MC”)
TP20E (1286 parts by mass) (1 mol) and caustic soda (40 parts by mass) (1 mol) were charged into a reaction vessel, and sodium monochloroacetate (116.5 parts by mass) (1 mol) at 50 to 60 ° C. in a nitrogen stream. Is added in 10 minute intervals at 10 minute intervals. Then, after reacting at 50 to 60 ° C. for about 2 hours, water was added to obtain a slightly yellow liquid composition containing 60% by mass of an anionic surfactant. The pH was 10.

Synthesis Example 7: Tristyrenated cumylphenol ethylene oxide 20 mol adduct, HLB = 12.5 (hereinafter referred to as “TC20E”)
A reaction vessel was charged with 212 parts by mass (1.0 mol) of 4-cumylphenol and 0.1 part by mass of sulfuric acid, heated with heating in a nitrogen gas stream while stirring, and 312 masses of styrene monomer at 110 to 130 ° C. Part (3 mol) was added dropwise, and an addition reaction was carried out at 125 to 135 ° C. for about 3 hours, followed by cooling to obtain a brown transparent viscous liquid tristyrenated cumylphenol.

  524 parts by mass (1 mol) of the tristyrenated cumylphenol and 4.5 parts by mass of caustic soda were charged into an autoclave, heated to about 130 ° C., and then 880 parts by mass (20 mol) of ethylene oxide was added. The reaction was performed at a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. After completion of the ethylene oxide addition reaction, the mixture was cooled and neutralized with glacial acetic acid to pH 7 to obtain a nonionic surfactant as a slightly yellow solid.

Synthesis Example 8: TC20E sulfate (hereinafter referred to as “TC20E-S”)
TC20E (1404 parts by mass) (1 mol) was charged into a reaction kettle and stirred with a homomixer, while sulfamic acid (78 parts by mass) (1.3 mol) was added at intervals of 20 minutes at 105 to 115 ° C. under a nitrogen stream. Added in 4 portions. Thereafter, reaction was carried out at 105 to 115 ° C. for about 2 hours, water, isopropyl alcohol and aqueous ammonia were added to obtain a yellow liquid composition containing 50% by mass of an anionic surfactant having a pH of 8.

Water Dispersion Equipment Disperser 1: Starburst HJP-25001, manufactured by Sugino Machine Co., Ltd. A type of disperser that collides high-pressure dispersion liquids from two directions and pulverizes and disperses them with high shear force.

Disperser 2: Nanomizer YSNM-1500, manufactured by Yoshida Kikai Kogyo Co., Ltd. In a diamond-type collision-type generator, high-pressure dispersions are collided with each other from two directions, and the resulting particles are dispersed with high shearing force. Disperser

Disperser 3: PANDA 2K type, manufactured by NIRO SOAVI
Disperser of the type that disperses fine particles with high shearing force when the high pressure dispersion liquid passes through the slit (gap)

Disperser 4: APV GAULIN LABORATORY HOMOGENIZER 15MR-8TA, manufactured by APV GAULIN Co., Ltd. A type of disperser that disperses fine particles by shearing force when a high-pressure dispersion liquid passes through a slit (gap).

Dispersing machine 5: DYNO-MILL KDL type, manufactured by Willy et Bakkofen Co., Ltd. A type of bead mill that disperses particles by grinding powder using a media.

Preparation of antibacterial agent for fibers Example 1
Antibacterial agent 1 (500 parts by mass), TP20E (2 parts by mass), ion-exchanged water (498 parts by mass) using a disperser 1, fine particles for 50 minutes at a processing pressure of 150 MPa and a processing speed of 100 mL / min The antibacterial agent for fibers (amount of antibacterial agent 50% by mass, amount of dispersant 0.2% by mass) was obtained. The 50% cumulative particle size was 0.3 μm, the 90% cumulative particle size was 0.7 μm, and the iron and copper contents were less than 0.5 ppm.

  Using this antibacterial agent for fibers, the polyester ponge fabric was padded, treated in a bath, or dyed together under the conditions for production of the following antibacterial fiber product to obtain an antibacterial fiber product.

Examples 2-19, Comparative Examples 1-6
Examples 2 to 19 and Comparative Examples are the same as in Example 1 except that the antibacterial agent, disperser, processing pressure, media used, dispersant, processing time, and processing speed are changed as shown in Tables 1 to 3. 2 to 6 antibacterial agents for fibers (antibacterial agent amount 50% by mass, dispersant amount 0.2% by mass) were obtained. Subsequently, using these antibacterial agents for fibers, the polyester ponge cloth was subjected to padding treatment, treatment in bath or dyeing same bath treatment as in Example 1 to obtain antibacterial fiber products.

  Here, in Examples 10, 11, and 17, the antibacterial agent for fibers was obtained by changing 2 parts by mass of the dispersant in Example 1 to 1 part by mass of the anionic surfactant and 1 part by mass of the nonionic surfactant shown in Table 2. Got. In addition, about the composition obtained by the synthesis example 3, the synthesis example 4, the synthesis example 5, the synthesis example 6, and the synthesis example 8, since an anionic surfactant will be 100 mass% because a composition contains a water | moisture content. It was collected in terms of.

Example 20
Using the antibacterial agent for fibers obtained in Example 1, polyester / cotton (65/35) was treated by treatment in a bath to obtain an antibacterial fiber product. In this treatment, the temperature time condition was 130 ° C. × 30 minutes, and the bath composition was 0.2% o. w. f. It was.

Examples 21-23
Except having changed the kind of fiber product as shown in Table 4, it carried out similarly to Example 20, and obtained the antimicrobial fiber product of Examples 21-23. In the case of triacetate, 6-nylon and acrylic, the temperature time condition of the treatment was 90 ° C. × 30 minutes.

Manufacture of antibacterial fiber products Padding processing Equipment used Pad: Pneumatic mangle NM-450, manufactured by Daiei Kagaku Seisakusho Co., Ltd. Dry, cure: Heat set tester HZ-85S, Uenoyama Kiko Co., Ltd. Processing conditions : Pad → Dry → Cure Pad: Bath composition: Antibacterial agent for fiber 0.1% soln. 1 dip-1 nip, 80% pickup
Drying: 120 ° C. × 2 minutes Cure: 180 ° C. × 30 seconds Treatment in bath Equipment used: MINI-COLOR® MC12EN, manufactured by TEXAM GIKEN Co., Ltd. Treatment conditions: treatment in bath → water washing (5 minutes) → drying (100 ° C. × 5 Min)
Temperature time: 130 ° C. × 30 minutes (temperature increase 2 ° C./min)
Bath ratio: 1:10
Bath composition: antibacterial agent for fibers 0.1% o. w. f.

Dyeing bath treatment Equipment used: MINI-COOLUR MC12EN, manufactured by Texam Giken Co., Ltd. Treatment conditions: Dyeing → RC → Washing (5 minutes) → Drying (100 ° C. × 5 minutes)
(staining)
Dyeing: 130 ° C x 30 minutes (temperature rise 2 ° C / min)
Bath ratio: 1:10
Bath composition: antibacterial agent for fibers 0.1% o. w. f.
Disperse dye (Dianix Blue AC-E, manufactured by Dystar Japan Co., Ltd.) 0.5% o. w. f.
80% aqueous acetic acid solution 0.5 g / L (bath pH = 4.2)
Dye dispersant (Nikka Sun Salt RM-340E (manufactured by Nikka Chemical Co., Ltd.)) 0.5g / L

(RC)
RC: 80 ° C. × 20 minutes Bath ratio: 1:20
Bath composition: soaping agent (Sunmall RC-700E, manufactured by Nikka Chemical Co., Ltd.) 1 g / L,
Hydrosulfite 1g / L, Soda ash 1g / L

Evaluation item The following evaluation was performed about the antibacterial agent and antibacterial fiber product which were obtained by the Example and the comparative example.
(Antimicrobial agent)
(1) Particle size A 50% cumulative particle size and a 90% cumulative particle size were measured with a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.).

(2) Iron and copper content After the antibacterial agent was decomposed with nitric acid, the iron content and the copper content were measured with an ICP emission spectrophotometer Optima 5300 DV (manufactured by Perkin Elmer).

(3) pH of aqueous dispersion
The pH of the stock solution before and after the preparation of the antibacterial agent for fibers was measured with a pH meter F-22 (manufactured by Horiba, Ltd.).

(4) Product stability The state when 500 ml of fiber antibacterial agents were placed in a 500 ml beaker and allowed to stand at room temperature for 12 hours was evaluated according to the following evaluation criteria.
A: A precipitate is not generated at the bottom of the beaker and is a uniform aqueous dispersion. Alternatively, even if sediment is generated, it can be easily dispersed with a glass rod.
B: Sediment is generated at the bottom of the beaker and is partially solidified, but can be dispersed with a glass rod.
C: Settling and solidification occurs at the bottom of the beaker and cannot be dispersed with a glass rod.

(5) Appearance change The appearance before and after the microparticle dispersion treatment of the antibacterial agent was evaluated according to the following evaluation criteria.
A: There is no change in appearance before and after the micronization treatment.
B: Some change in appearance before and after the micronization treatment.
C: There is a great change in appearance before and after the micronization treatment.

(6) Dye dispersibility (winding test)
The polyester knit was treated under the following conditions, and the effect on the disperse dye was investigated when an antibacterial agent was used in combination.
Equipment used: Color pet dyeing machine, manufactured by Texam Giken Co., Ltd. Test cloth: Polyester knit 300 mL of test bath is prepared in a pot for color pet dyeing machine.

(Bath composition)
Disperse dye (Dianix Blue AC-E, manufactured by Dystar Japan Co., Ltd.) 0.5% o. w. f.
80% aqueous acetic acid solution 0.5 g / L (bath pH = 4.2)
Dye dispersant (Nikka Sun Salt RM-340E, manufactured by Nikka Chemical Co., Ltd.)) 0.5g / L
Antibacterial agent for fibers 0.5% o. w. f.
Using the above test bath, the bath ratio is 1:30, the temperature is raised from 60 ° C. at 3 ° C./min, and held at 115 ° C. for 1 min. After cooling to 60 ° C., the product was taken out, and the stained spots of the fabric were evaluated according to the following criteria.
A: No staining spots B: Some staining spots C: Many staining spots

(7) Dye dispersibility (filtration test)
The treatment was carried out under the following conditions, and the effect on the disperse dye was investigated when an antibacterial agent was used in combination.
Equipment used: Color pet dyeing machine (made by Texam Engineering Co., Ltd.)
Adjust 300mL of test bath to pot for color pet dyeing machine.

(Bath composition)
Disperse dye (Dianix Blue AC-E, manufactured by Dystar Japan Co., Ltd.) 0.5% o. w. f.
80% aqueous acetic acid solution 0.5 g / L (bath pH = 4.2)
Dye dispersant (Nikka Sun Salt RM-340E, manufactured by Nikka Chemical Co., Ltd.) 0.5 g / L
Antibacterial agent for fibers 0.5% o. w. f.

Without using the dough, the temperature is increased from 60 ° C. at 3 ° C./min and maintained at 130 ° C. for 30 minutes. After cooling to 80 ° C., the test bath was filtered with 5A filter paper (manufactured by ADVANTEC), and the filtration state was evaluated according to the following criteria.
A: No dye spec (no clogging on filter paper)
B: There is a little dye spec (the filter paper is clogged a little)
C: Many dye specifications (clogged filter paper)

Antibacterial fiber products (1) Antibacterial properties The following tests were conducted in accordance with the antibacterial evaluation methods and standards of the Japan Fiber Evaluation Technology Council (hereinafter referred to as the Textile Technology Association).
About antibacterial activity before washing and after 10 washings, antibacterial staphylococci are used as test bacteria in accordance with the bacteria absorption method which is a quantitative method of JIS L 1902 (2008) The bacteriostatic activity value assuming deodorant processing was evaluated.

  In addition, about washing, it conformed to the washing method manual (JIS L 0217 (1995) Appendix 103 method 103) defined by the Japan Textile Technology Association. If the bacteriostatic activity value is greater than 2.2 for both the pre-washing and post-washing samples, it is determined that the effect is effective.

(2) Hue and dirt of the fabric The hue and dirt of the functional fiber product obtained by the padding treatment or the treatment in the bath are compared with the hue and dirt when no antibacterial agent is used (Comparative Example 1). Evaluation was performed according to the following evaluation criteria.
A: There is almost no change in hue, and there is no stain.
B: Slight change in hue or slight stain
C: There is a large change in hue, or there are many stains.

(3) Mangle dirt The dirt on the rubber roll surface during padding treatment was evaluated according to the following evaluation criteria.
A: There is no dirt on the surface of the rubber roll.
B: The rubber roll surface is slightly soiled.
C: There is a large stain on the surface of the rubber roll.

(4) Adsorption rate The functional fiber product obtained by treating with the antibacterial agent for fibers was rinsed with running water for 5 minutes to wash away the unadsorbed antibacterial agent and dispersant. The obtained sample was dissolved in nitric acid, the zinc content and silver content were measured with an ICP emission spectrophotometer Optima5300DV (manufactured by Perkin Elmer), converted into zinc pyrithione content, silver zeolite content and zinc oxide content, and the fiber base The adsorption amount (% by mass) of the antibacterial component to the material was determined. The adsorption rate (%) was calculated from the following formula based on the amount of the antibacterial agent adsorbed and the theoretical amount (% by mass) of the antibacterial component applied to the fiber base, which is determined from the concentration of the antibacterial component in the treatment bath .
Adsorption rate (%) = Adsorption amount of antibacterial agent component × 100 / Amount of application of antibacterial agent component

The results obtained are shown in the table below.

  As can be seen from the results of Tables 1 to 3, when a specific high-pressure treatment is performed using a specific surfactant, a fiber antibacterial agent having a sharp specific particle size distribution is obtained in a short time, and product stability However, the appearance was not changed. Moreover, in the Examples, antibacterial properties with wash resistance are obtained. The adsorption rate is also improved compared to the comparative example. There was no change in hue of the fabric, no stains, no mangle stains, and good dye dispersibility.

  On the other hand, when a specific surfactant is not used as in Comparative Example 2, for example, compared with Example 1 and Example 5, the particle size does not become small in the same processing time, and the product stability is poor. The dye dispersibility was also poor. Moreover, the antibacterial agent adsorption rate was low, and antibacterial properties with washing resistance were not obtained. Furthermore, changes in the hue of the fabric, dirt, and mangles were observed.

  When a high pressure of 50 MPa or more was not used as in Comparative Example 3, the metal antibacterial agent did not progress into fine particles even after long-term treatment, resulting in poor product stability and poor dye dispersibility. . Moreover, the antibacterial agent adsorption rate was low, and antibacterial properties with washing resistance were not obtained. Furthermore, changes in the hue of the fabric, dirt, and mangles were observed.

  In Comparative Examples 4 to 6 using a bead mill which is a conventional media type wet disperser, it took a long time to make fine particles. In addition, iron was mixed, product stability was poor, and dye dispersibility was also poor. In Comparative Example 4 and Comparative Example 5 using antibacterial agent 1 and antibacterial agent 2, the antibacterial agent for fibers was colored and a large change in appearance was observed. Also, the antibacterial agent adsorption rate was low, and antibacterial properties with washing resistance could not be obtained. Furthermore, changes in the hue of the fabric, dirt, and mangles were observed.

  From the results in Table 4, it can be seen that the antibacterial agent for fibers of the present invention is applicable to various fibers.

  According to the method for producing an antibacterial agent for fibers of the present invention, it can be produced in a shorter time than the conventional production method, and the problems of the conventional production method can be solved all at once. Furthermore, the antibacterial agent for fibers obtained by the method for producing an antibacterial agent for fibers of the present invention has product stability and treatment bath stability compared to the antibacterial agent for fibers obtained by a method using a conventional media-type wet disperser. It is possible to easily obtain a functional fiber product that is good, has high quality, and has antibacterial properties with washing resistance. Therefore, the present invention is industrially useful.

Claims (5)

The metal antibacterial agent is selected from the group of an anionic surfactant derived from a compound represented by the following general formula [1] and a nonionic surfactant represented by the following general formula [2] under a high pressure of 50 MPa or more. A method for producing an antibacterial agent for fibers, which comprises subjecting at least one type of dispersant to fine particle dispersion in an aqueous medium.
R- ^[O- (R 1 _-O) a -H] _m ··· [1]
(In the formula, m represents an integer of 1 or more, R represents a residue obtained by removing m hydroxy groups from an aromatic hydroxy compound having m hydroxy groups, and R ¹ represents an alkylene having 2 to 4 carbon atoms. A represents an integer of 0 or 1 or more)
R- ^[O- (R 1 _-O) b -H] _m · · · [2]
(In the formula, m represents an integer of 1 or more, R represents a residue obtained by removing m hydroxy groups from an aromatic hydroxy compound having m hydroxy groups, and R ¹ represents an alkylene having 2 to 4 carbon atoms. Represents a group, and b represents an integer of 3 or more)   The manufacturing method of the antibacterial agent for fibers of Claim 1 whose high pressure is 100 Mpa or more and whose dispersing agent is an anionic surfactant induced | guided | derived from the compound shown by General formula [1].   The aromatic hydroxy compound having m hydroxy groups represented by R is phenol, 4-cumylphenol, 4-phenylphenol or 2-naphthol, (3-8 mol) styrene adduct, (3-8 mol) The method for producing an antibacterial agent for fibers according to claim 1 or 2, which is an α-methylstyrene adduct or a (3 to 8 mol) benzyl chloride reaction product.   The antibacterial agent for fibers obtained by the manufacturing method of any one of Claims 1-3.   An antibacterial fiber product obtained by treating with the antibacterial agent for fibers according to claim 4.