WO2012049978A1

WO2012049978A1 - Antibacterial fiber treatment agent, manufacturing method thereof, and antibacterial fiber manufacturing method

Info

Publication number: WO2012049978A1
Application number: PCT/JP2011/072499
Authority: WO
Inventors: 裕幸土手; 勘藤　芳弘
Original assignee: 松本油脂製薬株式会社
Priority date: 2010-10-15
Filing date: 2011-09-30
Publication date: 2012-04-19
Also published as: CN103154356A; JPWO2012049978A1

Abstract

Disclosed is an antibacterial fiber treatment agent which wash-durable and capable of imparting excellent antibacterial properties to a fiber material; also disclosed are a manufacturing method of said antibacterial treatment agent, and a method of manufacturing antibacterial fiber treated with said antibacterial treatment agent. The disclosed antibacterial fiber treatment agent necessarily contains a silver-based inorganic antibacterial agent in which a silver-containing antibacterial metal is carried on an inorganic carrier, a compound (A) represented by general formula (1), and water, and is in a state in which said silver-based inorganic antibacterial agent is dispersed in water with an average particle diameter of 0.01-3μm.

Description

Antibacterial finishing agent for fibers, method for producing the same and method for producing antibacterial fibers

The present invention relates to an antibacterial processing agent for fibers used for imparting antibacterial properties to a fiber material, a method for producing the antibacterial processing agent, and a method for producing an antibacterial fiber for imparting the antibacterial processing agent to a fiber material.

In recent years, emphasis has been placed on comfort and hygiene, and antibacterial and deodorizing functions are one of the functions that bear that need. Nowadays, antibacterial functions have generally permeated deeply, and it has become natural that product materials are given antibacterial properties. Among the materials that impart antibacterial properties, antibacterial processing is especially attracting attention for textile materials used in clothing, bedding and living items.

As antibacterial agents for imparting antibacterial properties to fiber materials, conventionally, quaternary ammonium compounds, pyrithione organic antibacterial agents, antibacterial metals and metal oxides, and further, these are supported on a carrier such as zeolite. An inorganic antibacterial agent is used. Among such antibacterial agents, inorganic antibacterial agents are widely used for antibacterial processing of fiber materials. In particular, silver-based inorganic antibacterial agents are the mainstream of inorganic antibacterial agents currently used because they have a high antibacterial effect, a broad antibacterial spectrum, and high safety to the human body or the environment.

As a method for imparting antibacterial properties to a fiber material, a method in which an antibacterial agent is kneaded in advance into a spinning dope in the production stage of the fiber material, a method in which the antibacterial agent is imparted to the fiber material by post-processing, etc. are known.

In the method in which the antibacterial agent is kneaded in advance in the spinning dope, not only the antibacterial agent inside the resin is ineffective, but many of the antibacterial agents in the vicinity of the resin surface cannot exhibit a sufficient antibacterial effect by the resin coating Thread breakage may occur at the melt spinning stage. When a large amount of an antibacterial agent is added for the purpose of enhancing the antibacterial effect, the physical properties of the fiber are easily lost or the fiber is likely to become opaque. Conversely, when the amount of the antibacterial agent added is small, the antibacterial effect is not sufficiently exhibited. As described above, there are many problems in the method of kneading the antibacterial agent into the spinning dope in advance.

For these reasons, in order to impart excellent antibacterial properties, it is desirable to apply an antibacterial agent to the fiber material by post-processing, but the antibacterial agent has insufficient adhesive strength to the fiber material, and the washing durability is low. There was a problem of being inferior. In order to solve this problem, for example, the method for producing an antibacterial fiber of Patent Document 1 has been proposed. However, the antibacterial processing agent itself is used because it has obtained washing durability depending on processing conditions. It did not have excellent washing durability. Furthermore, this method requires complicated processes and conditions and is not practical.

Japanese Unexamined Patent Publication No. 7-243180

The present invention has been made in order to solve the problems in the antibacterial processing of such conventional fiber materials, and is a processing agent applied to the fiber material in post-processing, and imparts excellent antibacterial properties to the fiber material. It is an object of the present invention to provide an antibacterial finishing agent for fibers that can be used and has excellent washing durability, a method for producing the antibacterial finishing agent, and a method for producing an antibacterial fiber to which the antibacterial finishing agent is applied. To do.

As a result of intensive studies to solve the above problems, the present inventors have obtained an antibacterial processing agent for fibers in which a silver-based inorganic antibacterial agent is dispersed in the presence of a specific compound (A) and water. It has been found that excellent antibacterial properties can be imparted to the fiber material and that it is also excellent in washing durability.

That is, the antibacterial finishing agent for fibers of the present invention (hereinafter sometimes referred to as “antibacterial finishing agent”) is a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, The compound (A) represented by 1) and water are essential, the silver-based inorganic antibacterial agent is dispersed in water, and the average particle size is 0.01 to 3 μm.

(Wherein R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR ² R ³ or OR ⁴ . .R ^2, ^{R 3} and ^{R 4} are each independently hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms .M ¹ Is a hydrogen atom, an alkali metal or ^a group represented by NR ^a R ^b R ^c R ^d , R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or It is a polyoxyalkylene group.)

The inorganic carrier is preferably at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker.

The antibacterial processing agent of the present invention further includes a surfactant represented by the following general formula (2), a surfactant represented by the following general formula (3), a surfactant represented by the following general formula (4), and the following: It is preferable to include at least one surfactant (B) selected from surfactants represented by the general formula (5).

(Wherein R ⁵ is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M ² is a hydrogen atom, an alkali metal, an alkaline earth metal, or ^a group represented by NR ^a R ^b R ^c R ^d R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)

(Wherein A ² O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)

(Wherein A ³ O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M ³ is a hydrogen atom, an alkali metal , Alkaline earth metal or ^a group represented by NR ^a R ^b R ^c R ^d R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)

(In the formula, A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M ⁴ is a hydrogen atom, an alkali metal, an alkaline earth metal or ^a group represented by NR ^a R ^b R ^c R ^d R ^a , R ^b , R ^c and R ^d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)

The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.

The method for producing an antibacterial processing agent of the present invention includes a step of wet-grinding a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is supported on an inorganic carrier in the presence of the compound (A) and water, The average particle size of the wet-ground silver-based inorganic antibacterial agent is 0.01 to 3 μm.

In the method for producing an antibacterial processing agent of the present invention, the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate winker. preferable.

The wet pulverization step is preferably a step of wet pulverizing the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water. The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.

The method for producing an antibacterial fiber of the present invention includes a step of imparting to the fiber material the antibacterial processing agent and / or the antibacterial processing agent obtained by the production method.

The antibacterial finishing agent for fibers of the present invention can impart excellent antibacterial properties to fiber materials and is excellent in washing durability.
The method for producing an antibacterial processing agent for fibers of the present invention can provide an antibacterial agent for fibers that can impart excellent antibacterial properties to fiber materials and is also excellent in washing durability.
In addition, the method for producing an antibacterial fiber of the present invention can provide an antibacterial fiber that is excellent in antibacterial properties and excellent in washing durability.

The antibacterial processing agent for fibers of the present invention essentially contains a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, the compound (A) represented by the above general formula (1), and water. The silver-based inorganic antibacterial agent is dispersed in water. This will be described in detail below.

[Silver inorganic antibacterial agent]
The silver-based inorganic antibacterial agent is formed by supporting an antibacterial metal containing silver on an inorganic carrier.
As the inorganic carrier, powdery ones are used, and these are commercially available. Examples of the inorganic carrier include zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate whisker, but are not limited thereto. One inorganic carrier may be used, or two or more inorganic carriers may be used in combination. Among these inorganic carriers, zeolite, zirconium phosphate, silica gel, apatite, montmorillonite, glass powder and potassium titanate whisker are preferable, and zeolite, zirconium phosphate, apatite and potassium titanate whisker are more preferable.

The antibacterial metal carried on the inorganic carrier contains silver essential. As an antibacterial metal, silver alone may be supported, or an antibacterial metal other than silver and silver may be supported in combination. Examples of the antibacterial metal other than silver include copper, zinc, mercury, lead, bismuth, cadmium, chromium, cobalt, nickel and the like, and one kind may be used or two or more kinds may be used in combination. When using an antibacterial metal other than silver, copper, zinc, lead, bismuth, cobalt, and nickel are preferable.

The method for supporting an antibacterial metal containing silver on an inorganic carrier is not particularly limited, and a known method can be adopted. For example, a method of supporting an antibacterial metal by physical adsorption or chemical adsorption, a method of supporting an antibacterial metal by an ion exchange reaction, a method of supporting an antibacterial metal by a binder, or a method of supporting an antibacterial metal by implanting it into an inorganic compound And a method of forming an antibacterial metal thin film on the surface of an inorganic carrier by vapor deposition, dissolution precipitation reaction, sputtering, or the like. Among these, a method for supporting an antibacterial metal by physical adsorption or chemical adsorption and a method for supporting an antibacterial metal by ion exchange reaction are preferable.

The weight ratio of silver supported on the inorganic carrier is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, and further 0.05 to 7 parts by weight with respect to 100 parts by weight of the inorganic carrier. preferable. When the weight ratio of silver is less than 0.01 part by weight, antibacterial properties may not be exhibited. When the weight ratio of silver exceeds 20 parts by weight, all of the silver may not be supported on the inorganic carrier, and the unsupported silver has very low adhesion to the fiber, and exhibits excellent antibacterial properties and washing durability. There is a risk of not.

Preferable specific examples of the silver-based inorganic antibacterial agent include, for example, one in which silver is ion-bonded and supported on zeolite, one in which silver is supported on zirconium phosphate by ion exchange, one in which silver is supported on silica gel, apatite In this case, silver is supported by ion exchange, silver is supported on hydrous titanium oxide, silver is supported on montmorillonite, silver is supported on glass powder, silver is supported on potassium titanate whiskers. Can be mentioned.

[Compound (A)]
The antibacterial processing agent for fibers of the present invention contains the compound (A) in order to impart excellent antibacterial properties and washing durability to the fiber material. The compound (A) is a compound represented by the general formula (1). In formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR ² R ³ , OR ⁴ It is. R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.
R ¹ having higher hydrophilicity can impart antibacterial properties and washing durability superior as an antibacterial agent. From these points, R ¹ is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, NR ² R ³ , or OR ⁴ , and a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, NR ² R ³ and OR ⁴ are more preferable, and a hydrogen atom, NR ² R ³ and OR ⁴ are more preferable.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

When R ¹ is an alkyl group, an aryl group, or an aralkyl group, the following ranges are preferable as the carbon number of each group from the viewpoint that excellent antibacterial properties and washing durability can be imparted.
The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, and still more preferably 1-8. Examples of such alkyl groups include octyl, decyl, lauryl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, and behenyl groups.
The number of carbon atoms of the aryl group is preferably 6 to 22, more preferably 6 to 16, and still more preferably 6 to 10. Examples of such an aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
The number of carbon atoms in the aralkyl group is preferably 7 to 22, more preferably 7 to 16, and still more preferably 6 to 10. Examples of such an aralkyl group include a benzyl group, a phenylethyl group, a methylbenzyl group, and a naphthylmethyl group.

The aryl group and aralkyl group may have a substituent, and the number of carbon atoms of the substituent is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. Such substituents include methyl, ethyl, t-butyl, octyl, nonyl, lauryl, decyl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, behenyl, styryl. Groups and the like. The number of such substituents may be one or plural, and in the case of plural, plural kinds of substituents may be mixed.

Examples and preferred carbon numbers when R ² , R ³ and R ⁴ are an alkyl group, an aryl group or an aralkyl group are the same as those for R ¹ .

In Formula (1), M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal, or ^a group represented by NR ^a R ^b R ^c R ^d . Among these, M ¹ is preferably a hydrogen atom, an alkali metal, or ^a group represented by NR ^a R ^b R ^c R ^d from the viewpoint that excellent antibacterial properties and washing durability can be imparted, and an alkali metal, NR ^a R ^b A group represented by R ^c R ^d is more preferable.

Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium, calcium, barium and the like.
R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The carbon number of the alkanol group is preferably 1-30, and more preferably 1-10. Examples of such an alkanol group include a methanol group, an ethanol group, an n-propanol group, and an isopropanol group. The polyoxyalkylene group preferably has 2 to 4 carbon atoms. Examples of such a polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.

[Surfactant (B)]
The antibacterial finishing agent for fibers of the present invention includes a surfactant represented by the above general formula (2), a surfactant represented by the above general formula (3), a surfactant represented by the above general formula (4), and the above It is preferable to further contain at least one surfactant (B) selected from surfactants represented by the general formula (5). By using the surfactant (B), it is possible to improve the dispersibility of the silver-based inorganic antibacterial agent and the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. Sex can be imparted. From the above viewpoint, the surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferably at least one selected from the group consisting of a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4). More preferably, it is a surfactant represented by (3).

Regarding the surfactant represented by the general formula (2), in the formula (2), R ⁵ is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. is there. Preferred ranges and examples of the alkyl group, aryl group and aralkyl group are the same as those described for R ¹ . Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, R ¹ is preferably an alkyl group or an aralkyl group, and more preferably an alkyl group.

A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A ¹ O may be one type or two or more types, and in the case of two or more types, A ¹ O may constitute any of a block adduct, an alternating adduct, or a random adduct. A ¹ O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
n is an integer of 0 to 50. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, n is preferably 1 to 45, more preferably 2 to 40, and particularly preferably 3 to 35.
m is an integer of 1 to 3, and preferably 1 or 2.

M ² is a hydrogen atom, an alkali metal, an alkaline earth metal, or ^a group represented by NR ^a R ^b R ^c R ^d . R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR ^a R ^b R ^c R ^d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M ² is preferably an alkali metal, a group represented by NR ^a R ^b R ^c R ^d , and more preferably an alkali metal. preferable.

The phosphoric acid ester compound which is the surfactant represented by the general formula (2) may be any of phosphoric acid triester, phosphoric acid diester, and phosphoric acid monoester, or a mixture thereof.

The production method of the phosphate ester compound is not particularly limited, and a known method can be adopted. For example, as a method for producing a phosphoric acid ester compound, a method is generally known in which a phosphorylation reaction is performed with raw alcohol and phosphoric anhydride, and then, in some cases, the phosphoric acid ester compound is obtained by neutralization. Yes. Here, diesters and monoesters can be roughly prepared separately by changing the charged molar ratio of the raw material alcohol and phosphoric anhydride. For example, in the case of raw material alcohol: phosphoric anhydride = 1: 1 (molar ratio), monoester (m = 1 in the general formula (2)) is mainly obtained. In the case of raw material alcohol: phosphoric anhydride = 2: 1 (molar ratio), a diester (m = 2 in the general formula (2)) is mainly obtained.

Regarding the surfactant represented by the general formula (3), in the formula (3), A ² O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A ² O may be one type or two or more types, and in the case of two or more types, A ² O may constitute any of a block adduct, an alternating adduct, or a random adduct. A ² O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.

q is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
k is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, k is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.

Regarding the surfactant represented by the general formula (4), in the formula (4), A ³ O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A ³ O may be one type or two or more types, and in the case of two or more types, A ³ O may constitute any of a block adduct, an alternating adduct, or a random adduct. A ³ O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.

r is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
j is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, j is preferably from 3 to 60, more preferably from 4 to 50, and even more preferably from 5 to 40.
M ³ is a hydrogen atom, an alkali metal, an alkaline earth metal or ^a group represented by NR ^a R ^b R ^c R ^d . R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR ^a R ^b R ^c R ^d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M ³ is preferably an alkali metal, a group represented by NR ^a R ^b R ^c R ^d , and more preferably an alkali metal. preferable.

Regarding the surfactant represented by the general formula (5), in the formula (5), A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A ⁴ O may be one type or two or more types, and in the case of two or more types, A ⁴ O may constitute any of a block adduct, an alternating adduct, or a random adduct. A ⁴ O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.

s is an integer of 1 to 3, and preferably 2 to 3 from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
t is an integer of 1 or 2, and 2 is preferable from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
h is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, h is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.
M ⁴ is a hydrogen atom, an alkali metal, an alkaline earth metal, or ^a group represented by NR ^a R ^b R ^c R ^d . R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR ^a R ^b R ^c R ^d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M ⁴ is preferably an alkali metal, a group represented by NR ^a R ^b R ^c R ^d , and more preferably an alkali metal. preferable.

[Antimicrobial finishing agent for textiles]
The antibacterial finishing agent for fibers of the present invention is used for imparting antibacterial properties to fiber materials. That is, it is an antibacterial processing agent to be applied to the fiber material in post-processing.
The antibacterial processing agent of the present invention is obtained by dispersing the silver-based inorganic antibacterial agent having an average particle size of 0.01 to 3 μm in the presence of the compound (A) and water. With such a configuration, it is possible to impart excellent antibacterial properties to the fiber material, and even when the processed fiber material is washed, it is possible to prevent a decrease in antibacterial properties and to have excellent washing durability. It has the effect. Although it is not clear about this effect | action, it estimates as follows.

In the antibacterial processing agent, it is presumed that the compound (X) represented by the following general formula (6) is generated by the silver-based inorganic antibacterial agent and the compound (A) exchange-reacting silver atoms. Compound (X) is produced in a larger amount by wet-grinding the silver-based inorganic antibacterial agent in the presence of compound (A) and water and dispersing it to a predetermined average particle size as described later. It is presumed that The produced compound (X) is more organic than silver-based inorganic antibacterial agents, so it has good adhesion to the fiber material, and also holds silver ions, so it has antibacterial properties and washing durability. It is thought that there is. By attaching an antibacterial processing agent containing such a compound (X) together with the finely divided silver-based inorganic antibacterial agent and the compound (A) to the fiber material, excellent antibacterial properties can be imparted and washing It is presumed that the durability is also excellent.
Furthermore, the antibacterial processing agent of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented.

In the formula (6), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR ² R ³ or OR ⁴ It is. R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. R ¹ , R ² , R ³ and R ⁴ are the same as those described for the compound (A).

The average particle size of the silver-based inorganic antibacterial agent is 0.01 to 3 μm, preferably 0.03 to 2 μm, more preferably 0.05 to 1.5 μm, still more preferably 0.1 to 1 μm, and 0.1 ˜1 μm is particularly preferred. When the average particle diameter is less than 0.01 μm, the silver-based inorganic antibacterial agent enters the inside of the fiber material too much, and the antibacterial property is hardly exhibited. On the other hand, when the average particle diameter is more than 3 μm, it is difficult to adhere to the fiber surface, the fixing rate is lowered, and antibacterial properties are hardly exhibited. The average particle size used in the present invention is a value obtained by measuring the volume-based median particle size using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba, Ltd.).

The compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable.

The blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.

The antibacterial processing agent of the present invention essentially contains water. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.
Other components other than the above components may be included as long as the effects of the present invention are not impaired. Other components include antibacterial agents, fungicides, insecticides, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, and smoothing agents. And post-processing agents for fibers such as softeners or water-absorbing agents, oil agents, surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts) and the like.

The antibacterial processing agent of the present invention may contain a binder resin as long as the effects of the present invention are not impaired. However, when the antibacterial agent contains a binder resin, the texture of the fiber material may be reduced. From the viewpoint of preventing the deterioration of the texture, the blending ratio of the binder resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. More preferred is 0 part by weight.

Here, as a binder resin, polyvinyl acetate, polyglycerin, polyvinyl alcohol, polysaccharide compounds, melamine compounds, glyoxal compounds, urethane compounds, blocked isocyanate compounds, silicon compounds, acrylic resins, polyester resins Examples thereof include resins and acrylic resins containing silicon.

Examples of polysaccharide compounds include starch and carboxymethyl cellulose.
Examples of melamine compounds include synthetic resins obtained by polymerizing melamine and formaldehyde.

Examples of the glyoxal compound include glyoxal.
Examples of the urethane compound include a compound obtained by reacting a compound having two or more active hydrogens reactive with an isocyanate group and a polyisocyanate. Among these, examples of the compound having two or more active hydrogens include polyhydric alcohols, compounds having a carboxyl group and two hydroxyl groups, and polyamines. Examples of the polyisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate. Moreover, when it has an isocyanate group in the terminal of this urethane type compound, the compound which blocked a part of the isocyanate group with sodium bisulfite, methyl ethyl ketoxime, etc. can also be used.

As blocked isocyanate compounds, sodium bisulfite, acetylacetone, ethyl acetoacetate, diethylmalonate, etc. are reacted with isocyanate groups to form temporarily stable compounds, which are then dissociated by heat treatment to regenerate isocyanate groups. Obtained by reacting at least one compound containing at least one blocked isocyanate group in the molecule with a (meth) acrylic compound, a silicon-modified (meth) acrylic compound or a fluorine-modified (meth) acrylic compound And the like.
Examples of the silicon compound include condensation-crosslinking resins classified into silicone resins or silicone varnishes. This condensation-crosslinking resin can be obtained by polycondensing one or two or more silane compounds selected from silane compounds such as tetraethoxysilane and methyltrimethoxysilane.

Examples of the acrylic resin include one or two or more types of (meth) acrylic monomers such as (meth) acrylate monomers such as acrylic acid, methacrylic acid, methyl (meth) acrylate, and n-butyl (meth) acrylate. Examples thereof include a polymer and a copolymer with another vinyl monomer copolymerizable with these (meth) acrylic monomers.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolycondensate, and the like.
Examples of the acrylic resin containing silicon include a polycondensate of a (meth) acrylic acid ester monomer and an organopolysiloxane compound.

The concentration of the nonvolatile content of the antibacterial processing agent of the present invention is preferably 0.0001 to 90% by weight, more preferably 0.0005 to 70% by weight, and further preferably 0.001 to 50% by weight. In addition, the antibacterial processing chemical | medical agent of this invention contains not only the chemical | medical agent manufactured with the manufacturing method mentioned later but the processing liquid which diluted this chemical | medical agent with water etc., when providing to a fiber material. The non-volatile content in the present invention refers to an absolutely dry component when a sample is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.

[Manufacturing method of antibacterial agents for textiles]
The method for producing an antibacterial processing agent for fibers according to the present invention includes a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the compound (A) and water. The wet pulverization method is not particularly limited, and a known method can be adopted.

Specifically, first, a slurry solution is prepared by mixing and stirring the compound (A), water, and an unground silver-based inorganic antibacterial agent. The compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable. When the compounding ratio of the compound (A) is less than 0.1 parts by weight, it is estimated that the compound (X) is also produced in a small amount, and it may be difficult to develop the durability to washing. Furthermore, yellowing (coloring) due to silver ions may not be prevented. When it is larger than 10,000 parts by weight, the washing durability is not improved any more, which may be economically disadvantageous.
Further, the weight ratio of the nonvolatile content of the slurry is preferably 1 to 90% by weight, more preferably 3 to 70% by weight, and further preferably 5 to 50% by weight. If it is less than 1% by weight, the antibacterial component in the antibacterial processing agent may be small, and the treated fiber may not exhibit antibacterial properties. If it exceeds 90% by weight, aggregation of the silver-based inorganic antibacterial agent may occur over time, and it may be difficult to exhibit excellent antibacterial properties and washing durability.

Next, the slurry liquid prepared is passed through a wet pulverizer such as a bead mill, a sand grinder, an attritor, or a ball mill, and finely divided until the average particle size becomes 0.1 to 3 μm. The preferred range of the average particle size of the finely divided silver-based inorganic antibacterial agent and the method for measuring the average particle size are the same as those described for the antibacterial processing agent. Examples of the wet pulverization process include a continuous process such as a pass system or a tank internal circulation system, and a batch process.

In the method for producing an antibacterial processing agent of the present invention, the step is a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water. Is preferred. That is, it is a step of preparing a slurry liquid by mixing and stirring the compound (A), the surfactant (B), water and unmilled silver-based inorganic antibacterial agent, and finely pulverizing the slurry liquid with a wet pulverizer. Is preferred. By such a process, the dispersibility of the silver-based inorganic antibacterial agent and the stability over time of the dispersion of the silver-based inorganic antibacterial agent can be improved, and further excellent antibacterial properties and washing durability can be imparted. Can do. The surfactant (B) is at least one selected from a surfactant represented by the general formula (3), a surfactant represented by the general formula (4), and a surfactant represented by the general formula (5). It is preferable that it is at least one selected from a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4), and is represented by the general formula (3). More preferably, it is a surfactant.
The blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.

The antibacterial processing agent thus obtained is presumed to produce more compound (X) as described above. And by attaching the antibacterial processing agent containing the finely divided silver-based inorganic antibacterial agent, compound (A) and compound (X) to the fiber material, excellent antibacterial properties can be imparted and washing durability It is presumed that there is an effect that it is excellent. Furthermore, the antibacterial finishing agent obtained by the production method of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented. Yes.

[Method for producing antibacterial fibers]
The method for producing an antibacterial fiber of the present invention includes a step of applying to the fiber material an antibacterial processing agent of the present invention and / or an antibacterial processing agent obtained by the production method of the present invention. That is, the manufacturing method of the antibacterial fiber of this invention includes the process of providing an antibacterial processing chemical | medical agent to a fiber material by post-processing. Post-processing means processing after the fiber material is manufactured. According to this production method, antibacterial fibers having excellent antibacterial properties and excellent washing durability can be obtained. Furthermore, the antibacterial fiber which can prevent yellowing (coloring) of the fiber material by silver ion can be obtained.

The fiber material may be either natural fiber or chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm, and rush; animal fibers such as wool, goat wool, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos. Examples of the chemical fiber include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber; melt-spun cellulose fiber; Protein fibers such as milk protein and soybean protein; Regenerated and semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, Polyester fiber, Cationic dyeable polyester fiber, Polyvinyl fiber, Polyacrylic alcohol fiber, Polyurethane fiber, Acrylic fiber, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. Two or more of these fibers may be combined (mixed spinning, mixed fiber, union, union, etc.).
Among these, a water-absorbing fiber is preferably a plant fiber, an animal fiber, a regenerated cellulose fiber, a melt-spun cellulose fiber, or a fiber in which these are combined from the viewpoint of easily exhibiting antibacterial properties.

Examples of the form of the fiber material include forms such as a woven fabric, a knitted fabric, a fabric, a thread shape, and a non-woven fabric. Examples of the use of the fiber material include objects that impart antibacterial properties, water absorption, and washing resistance, such as underwear, sports clothing, bedding, and covers.

The method for applying the antibacterial agent to the fiber material is not particularly limited, and a known method can be employed. Among these, at least one method selected from the exhaust method, the pad dry method, the spray method, and the coating method is preferable, and the pad dry method is more preferable because the antibacterial processing agent is securely fixed to the fiber material.

As the exhaust method, pad dry method, spray method, and coating method, known methods can be employed. The exhaust method is a method in which a diluted solution of a drug is used, conditions such as temperature, immersion time, number of times of liquid circulation, etc. are set, and the drug is selectively adsorbed on a fiber to be exhausted and adhered. Thereafter, washing is usually carried out, followed by centrifugal dehydration and drying. The pad dry method is a method in which fibers are immersed in a drug solution for a short time and immediately attached by squeezing with a dehydrated mangle or the like. Then, drying is performed and curing is performed as necessary. The spray method is a method in which fibers are placed on a conveyor at a constant speed and adhered by spraying a predetermined amount of a solution of the drug from the fiber. Then, drying is performed and curing is performed as necessary. The coating method is a method in which a drug solution is usually applied by applying from one side with a mangle. Then, the excess drug is scraped off with a doctor, dried, and cured if necessary.

The weight ratio of the non-volatile content of the antibacterial processing agent (processing solution) when applied to the fiber material is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 7% by weight, and 0.001 to 5% by weight. % Is more preferable. The predetermined weight ratio can be prepared by diluting with water or the like.

The temperature at which the antibacterial processing agent of the present invention is applied to the fiber material is preferably 5 to 40 ° C. If the application temperature is lower than 5 ° C., it may be difficult to maintain the constant temperature, and thus it may not be possible to apply the constant to the fiber material. On the other hand, when the application temperature is higher than 40 ° C., the elution of dyes contained in the fiber material may increase.

The fiber material to which the antibacterial processing agent has been applied is dried by a method such as tensionless or applying tension, whereby the antibacterial fiber of the present invention can be obtained. Examples of the tensionless drying method include a non-touch dryer, a short loop dryer, a tensionless roller type, and a cylinder dryer. Examples of the method of applying a tension and drying include a pin tenter and a clip tenter.
The drying temperature is not particularly limited, but is preferably 100 ° C. or higher and more preferably 110 to 200 ° C. in order to fix the antibacterial processing agent to the fiber material. When the drying temperature is lower than 100 ° C., the antibacterial processing agent may not adhere to the fiber material.

The amount of the non-volatile component of the antibacterial processing agent applied to the fiber material is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.03 to 15% by weight, more preferably 0.05 to the fiber material. More preferred is ˜10% by weight. If the amount is less than 0.01% by weight, the antibacterial component in the antibacterial processing agent may be a small amount, and the treated fiber may not exhibit antibacterial properties. If it exceeds 20% by weight, no further improvement in antibacterial properties and washing durability is observed, which may be economically disadvantageous.

Processes that can be processed at the same time include insecticides, fungicides, mites, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, smoothing agents The process etc. which provide a softener or a water absorbing agent are mentioned. A plurality of these steps can be performed simultaneously. About each agent, a well-known thing can be employ | adopted.

Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail. However, the present invention is not limited to these examples. In the examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

Example 1
As shown in the mixing ratio of Table 1, 200 parts by weight of silver-based inorganic antibacterial agent 1 in which an antibacterial metal containing silver is ion-bonded to zeolite, 20 parts by weight of benzotriazole, and 780 parts by weight of soft water are added to the stirrer. A slurry liquid was prepared by stirring and dispersing. The silver-based inorganic antibacterial agent 1 contains 2.4% by weight of silver element and 5.2% by weight of zinc with respect to the whole antibacterial agent. Next, the slurry liquid was made into fine particles for 4 hours using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) to obtain an antibacterial agent for fibers having an average particle diameter of the silver-based inorganic antibacterial agent of 0.4 μm. The average particle size was measured by the following method. About the obtained antibacterial processing chemical | medical agent, stability was evaluated by the following method. The results are shown in Table 1.
Next, water was added to the antibacterial processing agent to prepare a processing solution having a nonvolatile content of 1% by weight. Cotton broad (100% cotton plain weave) was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight. In addition, the adhesion amount with respect to the fiber was calculated by the following formula.
Amount of adhesion to fiber (% by weight) = (weight of cotton broad including processing solution−weight of raw cotton broad) / weight of raw cotton broad × 100
Next, the cotton broad band containing this aqueous solution was dried with a pin tenter at 110 ° C. for 3 minutes to obtain a target sample (antibacterial fiber). The antibacterial properties, washing durability, texture and yellowing of the obtained samples were evaluated by the following methods. The results are shown in Table 1.

<Average particle size>
The antibacterial processing agent is diluted with distilled water so that the weight ratio of the non-volatile content is 3% by weight, and this diluted solution is volume-based using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba). The median particle size was measured.

<Stability of antibacterial agents for textiles>
100 mL of the antibacterial processing agent was put into a screw tube and sealed. This was left in an incubator adjusted to a temperature of 70 ° C. for 1 week, and the stability was determined by classifying into the following four stages.
A: Only less than 5% of the aqueous dispersion is precipitated.
○: 5% or more and less than 10% of the aqueous dispersion is precipitated.
Δ: 10% or more and less than 20% of the aqueous dispersion is precipitated.
X: 20% or more of the aqueous dispersion is precipitated.

<Antimicrobial (finished)>
About the obtained sample, antibacterial property was measured according to the SEK unification test method (JIS L1902, bacteria absorption method). In the test, Staphylococcus aureus was used as a test bacterium, and the growth value at that time was 2.1, which satisfied the test establishment condition. According to the SEK unified test method, in order to have antibacterial properties, the following conditions must be satisfied.
Antibacterial criteria: Bactericidal activity value ≧ 0
Antibacterial deodorization standard: bacteriostatic activity value ≧ 2.2

<Antimicrobial (after washing)>
About what wash | cleaned the obtained sample on the following conditions, antibacterial property was measured by the same method as the test method of said antibacterial property (processed finish), and washing durability was evaluated.
In accordance with JIS L 0217 103, using a JAFET standard detergent at a rate of 3 g / L, washing with water at 40 ° C. for 5 minutes at a bath ratio of 1:30, then rinsing twice at 40 ° C. for 2 minutes, and centrifugal dehydration After that, the work of drying in the shade was defined as one cycle, and this was performed for 10 cycles.

<Texture>
The texture of the obtained sample was evaluated by touch. In addition, the evaluation of the texture was determined by classifying into the following four stages based on the following criteria.
A: Flexible.
○: Slightly flexible (equivalent to raw cotton broad cloth)
Δ: Slightly coarse and hard
X: It is coarse and hard.

<Yellowing>
The sample was left in an incubator adjusted to a temperature of 70 ° C. and a humidity of 90% for 4 days to evaluate yellowing. Evaluation of yellowing was performed using a spectrocolorimeter (CM-3600d, manufactured by Konica Minolta) and measuring ΔYI with reference to an unprocessed cotton broad cloth.
If the evaluation criterion was ΔYI <5, it was regarded as not yellowing.

(Examples 2 to 5, 8 to 11, 14 to 36)
Examples 2 to 5, 8 to 11, and 14 to 36 were the same as Example 1 except that slurry liquids were prepared by changing the slurry liquid of Example 1 to the components and blending ratios shown in Tables 1 to 3. And evaluated. The results are shown in Tables 1 to 3.
Silver-based inorganic antibacterial agent 2 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 1.2% by weight of silver element and 2. It contains 6% by weight. Silver-based inorganic antibacterial agent 3 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 0.5% by weight of silver element and 1.1% of zinc with respect to the whole antibacterial agent % Content. The silver-based inorganic antibacterial agent 4 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zirconium phosphate. 0.5% by weight of silver element and 1. It contains 1% by weight.

(Examples 6 and 7)
Examples 6 and 7 are antibacterial processing agents in which the slurry liquid of Example 1 is finely divided by a star mill ZRS for 2 hours and 3 hours, respectively, and the average particle diameter of the silver-based inorganic antibacterial agent 1 is 1.3 μm and 2.6 μm. Evaluation was carried out in the same manner as in Example 1 except that the above was obtained. The results are shown in Table 1.

(Examples 12 and 13)
In Examples 12 and 13, water was added to the antibacterial processing agent for fibers of Example 1, and a processing solution was prepared in which the weight ratios of nonvolatile components were 0.1% by weight and 0.001% by weight, respectively. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 1 to 4)
Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1 except that the antibacterial processing agent of Example 1 was changed to the following antibacterial processing agent. The results are shown in Table 4.
Antibacterial finishing agents of Comparative Examples 1 to 4: Each component was added to a stirrer in the blending ratio shown in Table 4, and sufficiently stirred and dispersed to prepare antibacterial finishing agents of Comparative Examples 1 to 4, respectively. The average particle diameters of the antibacterial processing agents of Comparative Examples 1 to 4 were 4.1 μm, 4.2 μm, 4.1 μm, and 4.1 μm, respectively.

(Comparative Example 5)
As blank (BL), raw cotton broad was evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Examples 1A, 8A, 14A, 15A, 16A, 27A, 32A)
Examples 1A, 8A, 14A, 15A, 16A, 27A, and 32A are the antibacterial agents used for evaluating the stability of Examples 1, 8, 14, 15, 16, 27, and 32 (temperature 70 ° C, left for 1 week). Antibacterial properties were measured in the same manner as in Example 1 except that the performed drug was used. The results are shown in Table 5.

From Tables 1 to 5, the fiber material to which the antibacterial agent for fibers of the present invention has been applied has excellent antibacterial properties and maintains its antibacterial properties even after washing (has washing durability). I understand). In addition, the texture does not decrease. Furthermore, it is excellent also about yellowing.
In addition, it can be seen that the use of the surfactant (B) is effective in improving the dispersibility of the silver-based inorganic antibacterial agent and improving the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. . Furthermore, it can be seen from Table 5 that more excellent antibacterial properties and washing durability can be imparted.

The antibacterial processing agent of the present invention can be suitably used for imparting antibacterial properties to fiber materials.

Claims

A silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, a compound (A) represented by the following general formula (1), and water are essential.
An antibacterial processing agent for fibers, wherein the silver-based inorganic antibacterial agent is dispersed in water and has an average particle size of 0.01 to 3 μm.

(Wherein R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 . R 2, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, .M 1 is an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms is , A hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, , An alkanol group or a polyoxyalkylene group.)
The antibacterial processing agent according to claim 1, wherein the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker.
Furthermore, the surfactant represented by the following general formula (2), the surfactant represented by the following general formula (3), the surfactant represented by the following general formula (4), and the following general formula (5) The antibacterial processing agent according to claim 1 or 2, comprising at least one surfactant (B) selected from surfactants.

(Wherein R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)

(Wherein A 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)

(Wherein A 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)

(In the formula, A 4 O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). The antibacterial processing agent according to any one of claims 1 to 3, which is at least one kind.
Including a step of wet-grinding a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is supported on an inorganic carrier in the presence of the compound (A) represented by the following general formula (1) and water,
A method for producing an antibacterial agent for fibers, wherein the wet-pulverized silver-based inorganic antibacterial agent has an average particle size of 0.01 to 3 μm.

(Wherein R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 . .R 2, R 3 and R 4 are each independently hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms .M 1 Is a hydrogen atom, an alkali metal or a group represented by NR a R b R c R d , R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or It is a polyoxyalkylene group.)
The method for producing an antibacterial processing agent according to claim 5, wherein the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker. .
The step is a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water,
The surfactant (B) is a surfactant represented by the following general formula (2), a surfactant represented by the following general formula (3), a surfactant represented by the following general formula (4), and the following general formula The method for producing an antibacterial processing agent according to claim 5 or 6, which is at least one selected from surfactants represented by formula (5).

(Wherein R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)

(Wherein A 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)

(Wherein A 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)

(Wherein A 4 O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). The method for producing an antibacterial processing agent according to any one of claims 5 to 7, wherein there is at least one kind.
An antibacterial fiber comprising a step of applying to the fiber material an antibacterial processing agent according to any one of claims 1 to 4 and / or an antibacterial processing agent obtained by the production method according to any one of claims 5 to 8. Production method.