JP5140208B2 - Antibacterial fiber manufacturing method, antibacterial fiber and antibacterial finishing agent for fiber - Google Patents

Abstract

The purpose of the present invention is to provide: a method for producing antibacterial fibers that have excellent antibacterial properties and water absorption even after repeated washing, which is capable of providing a fiber material containing cellulose-based fibers with both antibacterial properties and water absorption; antibacterial fibers; and an antibacterial processing agent for cellulose-based fibers. A method for producing antibacterial fibers of the present invention comprises a step (A) wherein a fiber material containing cellulose-based fibers is processed with an organosiloxane having a quaternary ammonium salt group and a glycidyl ether compound or alternatively processed with a reaction product of the organosiloxane and the glycidyl ether compound. An antibacterial processing agent for cellulose-based fibers of the present invention contains an organosiloxane having a quaternary ammonium salt group and a glycidyl ether compound or alternatively contains a reaction product of the organosiloxane and the glycidyl ether compound.

Description

  The present invention relates to a method for producing antibacterial fibers that impart antibacterial properties to a fiber material containing cellulosic fibers, an antibacterial fiber obtained by the production method, and an antibacterial processing agent for cellulosic fibers.

  As a method for imparting washing-resistant antibacterial properties to a fiber material, a method using an organosiloxane having a quaternary ammonium base is known. Since this organosiloxane-containing alkoxysilyl group can be chemically condensed with a hydroxyl group contained in the fiber material, it can impart antibacterial properties with durability to washing to fiber materials such as cellulose fibers ( For example, Patent Document 1).

  However, in general, a fiber material treated with an organosiloxane having a quaternary ammonium base has a problem of high water repellency and low water absorption. In order to improve this problem, for example, the fiber processing agent of Patent Document 2 has been proposed, but the washing durability is insufficient, and the water absorption after repeated washing cannot be maintained. That is, antibacterial and water absorption properties with good washing durability cannot be achieved with the treatment agent of Patent Document 2.

  As other drugs, polyhexamethylene biguanidine hydrochloride, chlorhexidine gluconate and the like are known. None of them reduce the water absorption of the object to be treated, but it is difficult to impart antibacterial properties having washing durability to the object to be treated by a general method.

Japanese Unexamined Patent Publication No. Sho 62-177284 Japanese Unexamined Patent Publication No. 60-39478

  An object of the present invention is to provide a method for producing antibacterial fibers that can impart both antibacterial properties and water absorption properties to fiber materials containing cellulosic fibers and have excellent antibacterial properties and water absorption properties even after repeated washing. It is to provide an antibacterial finishing agent for antibacterial fibers and cellulosic fibers.

  As a result of intensive studies in order to solve the above problems, the present inventors have obtained antibacterial activity by treating a fiber material containing cellulosic fibers with an organosiloxane having a quaternary ammonium base and a glycidyl ether compound. It has been found that antibacterial fibers having excellent antibacterial properties and water absorbability can be produced even after repeated washing and having both compatibility and water absorption. In addition, if a fiber material containing cellulosic fibers is treated with a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, both antibacterial properties and water absorption can be achieved. Later, it was found that it has excellent antibacterial properties and water absorption.

  That is, in the present invention, a fiber material containing cellulosic fibers is treated with an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, or a reaction product of the organosiloxane and the glycidyl ether compound. It is a manufacturing method of an antimicrobial fiber including the process (A) to process.

（Ｒ^１は炭素数１〜２２のアルキル基である。Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して、炭素数１〜１０のアルキル基である。Ｒ^５は炭素数１〜１０のアルキレン基である。Ｘ⁻は、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻又はＣＨ_３ＣＯＯ⁻である。）The organosiloxane is preferably an organosiloxane represented by the following general formula (1).

(R ¹ is an alkyl group having 1 to 22 carbon atoms. R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms. R ⁵ is an alkyl group having 1 to 10 carbon atoms. An alkylene group, X ⁻ is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ^— .

The glycidyl ether compound includes a glycidyl ether of a monohydric alcohol, a glycidyl ether of a monohydric alcohol into which a polyalkylene glycol chain is introduced, a glycidyl ether of a polyhydric alcohol, and a glycidyl ether of a polyhydric alcohol into which a polyalkylene glycol chain is introduced. Glycidyl ether of monohydric phenol, glycidyl ether of monohydric phenol introduced with polyalkylene glycol chain, glycidyl ether of polyhydric phenol, and glycidyl ether of polyhydric phenol introduced with polyalkylene glycol chain A seed glycidyl ether is preferred.
The glycidyl ether-based compound is preferably a glycidyl ether having a polyalkylene glycol chain.

（Ｒ^６は、炭素数１〜１８のアルキル基、フェニル基又はグリシジル基である。Ａは炭素数２〜５のアルキレン基である。ポリアルキレングリコール鎖の繰り返し単位の数ｎは１〜２２である。）Furthermore, the glycidyl ether compound is preferably a glycidyl ether represented by the following general formula (2).

(R ⁶ is an alkyl group having 1 to 18 carbon atoms, a phenyl group or a glycidyl group. A is an alkylene group having 2 to 5 carbon atoms. The number n of repeating units of the polyalkylene glycol chain is 1 to 22. is there.)

The glycidyl ether compound is preferably a monoglycidyl ether in which R ^{6 in the} general formula (2) is an alkyl group having 1 to 18 carbon atoms.

  The step (A) is a step of treating the organosiloxane and the glycidyl ether compound with a weight ratio of 0.3 to 3.0 (organosiloxane / glycidyl ether compound) on a fiber material containing cellulosic fibers. It is preferable that

The step (A) is preferably a step of treating a fiber material containing cellulosic fibers with a treatment liquid containing the organosiloxane, the glycidyl ether compound and water.
Moreover, it is preferable that the manufacturing method of the antimicrobial fiber of this invention includes the process (B) which heat-processes the fiber material processed by the said process (A) further.

  In addition, the antibacterial fiber of the present invention is obtained by the above production method, and is obtained by fixing a reaction product of the organosiloxane and the glycidyl ether compound to a fiber material containing cellulosic fibers.

  The antibacterial finishing agent for cellulose fiber of the present invention contains an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, or a reaction product of the organosiloxane and the glycidyl ether compound. is there.

  In the antibacterial processing agent for cellulosic fibers, the organosiloxane is preferably an organosiloxane represented by the general formula (1).

In the antibacterial finishing agent for cellulosic fibers, the glycidyl ether compound includes a glycidyl ether of a monohydric alcohol, a glycidyl ether of a monohydric alcohol into which a polyalkylene glycol chain is introduced, a glycidyl ether of a polyhydric alcohol, and a polyalkylene glycol chain. Polyhydric alcohol glycidyl ether, monohydric phenol glycidyl ether, polyalkylene glycol chain monohydric phenol glycidyl ether, polyhydric phenol glycidyl ether, and polyalkylene glycol chain polyvalent Preference is given to at least one glycidyl ether selected from glycidyl ethers of phenol.
The glycidyl ether compound is preferably a glycidyl ether represented by the general formula (2).

According to the method for producing antibacterial fibers of the present invention, antibacterial properties and water absorption can be imparted to a fiber material containing cellulosic fibers at the same time, and excellent antibacterial properties and water absorption can be achieved even after repeated washing. Can be granted.
The antibacterial fiber of the present invention has excellent antibacterial properties and water absorption, and has excellent antibacterial properties and water absorption even after repeated washing.
The antibacterial finishing agent for cellulosic fibers of the present invention can impart both antibacterial properties and water absorption to fiber materials containing cellulosic fibers, and provides excellent antibacterial properties and water absorption even after repeated washing. it can.

  In the present invention, a fiber material containing cellulosic fibers is treated with an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, or a reaction product of the organosiloxane and the glycidyl ether compound is treated. It is a manufacturing method of an antimicrobial fiber including a process (A). This will be described in detail below.

[Organosiloxane having quaternary ammonium base]
Organosiloxane having a quaternary ammonium base (sometimes simply referred to as organosiloxane) generally has an excellent antibacterial effect against Gram-positive bacteria, Gram-negative bacteria, molds, algae, and the like. In the present invention, by treating an organosiloxane having a quaternary ammonium base with a fiber material containing a cellulosic fiber together with a glycidyl ether compound, antibacterial properties can be imparted and water absorption can be imparted at the same time. Excellent antibacterial properties and water absorption can be imparted even after repeated washing. The organosiloxane having a quaternary ammonium base preferably has at least one alkoxysilyl group in the molecule so as to be condensed with a hydroxyl group of cellulose and reacted with a glycidyl ether compound. It is more preferable to have two or more alkoxysilyl groups.

The organosiloxane having a quaternary ammonium base is preferably an organosiloxane represented by the above general formula (1) from the viewpoint of imparting an antibacterial effect having washing durability. In formula (1), R ¹ is an alkyl group having 1 to 22 carbon atoms. From the viewpoint of excellent antibacterial effect, the carbon number of R ¹ is preferably 8-22. The alkyl group for R ¹ may be linear or branched.
R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms. R ^{2, R 3} and the carbon number of ^{R 4} is from 1 to 5 preferably 1 to 3 is more preferable. R ⁴ is most preferably a methyl group having a low steric hindrance and a rapid silanol production rate by hydrolysis. The alkyl group of R ² , R ³ and R ⁴ may be linear or branched.
R ⁵ is an alkylene group having 1 to 10 carbon atoms. The number of carbon atoms of R ⁵ is 1 to 5 preferably 1 to 3 is more preferable. X ⁻ is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ⁻ , preferably Cl ⁻ , Br ⁻ or I ⁻ , and more preferably Cl ⁻ .

  As the organosiloxane having a quaternary ammonium base, a commercially available one can be used, and it is generally marketed as an alcohol solution.

[Glycidyl ether compounds]
The glycidyl ether compound can be imparted with both antibacterial properties and water absorbency by treating it with a fiber material containing cellulosic fibers together with the organosiloxane, and has excellent antibacterial properties and water absorbency even after repeated washing. Can be granted.
The glycidyl ether compound generates active hydrogen by opening the epoxy group by heat or the like, and reacts with the hydroxyl group of the cellulose fiber. Further, when the organosiloxane has an alkoxysilyl group, a reaction occurs with a silanol group derived from the alkoxysilyl group. Therefore, it is presumed that glycidyl ether compounds have a higher ratio of being retained by chemical bonding on fiber materials containing cellulosic fibers and have higher washing durability than amines and alcohols.

  The glycidyl ether compound is not particularly limited as long as it is a compound having at least one glycidyl ether group in the molecule. For example, glycidyl ether of monohydric alcohol, glycidyl ether of monohydric alcohol with polyalkylene glycol chain introduced, glycidyl ether of polyhydric alcohol, glycidyl ether of polyhydric alcohol with polyalkylene glycol chain introduced, monohydric phenol At least one glycidyl ether selected from glycidyl ether, glycidyl ether of monohydric phenol introduced with polyalkylene glycol chain, glycidyl ether of polyhydric phenol, and glycidyl ether of polyhydric phenol introduced with polyalkylene glycol chain, Can be mentioned.

  The monohydric alcohol may be either an aliphatic alcohol or an alicyclic alcohol, and may be either saturated or unsaturated. Among these, aliphatic alcohols are preferable, saturated aliphatic alcohols are more preferable, and saturated aliphatic alcohols having 1 to 18 carbon atoms are more preferable. Examples of the monohydric alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cyclohexyl alcohol and the like.

  The monohydric alcohol into which the polyalkylene glycol chain is introduced is an alkylene oxide adduct of the monohydric alcohol described above and has a (poly) oxyalkylene group. The oxyalkylene group includes an oxyalkylene group having 2 to 5 carbon atoms, preferably an oxyethylene group, an oxypropylene group, and an oxybutylene group, more preferably an oxyethylene group and an oxypropylene group, and even more preferably an oxyethylene group. . The repeating unit of the oxyalkylene group is preferably 1 to 22, and more preferably 8 to 22. The oxyalkylene groups constituting the polyoxyalkylene group may be the same, and may be different, such as a block copolymer or a random copolymer of an oxyethylene group and an oxypropylene group. From the viewpoint of imparting water absorption, it is preferable to contain an oxyethylene group essentially. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 30 mol% or more, more preferably 50 mol%, still more preferably 80 mol% or more.

  As glycidyl ether of monohydric alcohol, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether Oleyl glycidyl ether, cyclohexyl glycidyl ether, and the like.

  Examples of glycidyl ethers of monohydric alcohols into which polyalkylene glycol chains have been introduced include polyoxyethylene methyl glycidyl ether, polyoxyethylene ethyl glycidyl ether, polyoxyethylene propyl glycidyl ether, polyoxyethylene butyl glycidyl ether, polyoxyethylene octyl glycidyl ether Ether, polyoxyethylene dodecyl glycidyl ether, polyoxyethylene lauryl glycidyl ether, polyoxyethylene myristyl glycidyl ether, polyoxyethylene cetyl glycidyl ether, polyoxyethylene stearyl glycidyl ether, polyoxyethylene oleyl glycidyl ether, polyoxyethylene cyclohexyl glycidyl ether , Polyoxyethylene polyoxyp Pyrenemethyl glycidyl ether, polyoxyethylene polyoxypropylene ethyl glycidyl ether, polyoxyethylene polyoxypropylene propyl glycidyl ether, polyoxyethylene polyoxypropylene butyl glycidyl ether, polyoxyethylene polyoxypropylene octyl glycidyl ether, polyoxyethylene polyoxy Propylene dodecyl glycidyl ether, polyoxyethylene polyoxypropylene lauryl glycidyl ether, polyoxyethylene polyoxypropylene myristyl glycidyl ether, polyoxyethylene polyoxypropylene cetyl glycidyl ether, polyoxyethylene polyoxypropylene stearyl glycidyl ether, polyoxyethylene polyoxy Propylene Irglycidyl ether, polyoxyethylene polyoxypropylene cyclohexyl glycidyl ether, polyoxypropylene methyl glycidyl ether, polyoxypropylene ethyl glycidyl ether, polyoxypropylene propyl glycidyl ether, polyoxypropylene butyl glycidyl ether, polyoxypropylene octyl glycidyl ether, poly Oxypropylene dodecyl glycidyl ether, polyoxypropylene lauryl glycidyl ether, polyoxypropylene myristyl glycidyl ether, polyoxypropylene cetyl glycidyl ether, polyoxypropylene stearyl glycidyl ether, polyoxypropylene oleyl glycidyl ether, polyoxypropylene cyclohexyl glycidyl ether And the like.

The polyhydric alcohol may be either an aliphatic alcohol or an alicyclic alcohol, and may be either saturated or unsaturated. The polyhydric alcohol is preferably 2 to 5, more preferably 2 to 3.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyethylene polypropylene glycol, 1,4-butanediol, and 1,6-hexane. Diol, neopentyl glycol, glycerin, pentaerythritol, sorbitol and the like can be mentioned.

  The polyhydric alcohol introduced with a polyalkylene glycol chain is an alkylene oxide adduct of the aforementioned polyhydric alcohol and has at least one (poly) oxyalkylene group. The number of (poly) oxyalkylene groups is not particularly limited as long as at least one (poly) oxyalkylene group is present, and may include the same number as the valence of the polyhydric alcohol. The (poly) oxyalkylene group is the same as that described for the monohydric alcohol into which the polyalkylene glycol chain is introduced.

  Polyglycol glycidyl ethers include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diester. Glycidyl ether, polypropylene glycol diglycidyl ether, polyethylene polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol Polyglycidyl ether, sol Toll polyglycidyl ether, and the like.

  Examples of glycidyl ethers of polyhydric alcohols into which polyalkylene glycol chains have been introduced include polyoxyethylene glycerin triglycidyl ether, polyoxyethylene pentaerythritol polyglycidyl ether, polyoxyethylene sorbitol polyglycidyl ether, polyoxyethylene polyoxypropylene glycerin tris. Glycidyl ether, polyoxyethylene polyoxypropylene pentaerythritol polyglycidyl ether, polyoxyethylene polyoxypropylene sorbitol polyglycidyl ether, polyoxypropylene glycerin triglycidyl ether, polyoxypropylene pentaerythritol polyglycidyl ether, polyoxypropylene sorbitol polyglycidyl ether Etc.

  The monohydric phenol may be either an aromatic alcohol or a polycyclic aromatic alcohol. Examples of the monohydric phenol include phenol, benzyl alcohol, tert-butylphenol, hexylphenol, octylphenol, nonylphenol, cresol, naphthol and the like.

  The monohydric phenol into which the polyalkylene glycol chain is introduced is the above-mentioned alkylene oxide adduct of monohydric phenol and has a (poly) oxyalkylene group. The (poly) oxyalkylene group is the same as that described for the monohydric alcohol into which the polyalkylene glycol chain is introduced.

  Examples of the glycidyl ether of monohydric phenol include phenyl glycidyl ether, benzyl glycidyl ether, tert-butylphenyl glycidyl ether, hexylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, naphthyl glycidyl ether and the like.

  Examples of glycidyl ethers of monohydric phenol having a polyalkylene glycol chain introduced include polyoxyethylene phenyl glycidyl ether, polyoxyethylene benzyl glycidyl ether, polyoxyethylene tert-butylphenyl glycidyl ether, polyoxyethylene hexylphenyl glycidyl ether, Oxyethylene octylphenyl glycidyl ether, polyoxyethylene nonylphenyl glycidyl ether, polyoxyethylene naphthyl glycidyl ether, polyoxyethylene polyoxypropylene phenyl glycidyl ether, polyoxyethylene polyoxypropylene benzyl glycidyl ether, polyoxyethylene polyoxypropylene tert- Butyl phenyl glycidyl ether, polyoxy Tylene polyoxypropylene hexylphenyl glycidyl ether, polyoxyethylene polyoxypropylene octylphenyl glycidyl ether, polyoxyethylene polyoxypropylene nonylphenyl glycidyl ether, polyoxyethylene polyoxypropylene naphthyl glycidyl ether, polyoxypropylene phenyl glycidyl ether, polyoxy Examples include propylene benzyl glycidyl ether, polyoxypropylene tert-butylphenyl glycidyl ether, polyoxypropylene hexylphenyl glycidyl ether, polyoxypropylene octylphenyl glycidyl ether, polyoxypropylene nonylphenyl glycidyl ether, and polyoxypropylene naphthyl glycidyl ether.

The polyhydric phenol may be either an aromatic alcohol or a polycyclic aromatic alcohol. The polyhydric phenol is preferably 2 to 5, more preferably 2 to 3.
Examples of the polyhydric phenol include hydroquinone (1,4-benzenediol), resorcinol (1,3-benzenediol), catechol (1,2-benzenediol), bisphenol A, and virogalol (1,2,3-benzene). Triol) and the like.

  The polyhydric phenol into which the polyalkylene glycol chain is introduced is an alkylene oxide adduct of the aforementioned polyhydric phenol and has at least one (poly) oxyalkylene group. The number of (poly) oxyalkylene groups is not particularly limited as long as at least one (poly) oxyalkylene group is present, and may include the same number as the valence of the polyhydric phenol. The (poly) oxyalkylene group is the same as that described for the monohydric alcohol into which the polyalkylene glycol chain is introduced.

  Examples of the glycidyl ether of polyhydric phenol include benzenediol diglycidyl ether, bisphenol A diglycidyl ether, and benzenetriol triglycidyl ether.

  Examples of the glycidyl ether of polyhydric phenol into which a polyalkylene glycol chain is introduced include polyoxyethylenebenzenediol diglycidyl ether, polyoxyethylene bisphenol A diglycidyl ether, polyoxyethylenebenzenetriol triglycidyl ether, and polyoxyethylene poly Oxypropylene benzene diol diglycidyl ether, polyoxyethylene polyoxypropylene bisphenol A diglycidyl ether, polyoxyethylene polyoxypropylene benzene triol triglycidyl ether, polyoxypropylene benzene diol diglycidyl ether, polyoxypropylene bisphenol A diglycidyl ether, Polyoxypropylene benzene triol triglycidyl a Le, and the like.

  The glycidyl ether compound is preferably a monoglycidyl ether having one glycidyl ether group in the molecule. In the case of diglycidyl ether or polyglycidyl ether having two or more glycidyl ether groups in the molecule, there are two or more crosslinking points in one molecule. For this reason, the epoxy group remaining after the fiber treatment and the residual silanol group derived from the organosiloxane are cross-linked over time, resulting in polymerization, and water absorption may decrease. Examples of monoglycidyl ether include glycidyl ether of monohydric alcohol, glycidyl ether of monohydric alcohol with polyalkylene glycol chain introduced, glycidyl ether of monohydric phenol, glycidyl monohydric phenol with polyalkylene glycol chain introduced. Ether, glycidyl ether of polyhydric alcohol, glycidyl ether of polyhydric alcohol with polyalkylene glycol chain introduced, glycidyl ether of polyhydric phenol, glycidyl ether of polyhydric phenol with polyalkylene glycol chain introduced, Examples include those having only one glycidyl group.

The glycidyl ether compound is preferably a glycidyl ether having a polyalkylene glycol chain in the molecule from the viewpoint of further improving the antibacterial properties and water absorption after repeated washing, and further, glycidyl represented by the above general formula (2). Ether is preferred.
Wherein (2), ^{R 6} is alkyl, phenyl or C1-18 is a glycidyl group. As for carbon number of an alkyl group, 8-18 are preferable. The alkyl group for R ⁶ may be linear or branched. Among these, glycidyl ether-based compound, monoglycidyl ethers are preferred R ⁶ is an alkyl group having 1 to 18 carbon atoms, monoglycidyl ether R ⁶ is an alkyl group having 1 to 12 carbon atoms is more preferred. In the formula (2), A is an alkylene group having 2 to 5 carbon atoms, and in order to give better water absorption, the carbon number of A is preferably 2 to 4, and more preferably 2 to 3. The number n of repeating units of the polyalkylene glycol chain is 1 to 22, preferably 8 to 22. (AO) It is preferable that the oxyalkylene group which comprises _n contains an oxyethylene group essential. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 30 mol% or more, more preferably 50 mol%, still more preferably 80 mol% or more.

  There is no limitation in particular as a manufacturing method of a glycidyl ether type compound, A publicly known method is employable. A commercially available product can be used as the glycidyl ether compound.

[Reaction product of organosiloxane and glycidyl ether compound]
By treating a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound with a fiber material containing cellulosic fibers, antibacterial properties can be imparted and water absorption can be imparted in combination. Excellent antibacterial properties and water absorption can be imparted even after repeated washing. Furthermore, excellent water absorption can be imparted even with changes over time. Here, the reactant is a product in which a glycidyl ether compound is chemically bonded to an organosiloxane by dehydration and dealcoholization reactions that occur between an organosiloxane having a quaternary ammonium base and a glycidyl ether compound. The organosiloxane having a quaternary ammonium base and the glycidyl ether compound are the same as described above.

There is no particular limitation on the method for producing a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, and a known method can be employed. For example, an organosiloxane having a quaternary ammonium base and a glycidyl ether compound are reacted at 130 ° C. to 150 ° C. for 3 to 5 hours under a nitrogen stream, and the generated water and alcohol are distilled off to react. Can be manufactured.
The weight ratio (organosiloxane / glycidyl ether compound) of the organosiloxane having a quaternary ammonium base and the glycidyl ether compound in the production of the reaction product is preferably 0.3 to 3.0, preferably 0.5 to 2 .5 is more preferred.

[Fiber material containing cellulosic fibers]
Cellulosic fibers contain cellulose fibers, may be cellulose fibers alone, and may be blended, blended, woven or knitted with other fibers. Examples of cellulose fibers include natural cellulose fibers such as cotton, hemp, jute, and ramie, regenerated cellulose fibers such as rayon, cupra, polynosic, and purified cellulose fibers (trademark: Tencel), and melt-spun cellulose fibers. Examples of other fibers include polyester, cationic dyeable polyester, nylon, polyurethane, polyvinyl alcohol, acrylic, polyethylene, polypropylene, silk, and wool.
The fiber material containing cellulosic fibers is a fiber material used for an object imparting antibacterial properties, water absorption, and washing durability, for example, foundations, underwear, sports clothing, bedding, covers, and the like. Examples of the form of the fiber material include forms such as woven fabrics, knitted fabrics, fabrics, yarns, and nonwoven fabrics.

[Method for producing antibacterial fiber and antibacterial fiber]
The method for producing an antibacterial fiber of the present invention comprises treating a fiber material containing cellulosic fiber with an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, or an organosiloxane having a quaternary ammonium base. It includes a step (A) of treating a reaction product with a glycidyl ether compound. As a process (A), the process (A1) which processes simultaneously two components of this organosiloxane and this glycidyl ether type compound to the fiber material containing a cellulosic fiber, The process (A2) which processes these two components separately There is a step (A3) of treating a reaction product of the organosiloxane and the glycidyl ether compound.

As a process (A1), the process of processing the process liquid containing organosiloxane, a glycidyl ether type compound, and water is mentioned. There is no limitation in particular as a method of processing a processing liquid into a textile material, and a publicly known method is employable. For example, the fiber material can be treated by any of an immersion method, an impregnation method, a pad dry method, and a spray method. In more detail, the following are mentioned, for example.
First, the organosiloxane, glycidyl ether compound, and water are mixed and stirred in random order to prepare a treatment solution (preparation step). Next, the fiber material is sufficiently immersed in the treatment liquid to treat the organosiloxane and the glycidyl ether compound into the fiber material (step (A1)). After that, the fiber material is dehydrated and dried (drying process) to form a durable and durable film on the fiber surface, and it is possible to impart antibacterial and water absorption properties that are durable to washing. It becomes. The drying temperature for drying the fiber material may be room temperature, but it is preferably dried at a predetermined temperature from the viewpoint that a more durable coating can be formed. This will be described later in the heat treatment step (B).

  As a process (A2), the process which processes the process liquid containing one component and water among the said organosiloxane and a glycidyl ether type compound is included in the fiber material containing a cellulose fiber, and the other component and water are included. The process of processing a process liquid is mentioned. More specifically, for example, each treatment liquid is prepared by mixing and stirring one component each of an organosiloxane and a glycidyl ether compound and water in random order. After processing one treatment liquid into the fiber material by the same method as in step (A1), the other treatment liquid is also processed into the fiber material by the same method as in step (A1). From the viewpoint of imparting water absorption excellent in washing durability, it is preferable to treat the treatment liquid containing the glycidyl ether compound after treating the treatment liquid containing the organosiloxane. Subsequent steps are the same as those described in the step (A1).

Examples of the step (A3) include a step of treating a treatment liquid containing a reaction product of the organosiloxane and the glycidyl ether compound and water. The method for treating the fiber with the treatment liquid is the same as that described in the step (A1). In more detail, the following are mentioned, for example.
First, a reaction product of an organosiloxane and a glycidyl ether compound is obtained by treating an organosiloxane and a glycidyl ether compound in a nitrogen stream at 130 ° C. to 150 ° C. for 3 to 5 hours (reaction process). Next, this reaction product and water are mixed and stirred in random order to prepare a treatment liquid (preparation step). Next, the fiber material is sufficiently immersed in the treatment liquid to treat the reaction product into the fiber material (step (A3)). Subsequent steps are the same as those described in the step (A1).

  In addition, the antibacterial fiber obtained by the production method of the present invention is formed by adhering a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound to a fiber material containing cellulosic fibers. is there. When the reactant is fixed on the fiber material, it has excellent antibacterial properties and water absorption, and has excellent antibacterial properties and water absorption even after repeated washing. In addition, it has excellent water absorption even with changes over time. These effects are estimated as follows.

A silanol group derived from an alkoxysilyl group of an organosiloxane has reactivity with active hydrogen generated by ring opening of a hydroxyl group of a cellulosic fiber and an epoxy group of a glycidyl ether compound. The active hydrogen generated by the ring opening of the epoxy group of the glycidyl ether compound is reactive with the silanol group derived from the hydroxyl group of the cellulose fiber and the alkoxysilyl group of the organosiloxane.
Therefore, when treated in step (A1) or step (A2), not only the organosiloxane and glycidyl ether compound are fixed to the fiber material, but also the organosiloxane reacts with the glycidyl ether compound on the fiber material. Then, the reaction product is fixed. As a result, the glycidyl ether compound is presumed to have a higher ratio of being retained by chemical bonding on the fiber material containing cellulosic fibers, and to improve the washing durability.
In addition, the organosiloxane has high hydrophobicity, and when it is fixed to the fiber material alone, the water repellency after washing becomes high. However, when this reactant is fixed, the organosiloxane is fixed to the fiber material alone. A ratio becomes low and the water-repellent expression after washing is suppressed. Therefore, it is presumed that it has excellent antibacterial properties and water absorption even after repeated washing, and has excellent water absorption even with changes over time.

  Also, as in step (A3), a reaction product of an organosiloxane and a glycidyl ether compound can be prepared in advance, and the reaction product can be processed into a fiber material. In that case, compared with the step (A1) and the step (A2), the proportion of the organosiloxane alone fixed to the fiber material becomes lower, so that the washing durability and the water absorption in the aging change are further improved.

  Among the steps (A1), (A2), and (A3), the method for producing an antibacterial fiber of the present invention includes the steps (A1), ( A3) is preferred.

  It is preferable that the manufacturing method of the antimicrobial fiber of this invention further includes the process (B) of heat-processing the fiber material processed by the said process (A). In particular, in the case of the step (A1) and the step (A2), it is preferable to include a step (B) for heat treatment. By performing the heat treatment, ring opening of the epoxy group possessed by the glycidyl ether compound is promoted, and the reaction between the hydroxyl group of the cellulosic fiber and the silanol group derived from the organosiloxane is promoted. Leads to a good film formation. The heat treatment may be performed on the dried fiber material, but is preferably performed when the fiber material to which the treatment liquid is attached is dehydrated and dried. The temperature of the heat treatment is preferably 100 to 220 ° C, more preferably 110 ° C to 200 ° C. When the heat treatment temperature is lower than 100 ° C., it may be difficult to form a durable coating. On the other hand, when the heat treatment temperature exceeds 220 ° C., the physical properties of the fiber material itself may be deteriorated. The heat treatment time is preferably 1 to 30 minutes, more preferably 1 to 10 minutes. If the heat treatment time is less than 1 minute, it may be difficult to form a durable coating. On the other hand, when the heat treatment time exceeds 30 minutes, the hue of the fiber material and the dye fixed to the fiber material may be changed.

  The treatment liquid essentially contains water. The method for preparing the treatment liquid is not particularly limited, and a known method can be employed. For example, it can be prepared by mixing and stirring the organosiloxane, the glycidyl ether compound (or their reaction product), and water in any order. Moreover, it can also prepare by diluting the antibacterial processing agent mentioned later with water. The treatment liquid is composed of water except for an organosiloxane, a glycidyl ether compound (or a reaction product thereof), other components contained as necessary, and a solvent other than 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.

  In the treatment liquids of step (A1) and step (A2), the weight ratio of the organosiloxane to the whole treatment liquid is preferably 0.1 to 3.0% by weight, more preferably 0.3 to 1.0% by weight. . If the weight ratio is less than 0.1% by weight, antibacterial properties may not be obtained. On the other hand, when the weight ratio is more than 3.0% by weight, the hydrophobicity becomes strong and the cost may be increased.

  In the treatment liquid of step (A1) and step (A2), the weight ratio of the glycidyl ether compound to the whole treatment liquid is preferably 0.1 to 3.0% by weight, and 0.3 to 2.0% by weight. More preferred. When the weight ratio is less than 0.1% by weight, durable water absorption after washing may not be obtained. On the other hand, when the weight ratio is more than 3.0% by weight, the cost may increase, the texture of the fiber itself may deteriorate, and an unpleasant stimulus may be given from the viewpoint of skin safety and hygiene.

  In the treatment liquid of the step (A3), the weight ratio of the reaction product of the organosiloxane and the glycidyl ether compound to the whole treatment liquid is preferably 0.3 to 3.0% by weight, and 0.5 to 2.5% by weight. % Is more preferable. When the weight ratio is less than 0.3% by weight, the texture of the fiber itself may be deteriorated. If it exceeds 3.0% by weight, water absorption excellent in washing durability may not be imparted.

The bath ratio (bath ratio = weight of the fiber material: weight of the treatment liquid) is preferably 1: 5 to 1:50, more preferably 1:10 to 1:30. When the bath ratio is smaller than 1: 5 (the weight ratio of the treatment liquid to the fiber material is smaller than 5), the uniform adhesion of the components to the fibers is hindered, and uneven adhesion may occur. On the other hand, if the bath ratio is greater than 1:50 (the weight ratio of the treatment liquid to the fiber material is greater than 50), the treatment liquid tends to foam during processing, which may cause problems such as scum generation.
Further, the drawing rate (impregnation rate of the treatment liquid with respect to the fiber material) is preferably 70 to 110% by weight, and more preferably 80 to 100% by weight. If it is lower than 70% by weight, the adhesion rate of the component will be low, and the target performance may not be imparted. On the other hand, when it exceeds 110%, problems such as a decrease in the texture of the fiber itself and a failure to achieve the target performance may occur due to an increase in the adhesion rate of the component.

  In addition to the reaction product of the organosiloxane, the glycidyl ether compound, or the organosiloxane and the glycidyl ether compound, the treatment liquid may contain other components as long as the effects of the present invention are not impaired. . Examples of other components include a softening agent, an antistatic agent, a water absorbing agent, a fixing agent, and a penetrating agent used for finishing.

  The step (A1) or the step (A2) is a step of treating the fiber material with the organosiloxane and the glycidyl ether compound at a weight ratio of 0.3 to 3.0 (organosiloxane / glycidyl ether compound). Preferably there is. The weight ratio is more preferably 0.5 to 2.5. When the weight ratio is less than 0.3, the texture of the fiber itself may be deteriorated. When the weight ratio exceeds 3.0, it may not be possible to impart excellent water absorption. In order to adhere the organosiloxane and the glycidyl ether-based compound to the fiber material in the above weight ratio, the treatment liquid containing both components may be attached to the fiber material in the above weight ratio.

In the step (A1) or the step (A2), the adhesion amount of the organosiloxane to the fiber material is preferably 0.1 to 3.0% by weight, and more preferably 0.3 to 1.0% by weight. If it is less than 0.1% by weight, antibacterial properties may not be obtained. On the other hand, when it exceeds 3.0% by weight, the hydrophobicity becomes strong and the cost may be increased. Moreover, 0.1 to 3.0 weight% is preferable and the adhesion amount with respect to the fiber material of the said glycidyl ether type compound has more preferable 0.3 to 2.0 weight%. If it is less than 0.1% by weight, durable water absorption after washing may not be obtained. On the other hand, when the content exceeds 3.0% by weight, the cost may increase, the texture of the fiber itself may deteriorate, and skin irritation may be undesirable.
In the step (A3), the adhesion amount of the reaction product of the organosiloxane and the glycidyl ether compound to the fiber material is preferably 0.1 to 3.0% by weight, more preferably 0.3 to 1.0% by weight. . If it is less than 0.1% by weight, antibacterial properties and durable water absorption after washing may not be obtained. On the other hand, if it exceeds 3.0% by weight, the cost may increase, the texture of the fiber itself may deteriorate, and skin irritation may be undesirable.

  The antibacterial fibers obtained by the production method of the present invention have excellent antibacterial properties and water absorption, and further maintain these performances even after repeated washing. Further, it does not cause a decrease in the texture of the fiber itself.

[Antimicrobial processing agent for cellulosic fibers]
The antibacterial finishing agent for cellulosic fibers of the present invention is used in the method for producing an antibacterial fiber of the present invention, and is for cellulosic fibers containing an organosiloxane having a quaternary ammonium base and a glycidyl ether compound. An antibacterial finishing agent or an antibacterial finishing agent for cellulose fibers containing a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound. An organosiloxane having a quaternary ammonium base, a glycidyl ether compound, a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, and preferred modes and ranges thereof are the same as described above.

  When the antibacterial processing agent for cellulose fibers of the present invention contains an organosiloxane having a quaternary ammonium base and a glycidyl ether compound, the weight ratio of the organosiloxane in the nonvolatile content of the antibacterial processing agent is 10 to 80% by weight. % Is preferable, and 20 to 50% by weight is more preferable. When the weight ratio is less than 10%, excellent antibacterial properties may not be exhibited. On the other hand, when the weight ratio exceeds 80% by weight, excellent water absorption may not be exhibited. Moreover, 10 to 80 weight% is preferable and, as for the weight ratio of this glycidyl ether type compound to the non volatile matter of an antibacterial processing agent, 20 to 50 weight% is more preferable. When the weight ratio is less than 10% by weight, excellent water absorption may not be exhibited. On the other hand, when the weight ratio exceeds 80% by weight, excellent antibacterial properties may not be exhibited. In addition, the non-volatile matter as used in the field of this invention means the residual component when an antibacterial processing agent is heat-processed at 105 degreeC, and a solvent etc. are volatilized.

  The weight ratio of the organosiloxane to the glycidyl ether compound (organosiloxane / glycidyl ether compound) is preferably 0.3 to 3.0, more preferably 0.5 to 2.5. When the weight ratio is less than 0.3, the texture of the fiber itself may be deteriorated. When the weight ratio exceeds 3.0, it may not be possible to impart excellent water absorption.

  When the antibacterial processing agent for cellulose fibers of the present invention contains a reaction product of an organosiloxane and a glycidyl ether compound, the weight ratio of the reaction product in the nonvolatile content of the antibacterial processing agent is preferably 10 to 80% by weight. 20 to 70% by weight is more preferable. When the weight ratio is less than 10% by weight, excellent antibacterial properties and water absorption may not be exhibited.

  The antibacterial finishing agent for cellulosic fibers of the present invention may contain other components in addition to the aforementioned components as long as the effects of the present invention are not impaired. Examples of other components include a softening agent, an antistatic agent, a water absorbing agent, a fixing agent, and a penetrating agent used for finishing.

The antibacterial processing agent of the present invention contains an alcohol solvent as a solvent in order to suppress hydrolysis of the alkoxysilyl group of the organosiloxane. Therefore, it is better not to contain water substantially. When water is present, induction from the alkoxysilyl group of the organosiloxane to the silanol group is promoted, and a polycondensation reaction occurs between the silanols, which may solidify the processing agent.
Examples of alcohol solvents include methanol, ethanol, propanol, butanol and the like. Among these, methanol and ethanol are preferable.

10 to 90 weight% is preferable, as for the weight ratio of the non volatile matter which occupies for an antibacterial processing agent, 20 to 85 weight% is more preferable, and 30 to 80 weight% is further more preferable.
There is no limitation in particular about the method of preparing an antibacterial processing agent, A well-known method is employable. For example, it is prepared by mixing and stirring the organosiloxane, the glycidyl ether compound (or a reaction product thereof), and an alcohol solvent in any order.

EXAMPLES 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. Examples 6 to 9, 18, and 19 are used as reference examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

Example 1
As shown in Table 1, as the organosiloxane having a quaternary ammonium base, 1.0% by weight of 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride, and 0.1% of lauryl alcohol EO (15 mol) glycidyl ether. 5 wt% and 98.5 wt% of water were mixed and stirred, and a treatment liquid was prepared with a bath ratio of 1:20. A T / C fabric (polyester / cotton = 50% by weight / 50% by weight) was immersed in this treatment liquid, treated at a drawing rate of 90% by weight, and then heat treated at 130 ° C. for 3 minutes. The anti-bacterial property, water absorption, and water absorption change of the obtained treated cloth (test cloth) before and after washing 10 times were evaluated. The results are shown in Table 3. In addition, about the washing | cleaning method and the antibacterial property, water absorption, and the test method of the daily change of water absorption, it carried out by the following method.

[How to wash]
The test fabric was washed according to JIS-L-0217 103 method. As the detergent, Attack (registered trademark) (manufactured by Kao Corporation) was used, and the detergent concentration of the washing liquid was 1.0 g / L. Under the above conditions, repeated washing was performed 10 times.

[Antimicrobial]
The bacteriostatic activity value was measured by a JIS-L-1902 quantitative test (bacterial liquid absorption method) to evaluate the antibacterial performance of the test cloth. As a bacterium to be used, Staphylococcus aureus ATCC 6538P was used.
Evaluation criteria: In antibacterial processing, the bacteriostatic activity value is 2.0 or more. Moreover, the higher the bacteriostatic activity value, the better the antibacterial property. In Table 3, “5.9 <” indicates that the bacteriostatic activity value is greater than 5.9.

[Water absorption]
According to the JIS-L-1907 dropping method, 1 drop of water (about 12 mg) was dropped onto the test cloth, and the time (seconds) until reflection by the water drop disappeared was measured to evaluate the water absorption. It shows that water absorption is so high that a numerical value is small. In Table 4, “<1” indicates less than 1 second, and “180 <” indicates greater than 180 seconds.

[Change in water absorption over time (over-drying)]
About what dried the test cloth for 105 degreeC x 3 hours, the water absorption before washing and 10 times after washing was evaluated.

(Examples 2-15, Comparative Examples 1-14)
Examples 2 to 15 and Comparative Examples 2 to 14 are examples except that the organosiloxane having a quaternary ammonium base and the glycidyl ether compound of Example 1 were changed to the components and ratios shown in Tables 1 and 2. Evaluation was performed in the same manner as in 1. Further, as Comparative Example 1, a T / C fabric that was not processed was evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.

(Example 16)
In a three-necked flask, 30.0 parts by weight of 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride as an organosiloxane having a quaternary ammonium base and lauryl alcohol EO (15 mol) as a glycidyl ether compound By charging 15.0 parts by weight of glycidyl ether and 0.01 parts by weight of acetic anhydride as an acid catalyst, reacting at 130 to 150 ° C. for 3 to 5 hours under a nitrogen stream, and distilling off generated water and methanol A reaction product was obtained. The reaction product was cooled to room temperature, and 55.0 parts by weight of methanol was added to prepare a methanol solution of the reaction product.
Then, a methanol solution of this reaction product was mixed and stirred with 1.5% by weight and 98.5% by weight of water in terms of active ingredients, and a treatment liquid was prepared with a bath ratio of 1:20. A T / C fabric (polyester / cotton = 50% by weight / 50% by weight) was immersed in this treatment liquid, treated at a drawing rate of 90% by weight, and then heat treated at 130 ° C. for 3 minutes. The obtained treated cloth (test cloth) was evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 17)
Evaluation was conducted in the same manner as in Example 16 except that the glycidyl ether compound was changed to butanol EO (4.5 mol) glycidyl ether. The results are shown in Table 3.

(Example 18)
Evaluation was conducted in the same manner as in Example 16 except that EO (9 mol) diglycidyl ether was used as the glycidyl ether compound. The results are shown in Table 3.

(Example 19)
Evaluation was conducted in the same manner as in Example 16 except that EO (23 mol) diglycidyl ether was used as the glycidyl ether compound. The results are shown in Table 3.

(Example 20)
As organosiloxane having a quaternary ammonium base, 30.0 parts by weight of 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride, and 15.0% by weight of lauryl alcohol EO (15 mol) glycidyl ether as a glycidyl ether compound. The antibacterial processing agent for cellulosic fibers was prepared by mixing and stirring 55.0 parts by weight of methanol as a part and a solvent.
Next, this antibacterial finishing agent was mixed and stirred at 1.5% by weight and 98.5% by weight of water in terms of active ingredients, and a treatment liquid was prepared with a bath ratio of 1:20. A T / C fabric (polyester / cotton = 50% / 50%) was immersed in this treatment solution, treated at a drawing rate of 90% by weight, and then heat treated at 130 ° C. for 3 minutes. The obtained treated cloth (test cloth) was evaluated in the same manner as in Example 1. The results are shown in Table 3.

  Examples 1 to 20 have excellent antibacterial properties and water absorption. Moreover, as compared with Comparative Examples 1 to 14, it has excellent antibacterial properties and water absorption even after 10 washings. Further, Examples 1 to 5, 16, 17, and 20 have excellent water absorption even in the aging (overdrying).

  In Examples 1 to 15 in which two components of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound are simultaneously processed into a fiber material, water absorption is performed after washing as compared with the case where these two components are separately processed into a fiber material. Excellent in properties. Organosiloxane having antibacterial properties has high hydrophobicity, and when it is fixed to a fiber material alone, the water repellency after washing becomes high. In Examples 1 to 15, the ratio of formation of a reaction product of an organosiloxane and a glycidyl ether compound on the fiber material is increased, and the water repellency expression is suppressed after washing. The

  Examples 16-20 have antibacterial properties and water absorption superior to those of Examples 1-15. In addition, Examples 16 and 17 have excellent water absorption even with aging (overdrying). In Examples 16-20, since the reaction material of organosiloxane and a glycidyl ether compound is processed into a fiber material, the proportion of the organosiloxane alone fixed to the fiber material is lower than in Examples 1-15, and after washing It is estimated that the water absorption is excellent.

  The method for producing antibacterial fibers of the present invention can be suitably used when antibacterial properties are imparted to a fiber material containing cellulosic fibers.

Claims (11)

A step (A1) of treating a treatment liquid containing an organosiloxane having a quaternary ammonium base, a glycidyl ether compound and water on a fiber material containing cellulosic fibers, and a fiber treated by the step (A1). look including a step (B) heat-treating the material,
The organosiloxane is an organosiloxane represented by the following general formula (1):
The glycidyl ether compound is a glycidyl ether represented by the following general formula (2),
A reaction product of the organosiloxane and the glycidyl ether compound is fixed to the fiber material obtained through the steps (A1) and (B).
A method for producing antibacterial fibers.

(R ¹ is an alkyl group having 1 to 22 carbon atoms. R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms. R ⁵ is an alkyl group having 1 to 10 carbon atoms. An alkylene group, X ⁻ is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ^— .

(R ⁶ is an alkyl group having 1 to 18 carbon atoms, a phenyl group or a glycidyl group. A is an alkylene group having 2 to 5 carbon atoms. The number n of repeating units of the polyalkylene glycol chain is 1 to 22. is there.) Wherein the step (A 1), the fibrous material containing cellulosic fibers, processing the organosiloxane and the glycidyl ether compound in a weight ratio of 0.3 to 3.0 (organosiloxane / glycidyl ether compound) a method of manufacturing an antibacterial fiber according to claim 1. The weight ratio of the organosiloxane is 0.1 to 3.0% by weight and the weight ratio of the glycidyl ether compound is 0.1 to 3.0% by weight with respect to the entire treatment liquid in the step (A1). The manufacturing method of the antimicrobial fiber of Claim 1 or 2. Including a step (A3) of treating a treatment liquid containing a reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound and water in a fiber material containing cellulosic fibers;
The organosiloxane is an organosiloxane represented by the following general formula (1):
The glycidyl ether compound is a glycidyl ether represented by the following general formula (2),
A reaction product of the organosiloxane and the glycidyl ether compound is fixed to the fiber material obtained through the step (A3).
A method for producing antibacterial fibers.

(R ¹ Is an alkyl group having 1 to 22 carbon atoms. R ² , R ³ And R ⁴ Are each independently an alkyl group having 1 to 10 carbon atoms. R ⁵ Is an alkylene group having 1 to 10 carbon atoms. X ⁻ Is Cl ⁻ , Br ⁻ , I ⁻ Or CH ₃ COO ⁻ It is. )

(R ⁶ Is a C1-C18 alkyl group, a phenyl group, or a glycidyl group. A is an alkylene group having 2 to 5 carbon atoms. The number n of repeating units of the polyalkylene glycol chain is 1 to 22. ) The manufacturing method of the antimicrobial fiber of Claim 4 whose weight ratio of the said reaction material with respect to the whole process liquid of a process (A3) is 0.1 to 3.0 weight%. The method for producing an antibacterial fiber according to any one of claims 1 to 5 , wherein the glycidyl ether compound is a monoglycidyl ether in which R ^{6 in the} general formula (2) is an alkyl group having 1 to 18 carbon atoms. . Containing organosiloxane, glycidyl ether compounds and alcohol solvent having a quaternary ammonium base,
The organosiloxane is an organosiloxane represented by the following general formula (1):
The glycidyl ether compound is a glycidyl ether represented by the following general formula (2).
Antibacterial finishing agent for cellulosic fibers.

(R ¹ is an alkyl group having 1 to 22 carbon atoms. R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms. R ⁵ is an alkyl group having 1 to 10 carbon atoms. An alkylene group, X ⁻ is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ^— .

(R ⁶ is an alkyl group having 1 to 18 carbon atoms, a phenyl group or a glycidyl group. A is an alkylene group having 2 to 5 carbon atoms. The number n of repeating units of the polyalkylene glycol chain is 1 to 22. is there.) The antibacterial finishing agent for cellulose fibers according to claim 7, wherein a weight ratio of the organosiloxane to the glycidyl ether compound (organosiloxane / glycidyl ether compound) is 0.3 to 3.0 . The cellulose type according to claim 7 or 8 , wherein a weight ratio of the organosiloxane in a nonvolatile content of the antibacterial processing agent is 10 to 80% by weight, and a weight ratio of the glycidyl ether compound is 10 to 80% by weight. Antibacterial finishing agent for textiles . A reaction product of an organosiloxane having a quaternary ammonium base and a glycidyl ether compound and an alcohol solvent;
The organosiloxane is an organosiloxane represented by the following general formula (1):
The glycidyl ether compound is a glycidyl ether represented by the following general formula (2).
Antibacterial finishing agent for cellulosic fibers.

(R ¹ Is an alkyl group having 1 to 22 carbon atoms. R ² , R ³ And R ⁴ Are each independently an alkyl group having 1 to 10 carbon atoms. R ⁵ Is an alkylene group having 1 to 10 carbon atoms. X ⁻ Is Cl ⁻ , Br ⁻ , I ⁻ Or CH ₃ COO ⁻ It is. )

(R ⁶ Is a C1-C18 alkyl group, a phenyl group, or a glycidyl group. A is an alkylene group having 2 to 5 carbon atoms. The number n of repeating units of the polyalkylene glycol chain is 1 to 22. ) The antibacterial processing agent for cellulosic fibers according to claim 10, wherein a weight ratio of the reaction product to a nonvolatile content of the antibacterial processing agent is 10 to 80% by weight .