CN103025951A - Method for producing antibacterial fibers, antibacterial fibers and antibacterial processing agent for fibers - Google Patents
Method for producing antibacterial fibers, antibacterial fibers and antibacterial processing agent for fibers Download PDFInfo
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- CN103025951A CN103025951A CN201180036029XA CN201180036029A CN103025951A CN 103025951 A CN103025951 A CN 103025951A CN 201180036029X A CN201180036029X A CN 201180036029XA CN 201180036029 A CN201180036029 A CN 201180036029A CN 103025951 A CN103025951 A CN 103025951A
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- glycidol ether
- organosiloxane
- based compound
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
- D06M15/652—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups comprising amino groups
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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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
Technical field
The present invention relates to the antibiotic fiber of the fibrous material endowing antibacterial that contains cellulose fibre manufacture method, utilize this manufacture method and the antibiotic fiber and the antibiotic processing agent of cellulose fibre that obtain.
Background technology
As the method for fibrous material being given the antibiotic property with washing resistance, the known method that has use to have the organosiloxane of quaternary ammonium salt base.The alkoxysilyl that this organosiloxane is contained, can be in fibrous material contained hydroxyl with chemical condensation mode be combined, therefore can give the antibiotic property with washing resistance (for example, patent documentation 1) to fibrous materials such as cellulose fibres.
But there is the problem that its hydrophobicity raises, water imbibition descends in the fibrous material that the organosiloxane that common use has quaternary ammonium salt base was processed.In order to improve this problem, for example propose to have the fiber process finishing agent of patent documentation 2, but washing resistance is insufficient, can't keep the water imbibition behind the cyclic washing.That is antibiotic, water imbibition that, washing resistance is good can't be realized by the finishing agent of patent documentation 2.
As other medicament, known have hexamethylene, a chlorhexidine gluconate etc.Water imbibition with respect to object being treated is reduced, but be difficult to give the antibiotic property with washing resistance to object being treated with general method.
[prior art document]
Patent documentation 1: Japanese kokai publication sho 62-177284 communique
Patent documentation 2: Japanese kokai publication sho 60-39478 communique
Summary of the invention
The object of the invention is to, can be to fibrous material endowing antibacterial and the water imbibition that contains cellulose fibre and the antibiotic processing agent of manufacture method, antibiotic fiber, cellulose fibre that behind cyclic washing, also has outstanding antibiotic property and absorptive antibiotic fiber even if provide.
[being used for solving the means of problem]
The inventor etc. concentrate on studies in order to solve above-mentioned problem, found that: if with the organosiloxane with quaternary ammonium salt base and glycidol ether based compound the fibrous material that contains cellulose fibre is processed, then can make antibiotic property and water imbibition and deposit, even and if then also have outstanding antibiotic property and absorptive antibiotic fiber after can making cyclic washing.In addition, if the reactant with the organosiloxane with quaternary ammonium salt base and glycidol ether based compound is processed the fibrous material that contains cellulose fibre, then can make antibiotic property and water imbibition and deposit, even and if then behind cyclic washing, also have outstanding antibiotic property and a water imbibition.
Namely, the present invention is the manufacture method of antibiotic fiber, and it comprises following operation (A): the fibrous material that contains cellulose fibre is processed or with the reactant of this organosiloxane and this glycidol ether based compound the fibrous material that contains cellulose fibre is processed with organosiloxane and glycidol ether based compound with quaternary ammonium salt base.
The organosiloxane of the preferred following general formula of above-mentioned organosiloxane (1) expression.
[changing 1]
(R
1It is the alkyl of carbon number 1～22.R
2, R
3And R
4Be the alkyl of carbon number 1～10 independently respectively.R
5It is the alkylidene of carbon number 1～10.X
-Cl
-, Br
-, I
-Or CH
3COO
-)
Above-mentioned glycidol ether based compound is preferably from the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether of monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyhydric phenols and imported at least a kind of glycidol ether selecting the glycidol ether of polyhydric phenols of polyalkylene glycol chain.
In addition, above-mentioned glycidol ether based compound preferably has the glycidol ether of polyalkylene glycol chain.
And then, the glycidol ether of the preferred following general formula of above-mentioned glycidol ether based compound (2) expression.
[changing 2]
(R
6Alkyl, phenyl or the glycidyl of carbon number 1～18.A is the alkylidene of carbon number 2～5.The quantity n of the repetitive of polyalkylene glycol chain is 1～22.)
Above-mentioned glycidol ether based compound, the R of preferred above-mentioned general formula (2)
6Monoglycidyl ether for the alkyl of carbon number 1～18.
Above-mentioned operation (A), the operation of preferably fibrous material that contains cellulose fibre being processed with above-mentioned organosiloxane and above-mentioned glycidol ether based compound with 0.3～3.0 part by weight (organosiloxane/glycidol ether based compound).
Above-mentioned operation (A), the operation of preferably with the treatment fluid that contains above-mentioned organosiloxane, above-mentioned glycidol ether based compound and water the fibrous material that contains cellulose fibre being processed.
In addition, the manufacture method of antibiotic fiber of the present invention preferably also comprises the operation (B) that the fibrous material of processing through above-mentioned operation (A) is heat-treated.
In addition, antibiotic fiber of the present invention is obtained by above-mentioned manufacture method, is that the reactant of above-mentioned organosiloxane and above-mentioned glycidol ether based compound is bonded to the fibrous material that contains cellulose fibre and forms.
The antibiotic processing agent of cellulose fibre of the present invention contains organosiloxane and glycidol ether based compound with quaternary ammonium salt base, or contains the reactant of this organosiloxane and this glycidol ether based compound.
Cellulose fibre with antibiotic processing agent in, the organosiloxane of the preferred above-mentioned general formula of above-mentioned organosiloxane (1) expression.
Cellulose fibre with antibiotic processing agent in, above-mentioned glycidol ether based compound is preferably from the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether of monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyhydric phenols and imported at least a kind of glycidol ether selecting the glycidol ether of polyhydric phenols of polyalkylene glycol chain.
In addition, the glycidol ether of the preferred above-mentioned general formula of above-mentioned glycidol ether based compound (2) expression.
[effect of invention]
According to the manufacture method of antibiotic fiber of the present invention, can give and deposit antibiotic property and water imbibition to the fibrous material that contains cellulose fibre, even and if can give behind cyclic washing also outstanding antibiotic property and water imbibition.
Antibiotic fiber of the present invention has outstanding antibiotic property and water imbibition, even if also have behind cyclic washing also outstanding antibiotic property and water imbibition.
The antibiotic processing agent of cellulose fibre of the present invention can be to containing fibrous material endowing antibacterial and the water imbibition of cellulose fibre, even if can also give behind cyclic washing also outstanding antibiotic property and water imbibition.
The specific embodiment
The present invention is the manufacture method of antibiotic fiber, and it comprises following operation (A): with having the organosiloxane of quaternary ammonium salt base and the glycidol ether based compound is processed the fibrous material that contains cellulose fibre or the operation (A) the fibrous material that contains cellulose fibre processed with the reactant of this organosiloxane and this glycidol ether based compound.Below be elaborated.
[organosiloxane with quaternary ammonium salt base]
Have the organosiloxane (sometimes referred to as organosiloxane) of quaternary ammonium salt base, usually gram-positive bacteria, Gram-negative bacteria, mould class, algae etc. are had outstanding antibacterial effect.In the present invention, the fibrous material that contains cellulose fibre is processed with the glycidol ether based compound with the organosiloxane with quaternary ammonium salt base, thus can endowing antibacterial, also can give simultaneously water imbibition, even and if then can give behind the cyclic washing also outstanding antibiotic property and water imbibition.As the organosiloxane with quaternary ammonium salt base, owing to being combined with the form of condensation with cellulosic hydroxyl and reacting with the glycidol ether based compound, so have at least 1 alkoxysilyl in the preferred molecule, have 2 above alkoxysilyls in the further preferred molecule.
From giving the viewpoint of the antibacterial effect with washing resistance, has the organosiloxane of the preferred above-mentioned general formula of organosiloxane (1) expression of quaternary ammonium salt base.In formula (1), R
1It is the alkyl of carbon number 1～22.From embodying the viewpoint of outstanding antibacterial effect, preferred R
1Carbon number be 8～22.R
1Alkyl can be the straight chain shape, can also be chain.
R
2, R
3And R
4Be the alkyl of carbon number 1～10 independently respectively.R
2, R
3And R
4Carbon number preferred 1～5, more preferably 1～3.About R
4, most preferably steric restriction low, based on the hydrolysis the fast methyl of silanol formation speed.R
2, R
3And R
4Alkyl can be the straight chain shape, can also be chain.
R
5It is the alkylidene of carbon number 1～10.R
5Carbon number preferred 1～5, more preferably 1～3.X
-Cl
-, Br
-, I
-Or CH
3COO
-, preferred Cl
-, Br
-, I
-, more preferably Cl
-
Organosiloxane with quaternary ammonium salt base can use commercially available siloxanes, and is usually in addition commercially available as alcoholic solution.
[glycidol ether based compound]
The glycidol ether based compound is processed the fibrous material of cellulose fibre with above-mentioned organosiloxane, thus can endowing antibacterial and water imbibition, and then can give behind the cyclic washing also outstanding antibiotic property and water imbibition.
The glycidol ether based compound, the open loop by the epoxy radicals that caused by heat etc. generates reactive hydrogen, and the reaction with the hydroxyl of cellulose fibre occurs.And then, have at above-mentioned organosiloxane in the situation of alkoxysilyl, react with the silanol group of deriving from alkoxysilyl.For this reason, supposition is compared with amine, alcohol etc., and the ratio that the glycidol ether based compound is maintained at by chemical bond on the fibrous material that contains cellulose fibre raises, and washing resistance also raises.
As the glycidol ether based compound, so long as have the compound of at least 1 glycidyl ether in the molecule, just be not particularly limited.For example can enumerate the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether from monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyhydric phenols and import at least a kind of glycidol ether selecting the glycidol ether of polyhydric phenols of polyalkylene glycol chain.
As monohydric alcohol, can be in aliphatic alcohol, the alicyclic alcohol any one, can be saturated, undersaturated any one.In the middle of these, preferred aliphat alcohol, more preferably representative examples of saturated aliphatic is pure, the representative examples of saturated aliphatic alcohol of further preferred carbon number 1～18.As monohydric alcohol, such as enumerating methyl alcohol, ethanol, propyl alcohol, butanols, 2-Ethylhexyl Alcohol, lauryl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, cyclohexanol etc.
Import the monohydric alcohol of polyalkylene glycol chain, referred to the alkylene oxide addition product of aforesaid monohydric alcohol, and had (gathering) oxyalkylene.As oxyalkylene, can enumerate the oxyalkylene of carbon number 2～5, preferred oxygen ethylidene, oxygen propylidene, oxygen butylidene, more preferably oxygen ethylidene, oxygen propylidene, further preferred oxygen ethylidene.The repetitive of oxyalkylene is preferred 1～22, and more preferably 8～22.The oxyalkylene that consists of polyoxy alkylidene can be identical, for example can be different as the block copolymer of oxygen ethylidene and oxygen propylidene, random copolymer.From giving absorptive viewpoint, preferably must contain the aerobic ethylidene.Oxygen ethylidene shared ratio in whole oxyalkylenes is preferably more than 30 % by mole, and is more preferably 50 % by mole, further preferred more than 80 % by mole.
As the glycidol ether of monohydric alcohol, can enumerate methyl glycidyl ether, ethyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidol ether, lauryl diglycidyl ether, lauryl glycidol ether, myristyl glycidol ether, cetyl glycidol ether, stearyl glycidol ether, oil base glycidol ether, cyclohexyl glycidol ether etc.
As the glycidol ether of the monohydric alcohol that has imported polyalkylene glycol chain, can enumerate the polyoxyethylene methyl glycidyl ether, the polyoxyethylene ethyl ether, the polyoxyethylene propyl glycidyl ether, the polyoxyethylene butyl glycidyl ether, the polyoxyethylene octyl glycidyl ether, the polyoxyethylene lauryl diglycidyl ether, polyoxyethylene lauryl glycidol ether, polyoxyethylene myristyl glycidol ether, polyoxyethylene cetyl glycidol ether, polyoxyethylene stearyl glycidol ether, polyoxyethylene oil base glycidol ether, polyoxyethylene cyclohexyl glycidol ether, polyoxyethylene polyoxy propylidene methyl glycidyl ether, polyoxyethylene polyoxy propylidene ethyl ether, polyoxyethylene polyoxy propylidene propyl glycidyl ether, polyoxyethylene polyoxy propylidene butyl glycidyl ether, polyoxyethylene polyoxy propylidene octyl glycidyl ether, polyoxyethylene polyoxy propylidene lauryl diglycidyl ether, polyoxyethylene polyoxy propylidene lauryl glycidol ether, polyoxyethylene polyoxy propylidene myristyl glycidol ether, polyoxyethylene polyoxy propylidene cetyl glycidol ether, polyoxyethylene polyoxy propylidene stearyl glycidol ether, polyoxyethylene polyoxy propylidene oil base glycidol ether, polyoxyethylene polyoxy propylidene cyclohexyl glycidol ether, polyoxy propylidene methyl glycidyl ether, polyoxy propylidene ethyl ether, polyoxy propylidene propyl glycidyl ether, polyoxy propylidene butyl glycidyl ether, polyoxy propylidene octyl glycidyl ether, polyoxy propylidene lauryl diglycidyl ether, polyoxy propylidene lauryl glycidol ether, polyoxy propylidene myristyl glycidol ether, polyoxy propylidene cetyl glycidol ether, polyoxy propylidene stearyl glycidol ether, polyoxy propylidene oil base glycidol ether, polyoxy propylidene cyclohexyl glycidol ether etc.
As polyalcohol, can be any one of aliphatic alcohol, alicyclic alcohol, can be saturated, undersaturated any one.As polyalcohol, preferred 2～5 yuan of alcohol, further preferred 2～3 yuan of alcohol.
As polyalcohol, for example can enumerate ethylene glycol, diethylene glycol (DEG), triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyethylene polypropylene glycol, 1,4-butanediol, 1,6-hexane diol, neopentyl glycol, glycerine, pentaerythrite, D-sorbite etc.
Import the polyalcohol of polyalkylene glycol chain, referred to the alkylene oxide addition product of aforesaid polyalcohol, had at least 1 (gathering) oxyalkylene.About the quantity of (gathering) oxyalkylene, just be not particularly limited as long as have at least 1, can comprise the number identical with first number of polyalcohol.About (gathering) oxyalkylene, identical with the group of in the monohydric alcohol that has imported polyalkylene glycol chain, putting down in writing.
Glycidol ether as polyalcohol, can enumerate ethylene glycol diglycidylether, the diethylene glycol (DEG) diglycidyl ether, triethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, the dipropylene glycol diglycidyl ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, the polyethylene polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether, neopentylglycol diglycidyl ether, T 55, the pentaerythrite polyglycidyl ether, D-sorbite polyglycidyl ether etc.
As the glycidol ether of the polyalcohol that has imported polyalkylene glycol chain, can enumerate the polyoxyethylene T 55, polyoxyethylene pentaerythrite polyglycidyl ether, polyoxyethylene D-sorbite polyglycidyl ether, polyoxyethylene polyoxy propylidene T 55, polyoxyethylene polyoxy propylidene pentaerythrite polyglycidyl ether, polyoxyethylene polyoxy propylidene D-sorbite polyglycidyl ether, polyoxy propylidene T 55, polyoxy propylidene pentaerythrite polyglycidyl ether, polyoxy propylidene D-sorbite polyglycidyl ether etc.
As monohydric phenol, can be any one of aromatic alcohols, Ppolynuclear aromatic alcohol.As monohydric phenol, such as enumerating phenol, benzylalcohol, tert-butylphenol, hexylphenol, octyl phenol, nonyl phenol, cresols, naphthols etc.
Import the monohydric phenol of polyalkylene glycol chain, referred to the alkylene oxide addition product of aforesaid monohydric phenol, had (gathering) oxyalkylene.About (gathering) oxyalkylene, identical with the group of in the monohydric alcohol that has imported polyalkylene glycol chain, putting down in writing.
As the glycidol ether of monohydric phenol, can enumerate phenyl glycidyl ether, benzyl glycidyl ether, tert-butylphenyl glycidyl ether, hexyl phenyl glycidyl ether, octyl phenyl glycidol ether, nonyl phenyl glycidyl ether, naphthyl glycidyl ether etc.
As the glycidol ether of the monohydric phenol that has imported polyalkylene glycol chain, can enumerate the polyoxyethylene phenyl glycidyl ether, the polyoxyethylene benzyl glycidyl ether, polyoxyethylene tert-butylphenyl glycidyl ether, polyoxyethylene hexyl phenyl glycidyl ether, polyoxyethylene octyl phenyl glycidol ether, polyoxyethylene nonyl phenyl glycidyl ether, the polyoxyethylene naphthyl glycidyl ether, polyoxyethylene polyoxy propylidene phenyl glycidyl ether, polyoxyethylene polyoxy propylidene benzyl glycidyl ether, polyoxyethylene polyoxy propylidene tert-butylphenyl glycidyl ether, polyoxyethylene polyoxy propylidene hexyl phenyl glycidyl ether, polyoxyethylene polyoxy propylidene octyl phenyl glycidol ether, polyoxyethylene polyoxy propylidene nonyl phenyl glycidyl ether, polyoxyethylene polyoxy propylidene naphthyl glycidyl ether, polyoxy propylidene phenyl glycidyl ether, polyoxy propylidene benzyl glycidyl ether, polyoxy propylidene tert-butylphenyl glycidyl ether, polyoxy propylidene hexyl phenyl glycidyl ether, polyoxy propylidene octyl phenyl glycidol ether, polyoxy propylidene nonyl phenyl glycidyl ether, polyoxy propylidene naphthyl glycidyl ether etc.
As polyhydric phenols, can be any one of aromatic alcohols, Ppolynuclear aromatic alcohol.Preferred 2～5 yuan of polyhydric phenols, further preferred 2～3 yuan.
As polyhydric phenols, for example can enumerate quinhydrones (Isosorbide-5-Nitrae-Benzenediol), resorcinol (1,3-Benzenediol), catechol (1,2-Benzenediol), bisphenol-A, pyrogallol (1,2,3-benzene triol) etc.
Import the polyhydric phenols of polyalkylene glycol chain, referred to the alkylene oxide addition product of aforesaid polyhydric phenols, had at least 1 (gathering) oxyalkylene.About the quantity of (gathering) oxyalkylene, just be not particularly limited as long as have at least 1, can comprise the number identical with first number of polyalcohol.About (gathering) oxyalkylene, identical with the group of in the monohydric alcohol that has imported polyalkylene glycol chain, putting down in writing.
As the glycidol ether of polyhydric phenols, such as enumerating Benzenediol diglycidyl ether, bisphenol A diglycidyl ether, benzene triol triglycidyl ether etc.
As the glycidol ether of the polyhydric phenols that has imported polyalkylene glycol chain, for example can enumerate polyoxyethylene Benzenediol diglycidyl ether, the polyoxyethylene bisphenol A diglycidyl ether, polyoxyethylene benzene triol triglycidyl ether, polyoxyethylene polyoxy propylidene Benzenediol diglycidyl ether, polyoxyethylene polyoxy propylidene bisphenol A diglycidyl ether, polyoxyethylene polyoxy propylidene benzene triol triglycidyl ether, polyoxy propylidene Benzenediol diglycidyl ether, polyoxy propylidene bisphenol A diglycidyl ether, polyoxy propylidene benzene triol triglycidyl ether etc.
The glycidol ether based compound has the monoglycidyl ether of 1 glycidyl ether in the preferred molecule.Have in molecule in the situation of diglycidyl ether, polyglycidyl ether of 2 above glycidyl ethers, crosslinking points has more than 2 in 1 molecule.For this reason, after the fiber treatment residual epoxy radicals and the residual silanol groups that is derived from above-mentioned organosiloxane through day ground crosslinked, producing high-molecular occurs, have the situation that water imbibition descends.As monoglycidyl ether, can enumerate the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether of aforesaid monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, polyhydric phenols, the glycidol ether etc. that has imported the polyhydric phenols of polyalkylene glycol chain only has glycidol ether of 1 glycidyl etc.
About the glycidol ether based compound, from further antibiotic property and the absorptive viewpoint of improving behind the cyclic washing, have the glycidol ether of polyalkylene glycol chain in the preferred molecule, and then the glycidol ether of preferred above-mentioned general formula (2) expression.
In the formula (2), R
6Alkyl, phenyl or the glycidyl of carbon number 1～18.The carbon number of alkyl preferred 8～18.R
6Alkyl can be the straight chain shape, can also be chain.In the middle of these, glycidol ether based compound, preferred R
6Be the monoglycidyl ether of the alkyl of carbon number 1～18, more preferably R
6Monoglycidyl ether for the alkyl of carbon number 1～12.In the formula (2), A is the alkylidene of carbon number 2～5, in order to give more outstanding water imbibition, the carbon number of A preferred 2～4, further preferred 2～3.The quantity n of the repetitive of polyalkylene glycol chain is 1～22, preferred 8～22.Consist of (AO)
nOxyalkylene, preferably must contain the aerobic ethylidene.Oxygen ethylidene shared ratio in whole oxyalkylenes is preferably more than 30 % by mole, and is more preferably 50 % by mole, further preferred more than 80 % by mole.
Manufacture method as the glycidol ether based compound is not particularly limited, and can adopt known gimmick.In addition, the glycidol ether based compound can use commercially available product.
[reactant of organosiloxane and glycidol ether based compound]
Reactant with the organosiloxane with quaternary ammonium salt base and glycidol ether based compound is processed the fibrous material that contains cellulose fibre, can in endowing antibacterial, give water imbibition thus, even and if then can give behind the cyclic washing also outstanding antibiotic property and water imbibition.And then, even if can give through diurnal variation also outstanding water imbibition.Here, reactant refers to that the dehydration, the dealcoholization that occur by between the organosiloxane with quaternary ammonium salt base and glycidol ether based compound, glycidol ether based compound are chemically bound in organosiloxane and the product that obtains.About organosiloxane and the glycidol ether based compound with quaternary ammonium salt base, with aforementioned the same.
Manufacture method about the reactant of organosiloxane with quaternary ammonium salt base and glycidol ether based compound is not particularly limited, and can adopt known gimmick.For example, make organosiloxane with quaternary ammonium salt base and glycidol ether based compound under stream of nitrogen gas, 130 ℃～150 ℃ reactions 3～5 hours, the water, the alcohol distillation that generate are removed, can make reactant thus.
The organosiloxane with quaternary ammonium salt base when making reactant and the part by weight (organosiloxane/glycidol ether based compound) of glycidol ether based compound preferred 0.3～3.0, further preferred 0.5～2.5.
[fibrous material that contains cellulose fibre]
Cellulose fibre refers to contain the material of cellulose fibre, can be simple cellulose fibre, can also with other fiber blends, mixed fine, interweave, hand over volume.For example, as cellulose fibre, can enumerate the native cellulose fibres such as cotton, fiber crops, jute, ramie, artificial silk, copper ammonia fibre, Pori's nosik, refined fiber cellulose fiber (trade mark: regenerated celulose fibre, the melt-spinning fiber cellulose fiber etc. such as TENCEL).As other fibers, can enumerate polyester, cation dyeable polyester, nylon, polyurethane, polyvinyl alcohol, acrylic, polyethylene, polypropylene, silk, wool etc.
The fibrous material that contains cellulose fibre refers to the object of endowing antibacterial, water imbibition, washing resistance, such as the fibrous material that uses in substrate (foundation), underwear, motion dress material, bed clothes class, the protective layer class etc.As the form of fibrous material, such as can enumerate fabric, compile thing, the forms such as cloth and silk, thread, nonwoven fabric.
[manufacture method of antibiotic fiber and antibiotic fiber]
The manufacture method of antibiotic fiber of the present invention comprises following operation (A): with having the organosiloxane of quaternary ammonium salt base and the glycidol ether based compound is processed the fibrous material that contains cellulose fibre or the operation the fibrous material that contains cellulose fibre processed with the reactant of the organosiloxane with quaternary ammonium group and glycidol ether based compound.As operation (A), have and utilize this organosiloxane and these 2 kinds of compositions of this glycidol ether based compound to the fibrous material that contains cellulose fibre carries out simultaneously treated operation (A1), utilizes the operation (A2) that these 2 kinds of compositions process respectively and utilizes this organosiloxane and the reactant of this glycidol ether based compound is processed operation (A3).
As operation (A1), can enumerate the operation of utilizing the treatment fluid contain organosiloxane, glycidol ether based compound and water to process.Method as with treatment fluid fibrous material being processed just is not particularly limited, and can adopt known method.For example, can utilize any method of infusion process, method of impregnation, pad dry method, gunite that fibrous material is processed.More specifically, for example can enumerate following methods.
At first, above-mentioned organosiloxane, glycidol ether based compound, water are mixed at random, stir, preparation treatment fluid (preparation section).Then, abundant impregnation of fibers material utilizes above-mentioned organosiloxane and glycidol ether based compound that fibrous material is processed (operation (A1)) in this treatment fluid.Then, make fibrous material dehydration, dry (drying process), form the firmly tunicle with durability at fiber surface thus, can give antibiotic property, the water imbibition with washing resistance to fibrous material.Baking temperature when making fibrous material dries can be normal temperature, but from forming the viewpoint of the tunicle with better durability, and is preferably in addition dry with the temperature of regulation.About this point, the back is narrated in heat treated operation (B).
As operation (A2), can enumerate the operation of the fibrous material that contains cellulose fibre being processed with the treatment fluid that contains a kind of composition in above-mentioned organosiloxane and the glycidol ether based compound and water and the operation of processing with the treatment fluid that contains another kind of composition and water.More specifically, for example, each treatment fluid prepares by organosiloxane, glycidol ether based compound a kind of composition and water separately being mixed at random, stirring.After fibrous material being processed with a kind for the treatment of fluid by the method identical with operation (A1), fibrous material is processed with another kind for the treatment of fluid by the method identical with operation (A1).From giving washing resistance outstanding absorptive viewpoint, preferably after having carried out processing with the treatment fluid that contains organosiloxane, process with the treatment fluid that contains the glycidol ether based compound.Operation subsequently is identical with the operation of putting down in writing in the explanation of relevant operation (A1).
As operation (A3), can enumerate the operation that the treatment fluid that utilizes the reactant contain above-mentioned organosiloxane and above-mentioned glycidol ether based compound and water is processed.As with treatment fluid fibrous material being carried out processing method, identical with the operation of in the explanation of relevant operation (A1), putting down in writing.More specifically, for example can enumerate following methods.
At first, to organosiloxane and glycidol ether based compound under stream of nitrogen gas, 130 ℃～150 ℃ lower processing 3～5 hours, obtain thus the reactant (reaction process) of organosiloxane and glycidol ether based compound.Then, this reactant and water are mixed at random, stir, preparation treatment fluid (preparation section).Then, abundant impregnation of fibers material is processed (operation (A3)) with this reactant to fibrous material in this treatment fluid.Operation subsequently is identical with the operation of putting down in writing in the explanation of relevant operation (A1).
In addition, the antibiotic fiber that utilizes manufacture method of the present invention to obtain is that reactant with the organosiloxane of quaternary ammonium salt base and glycidol ether based compound is bonded to the fibrous material that contains cellulose fibre and forms.By set on fibrous material this reactant is arranged, have outstanding antibiotic property and water imbibition, even and if have behind cyclic washing also outstanding antibiotic property and a water imbibition.In addition, even if also have outstanding water imbibition through diurnal variation.About these effects following supposition is arranged.
The silanol group of deriving from the alkoxysilyl of organosiloxane, the reactive hydrogen that produces with the open loop of the hydroxyl of cellulose fibre and the epoxy radicals by the glycidol ether based compound has reactivity.In addition, the reactive hydrogen that the open loop of the epoxy radicals by the glycidol ether based compound produces has reactivity with the hydroxyl of cellulose fibre and the silanol group of deriving from the alkoxysilyl of organosiloxane.
For this reason, in situation about processing with operation (A1), operation (A2), be not only that organosiloxane and glycidol ether based compound are bonded to fibrous material, and organosiloxane and glycidol ether based compound react on fibrous material, and its reactant carries out set.Its result infers that the glycidol ether based compound raises by the maintained ratio of chemical bond at the fibrous material that contains cellulose fibre, and washing resistance also raises.
In addition, above-mentioned organosiloxane has high hydrophobicity, when being bonded to fibrous material separately, hydrophobicity after the washing raises, but by the set of this reactant, the ratio that simple organosiloxane is bonded to fibrous material reduces, and the hydrophobicity after the washing embodies and is suppressed.For this reason, even if infer to have behind cyclic washing also outstanding antibiotic property and water imbibition, even if also have outstanding water imbibition through diurnal variation.
In addition, as operation (A3), be prepared with in advance the reactant of organic siloxane and glycidol ether based compound, also can process fibrous material with its reactant.At this moment, compare with operation (A1), operation (A2), the ratio that simple organosiloxane is bonded to fibrous material reduces washing resistance, more outstanding through the water imbibition of diurnal variation.
The manufacture method of antibiotic fiber of the present invention, in operation (A1), operation (A2), operation (A3), from forming durable water imbibition viewpoint outstanding tunicle, operating cost, preferable process (A1), operation (A3).
The manufacture method of antibiotic fiber of the present invention, preferred and then contain the operation (B) that the fibrous material of processing through above-mentioned operation (A) is heat-treated.Particularly in the situation of operation (A1), operation (A2), preferably contain heat treated operation (B).By heat-treating, promote the open loop of the epoxy radicals that the glycidol ether based compound has, reaction by the silanol group that promotes to derive with the hydroxyl of cellulose fibre and from above-mentioned organosiloxane forms relevant with the firmly tunicle with durability thus.Heat treatment can be carried out dried fibrous material, but preferably the fibrous material that is attached with treatment fluid is being dewatered, and carries out when dry.About heat treated temperature, preferred 100～220 ℃, further preferred 110 ℃～200 ℃.When heat treatment temperature is lower than 100 ℃, have the situation that is difficult to form the tunicle with durability.On the other hand, when heat treatment temperature surpasses 220 ℃, have the situation of the physical property reduction of fibrous material self.Preferred 1～30 minute of heat treated time, further preferred 1～10 minute.When heat treatment time is less than 1 minute, have the situation that is difficult to form the tunicle with durability.On the other hand, when the heat treatment time more than 30 minutes, have with fibrous material and be bonded to the relevant situation of the variation of form and aspect of dyestuff of this fibrous material.
Treatment fluid must contain water.About preparing the method for the treatment of fluid, be not particularly limited, can adopt known gimmick.For example, can prepare by above-mentioned organosiloxane, above-mentioned glycidol ether based compound (or these reactant), water being mixed at random, stirring.In addition, also can water antibiotic processing agent described later is diluted and prepare.About treatment fluid, outside the solvent except organosiloxane, glycidol ether based compound (or these reactant), other compositions that contain as required and water, also consisted of by water.As the water that uses among the present invention, can be any one of pure water, distilled water, Purified Water, soft water, ion exchange water, running water etc.
In the treatment fluid of operation (A1), operation (A2), above-mentioned organosiloxane is preferably 0.1～3.0 % by weight with respect to the part by weight of whole treatment fluids, more preferably 0.3～1.0 % by weight.Be lower than at part by weight in the situation of 0.1 % by weight, have the situation that can not get antibiotic property.On the other hand, surpass in the situation of 3.0 % by weight at part by weight, have hydrophobicity and strengthen, and the situation of cost rising.
In the treatment fluid of operation (A1), operation (A2), above-mentioned glycidol ether based compound is with respect to preferred 0.1～3.0 % by weight of the part by weight of whole treatment fluids, more preferably 0.3～2.0 % by weight.Be lower than at part by weight in the situation of 0.1 % by weight, have the durable absorptive situation after can not get washing.On the other hand, surpass in the situation of 3.0 % by weight at part by weight, from the feel deterioration of cost rising, fiber self, other skin safe health aspect, can give bad stimulation.
In the treatment fluid of operation (A3), the reactant of above-mentioned organosiloxane and glycidol ether based compound is preferably 0.3～3.0 % by weight with respect to the part by weight of whole treatment fluids, more preferably 0.5～2.5 % by weight.Be lower than at part by weight in the situation of 0.3 % by weight, can become the reason of the feel deterioration that makes fiber self.Surpassing in the situation of 3.0 % by weight, have and to give washing resistance outstanding absorptive situation.
Bath raio (weight of bath raio=fibrous material: the weight for the treatment of fluid) preferred 1: 5～1: 50, more preferably 1: 10～1: 30.Less than (treatment fluid with respect to the weight ratio of fibrous material less than 5 o'clock), hinder this composition to evenly the adhering to of fiber in bath raio at 1: 5 o'clock, might produce attachment plaque.On the other hand,, add man-hour this treatment fluid and bubble easily greater than 1: 50 o'clock (treatment fluid with respect to the weight ratio of fibrous material greater than 50 o'clock) in bath raio, have problems such as causing the scum silica frost generation.
In addition, shrinkage factor (treatment fluid is with respect to the infiltration rate of fibrous material) preferred 70～110 % by weight, more preferably 80～100 % by weight.When being lower than 70 % by weight, the adhesive rate of this composition reduces, and has the situation that can't give target capabilities.On the other hand, greater than 110% the time, the adhesive rate of this composition raises, have thus the feel that produces fiber self reduction, can not get the problem of target capabilities etc.
In above-mentioned treatment fluid, except the described reactant of above-mentioned organosiloxane, above-mentioned glycidol ether based compound, organosiloxane and glycidol ether based compound, can contain other compositions in the scope that does not hinder effect of the present invention.As other compositions, can enumerate the softener that uses in the fine finishining, antistatic agent, water absorbing agent, fixer, penetrant etc.
Operation (A1) or operation (A2), preferably utilizing part by weight (organosiloxane/glycidol ether based compound) is the operation that 0.3～3.0 above-mentioned organosiloxane and above-mentioned glycidol ether based compound are processed above-mentioned fibrous material.Part by weight more preferably 0.5～2.5.Be lower than at part by weight in 0.3 the situation, have the situation that the feel that makes fiber self worsens.Surpass in 3.0 the situation at part by weight, have and to give outstanding absorptive situation.In order to make organosiloxane and glycidol ether based compound be attached to fibrous material with above-mentioned part by weight, make the treatment fluid that contains two compositions with above-mentioned part by weight be attached to fibrous material and get final product.
In operation (A1) or operation (A2), above-mentioned organosiloxane is with respect to preferred 0.1～3.0 % by weight of the adhesion amount of fibrous material, more preferably 0.3～1.0 % by weight.In the situation that is lower than 0.1 % by weight, the situation of the antibiotic property of can not get is arranged.On the other hand, surpassing in the situation of 3.0 % by weight, having the situation that hydrophobicity strengthens and cost raises.In addition, above-mentioned glycidol ether based compound is with respect to preferred 0.1～3.0 % by weight of the adhesion amount of fibrous material, more preferably 0.3～2.0 % by weight.In the situation that is lower than 0.1 % by weight, have the durable absorptive situation after can not get washing.On the other hand, surpassing in the situation of 3.0 % by weight, from the feel deterioration of cost rising, fiber self, other skin safe health aspect, can give bad stimulation.
In operation (A3), the above-mentioned reactant of organosiloxane and glycidol ether based compound is with respect to the adhesion amount of fibrous material, preferred 0.1～3.0 % by weight, more preferably 0.3～1.0 % by weight.In the situation that is lower than 0.1 % by weight, the durable absorptive situation after having and can not get antibiotic property, washing.On the other hand, surpassing in the situation of 3.0 % by weight, from the feel deterioration of cost rising, fiber self, other skin safe health aspect, can give bad stimulation situation.
With the antibiotic fiber that manufacture method of the present invention obtains, have outstanding antibiotic property and water imbibition, and then behind cyclic washing, also can keep these performances.The feel that in addition, can not cause fiber self reduces.
[the antibiotic processing agent of cellulose fibre]
The antibiotic processing agent of cellulose fibre of the present invention, the manufacture method that is used for antibiotic fiber of the present invention, be contain organosiloxane with quaternary ammonium salt base and glycidol ether based compound cellulose fibre with antibiotic processing agent or contain the antibiotic processing agent of cellulose fibre of the reactant of organosiloxane with quaternary ammonium salt base and glycidol ether based compound.About the reactant of organosiloxane, glycidol ether based compound, the organosiloxane with quaternary ammonium salt base and glycidol ether based compound with quaternary ammonium salt base and their preferred embodiment, scope, as hereinbefore.
Contain with antibiotic processing agent at cellulose fibre of the present invention in the situation of organosiloxane with quaternary ammonium salt base and glycidol ether based compound, this organosiloxane shared preferred 10～80 % by weight of part by weight in the nonvolatile component of antibiotic processing agent, more preferably 20～50 % by weight.Be lower than at this part by weight in 10% the situation, have the situation that does not embody outstanding antibiotic property.On the other hand, surpass in the situation of 80 % by weight at this part by weight, have the outstanding absorptive situation that do not embody.In addition, this glycidol ether based compound shared part by weight in the nonvolatile component of antibiotic processing agent, preferred 10～80 % by weight, more preferably 20～50 % by weight.Be lower than at this part by weight in the situation of 10 % by weight, have the outstanding absorptive situation that do not embody.On the other hand, surpass in the situation of 80 % by weight at this part by weight, have the situation that does not embody outstanding antibiotic property.Need to prove that the said nonvolatile component of the present invention refers to antibiotic processing agent be heat-treated and remaining composition when making the volatilization such as solvent at 105 ℃.
In addition, the part by weight (organosiloxane/glycidol ether based compound) of this organosiloxane and this glycidol ether based compound is preferred 0.3～3.0, and more preferably 0.5～2.5.Be lower than at part by weight in 0.3 the situation, have the situation that the feel that makes fiber self worsens.Surpass in 3.0 the situation at part by weight, have and to give outstanding absorptive situation.
Contain with antibiotic processing agent at cellulose fibre of the present invention in the situation of reactant of organosiloxane and glycidol ether based compound, this reactant shared part by weight in the nonvolatile component of antibiotic processing agent, preferred 10～80 % by weight, more preferably 20～70 % by weight.Be lower than at this part by weight in the situation of 10 % by weight, have outstanding antibiotic property, the absorptive situation of not embodying.
The antibiotic processing agent of cellulose fibre of the present invention except aforesaid composition, can also contain other compositions in the scope that does not hinder effect of the present invention.As other composition, can enumerate the softener that in fine finishining, uses, antistatic agent, water absorbing agent, fixer, penetrant etc.
Antibiotic processing agent of the present invention, the hydrolysis for the alkoxysilyl that suppresses organosiloxane contains pure series solvent as solvent.Therefore, not moisture in fact for well.When having water to exist, might promote the deriving from the alkoxysilyl of organosiloxane to silanol group based on hydrolysis, polycondensation reaction occurs between silanol, make the processing agent solid.
As pure series solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols etc.In the middle of these, particular methanol, ethanol.
Nonvolatile component shared part by weight in antibiotic processing agent, preferred 10～90 % by weight, more preferably 20～85 % by weight, further preferred 30～80 % by weight.
About preparing the method for antibiotic processing agent, be not particularly limited, can adopt known gimmick.For example, can be by above-mentioned organosiloxane, glycidol ether based compound (or these reactant), pure series solvent be mixed at random, stir and prepared.
[embodiment]
Below, embodiments of the invention are shown, the present invention will be described in more detail, but the present invention is not limited by these embodiment.Need to prove that " part " in the example and " % " represent respectively " weight portion " and " % by weight ".
(embodiment 1)
As shown in table 1, will be as the 3-(trimethoxysilyl) of the organosiloxane with quaternary ammonium salt base-propyl group octadecyl alkyl dimethyl ammonium chloride 1.0 % by weight, laruyl alcohol EO (15 moles) glycidol ether 0.5 % by weight, water 98.5 % by weight mix and blends, making bath raio is to have prepared treatment fluid at 1: 20.Dipping T/C cloth and silk (polyester/cotton=50 % by weight/50 % by weight) is processed with shrinkage factor 90 % by weight in this treatment fluid, then, carries out 3 minutes heat treatment under 130 ℃.To before the washing of the treatment cloth (test cloth) that obtains and the antibiotic property after the washing 10 times, water imbibition and absorptively estimate through diurnal variation.The results are shown in table 3.Need to prove, about washing methods and antibiotic property, water imbibition, absorptive test method through diurnal variation, carry out with following method.
[washing methods]
According to the JIS-L-0217103 method, test cloth is washed.Washing agent uses ATTACK (registration mark) (flower king (strain) system), and the detergent concentration of cleaning solution is 1.0g/L.By above-mentioned condition, carry out cyclic washing 10 times.
[antibiotic property]
By JIS-L-1902 quantitative test (bacterium liquid absorption process) the bacteriostatic activity value is measured, the anti-microbial property of test cloth is estimated.As using bacterium, used staphylococcus aureus Staphylococcus aureus ATCC6538P.
Metewand: the bacteriostatic activity value is more than 2.0 in the antibiotic processing.In addition, the higher antibiotic property of bacteriostatic activity value runs off look.Need to prove that in table 3, " 5.9＜" expression bacteriostatic activity value is greater than 5.9.
[water imbibition]
According to the JIS-L-1907 dripping method, with 1 drip (about 12mg) drip to test cloth, to until the time of the areflexia due to the water droplet (second) is measured, water imbibition is estimated.Numerical value is less to represent that then water imbibition is higher.Need to prove that in table 4, "＜1 " expression is lower than 1 second, " 180＜" represented greater than 180 seconds.
[absorptive through diurnal variation (overdrying)]
With 105 ℃ * 3 hours condition drying test cloth, the test cloth that obtains is washed front water imbibition with washing after 10 times.
(embodiment 2～15, comparative example 1～14)
In embodiment 2～15, comparative example 2～14, except the organosiloxane with quaternary ammonium salt base of embodiment 1 and glycidol ether based compound being altered to the composition shown in table 1 and the table 2 and ratio, estimate similarly to Example 1.In addition, as a comparative example 1, estimated similarly to Example 1 and implemented the T/C cloth and silk that processing is processed.The results are shown in table 3,4.
(embodiment 16)
In 3 mouthfuls of flasks, put into as have the 3-(trimethoxysilyl) of the organosiloxane of quaternary ammonium salt base-propyl group octadecyl alkyl dimethyl ammonium chloride 30.0 weight portions, as laruyl alcohol EO (15 moles) glycidol ether 15.0 weight portions of glycidol ether based compound, as acetic anhydride 0.01 weight portion of acid catalyst, under stream of nitrogen gas, under 130～150 ℃, make its reaction 3～5 hours, the water, the methyl alcohol distillation that generate are removed, obtained thus reactant.After this reactant is cooled to normal temperature, puts into methyl alcohol 55.0 weight portions and enter, prepared the methanol solution of reactant.
Then, will be with the convert water mix and blend in addition of methanol solution, 98.5 % by weight of this reactant of counting 1.5 % by weight of active ingredient, making bath raio is to have prepared treatment fluid at 1: 20.Dipping T/C cloth and silk (polyester/cotton=50 % by weight/50 % by weight) is processed with shrinkage factor 90 % by weight in this treatment fluid, then, and 130 ℃ of heat treatments of carrying out 3 minutes.Similarly to Example 1 the treatment cloth (test cloth) that obtains is estimated.The results are shown in table 3.
(embodiment 17)
As the glycidol ether based compound, be altered to butanols EO (4.5 moles) glycidol ether, in addition, estimate similarly to Example 16.The results are shown in table 3.
(embodiment 18)
As the glycidol ether based compound, be altered to EO (9 moles) diglycidyl ether, in addition, estimate similarly to Example 16.The results are shown in table 3.
(embodiment 19)
As the glycidol ether based compound, be altered to EO (23 moles) diglycidyl ether, in addition, estimate similarly to Example 16.The results are shown in table 3.
(embodiment 20)
Will be as the 3-(trimethoxysilyl) of the organosiloxane with quaternary ammonium salt base-propyl group octadecyl alkyl dimethyl ammonium chloride 30.0 weight portions, as laruyl alcohol EO (15 moles) glycidol ether 15.0 weight portions of glycidol ether based compound, as methyl alcohol 55.0 weight portions of solvent mix and blend in addition, it is standby with antibiotic processing agent to have prepared thus cellulose fibre.
Then, will be with the convert water mix and blend in addition of this antibiotic processing agent of counting 1.5 % by weight, 98.5 % by weight of active ingredient, making bath raio is to have prepared treatment fluid at 1: 20.Dipping T/C cloth and silk (polyester/cotton=50%/50%) is processed with shrinkage factor 90 % by weight in this treatment fluid, then, and 130 ℃ of heat treatments of carrying out 3 minutes.Similarly to Example 1 the treatment cloth (test cloth) that obtains is estimated.The results are shown in table 3.
[table 3]
[table 4]
Embodiment 1～20 has outstanding antibiotic property and water imbibition.In addition, compare as can be known with comparative example 1～14: wash after 10 times also outstanding antibiotic property and water imbibition even if having.And then, even if embodiment 1～5,16,17,20 also has outstanding water imbibition through diurnal variation (overdrying).
Utilization has the organosiloxane of quaternary ammonium salt base and the embodiment 1～15 that 2 kinds of compositions of glycidyl ether compound are processed fibrous material simultaneously, compares with situation about fibrous material being processed respectively with these 2 kinds of compositions, and water imbibition is outstanding after the washing.Have the organosiloxane of antibiotic property, have high hydrophobicity, when being bonded to fibrous material separately, the hydrophobicity after the washing raises.Embodiment 1～15, and the ratio that the reactant of organosiloxane and glycidol ether based compound generates on the fibrous material raises, and hydrophobic embodiment is suppressed after the washing, so infer that water imbibition is outstanding.
About embodiment 16～20, compare with embodiment 1～15, have outstanding antibiotic property and water imbibition.In addition, embodiment 16,17 is even if also have outstanding water imbibition through diurnal variation (overdrying).In embodiment 16～20, owing to the reactant of organosiloxane and glycidol ether based compound fibrous material is processed, so compare with embodiment 1～15, the ratio that simple organosiloxane is bonded to fibrous material reduces, and infers that water imbibition is outstanding after washing.
[utilizability on the industry]
The manufacture method of antibiotic fiber of the present invention can suitably used when containing the fibrous material endowing antibacterial of cellulose fibre.
Claims (14)
1. the manufacture method of an antibiotic fiber, it comprises following operation (A):
To containing the fibrous material of cellulose fibre, have the processing of the organosiloxane of quaternary ammonium salt base and glycidol ether based compound or carry out this organosiloxane and the operation of the processing of the reactant of this glycidol ether based compound.
2. the manufacture method of antibiotic fiber as claimed in claim 1, wherein,
Described organosiloxane is the organosiloxane of following general formula (1) expression,
[changing 1]
R
1The alkyl of carbon number 1～22, R
2, R
3And R
4Be the alkyl of carbon number 1～10 independently respectively, R
5The alkylidene of carbon number 1～10, X
-Cl
-, Br
-, I
-Or CH
3COO
-
3. such as the manufacture method of claim 1 or 2 described antibiotic fibers, wherein,
Described glycidol ether based compound is at least a kind of glycidol ether selecting the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether from monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyhydric phenols and the polyhydric phenols that has imported polyalkylene glycol chain.
4. such as the manufacture method of the described antibiotic fiber of any one in the claim 1～3, wherein, described glycidol ether based compound is the glycidol ether with polyalkylene glycol chain.
5. such as the manufacture method of the described antibiotic fiber of any one in the claim 1～4, wherein, described glycidol ether based compound is the glycidol ether of following general formula (2) expression,
[changing 2]
R
6Be alkyl, phenyl or the glycidyl of carbon number 1～18, A is the alkylidene of carbon number 2～5, and the quantity n of the repetitive of polyalkylene glycol chain is 1～22.
6. the manufacture method of antibiotic fiber as claimed in claim 5, wherein,
Described glycidol ether based compound is the R of described general formula (2)
6Monoglycidyl ether for the alkyl of carbon number 1～18.
7. such as the manufacture method of the described antibiotic fiber of any one in the claim 1～6, wherein,
Described operation (A), be the operation of the fibrous material that contains cellulose fibre being processed with described organosiloxane and described glycidol ether based compound, described organosiloxane and described glycidol ether based compound part by weight are that organosiloxane/glycidol ether based compound is 0.3～3.0.
8. such as the manufacture method of the described antibiotic fiber of any one in the claim 1～7, wherein,
Described operation (A) is with containing the treatment fluid of described organosiloxane, described glycidol ether based compound and water, the operation that the fibrous material that contains cellulose fibre is processed.
9. such as the manufacture method of the described antibiotic fiber of any one in the claim 1～8, wherein,
Also contain the operation (B) that the fibrous material of processing through described operation (A) is heat-treated.
10. antibiotic fiber, it is the antibiotic fiber that obtains with the described manufacture method of any one in the claim 1～9,
That the reactant of described organosiloxane and described glycidol ether based compound is bonded to the fibrous material that contains cellulose fibre and forms.
11. the antibiotic processing agent of cellulose fibre, wherein,
Contain organosiloxane and glycidol ether based compound with quaternary ammonium salt base, or contain the reactant of this organosiloxane and this glycidol ether based compound.
12. the antibiotic processing agent of cellulose fibre as claimed in claim 11, wherein,
Described organosiloxane is the organosiloxane of following general formula (1) expression,
[changing 3]
R
1The alkyl of carbon number 1～22, R
2, R
3And R
4Be the alkyl of carbon number 1～10 independently respectively, R
5The alkylidene of carbon number 1～10, X
-Cl
-, Br
-, I
-Or CH
3COO
-
13. such as claim 11 or the antibiotic processing agent of 12 described cellulose fibres, wherein,
Described glycidol ether based compound is at least a kind of glycidol ether selecting the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether of the glycidol ether from monohydric alcohol, the glycidol ether that has imported the monohydric alcohol of polyalkylene glycol chain, polyalcohol, the glycidol ether that has imported the polyalcohol of polyalkylene glycol chain, monohydric phenol, the glycidol ether that has imported the monohydric phenol of polyalkylene glycol chain, polyhydric phenols and the polyhydric phenols that has imported polyalkylene glycol chain.
14. such as the antibiotic processing agent of the described cellulose fibre of any one in the claim 11～13, wherein,
Described glycidol ether based compound is the glycidol ether of following general formula (2) expression,
[changing 4]
R
6Be alkyl, phenyl or the glycidyl of carbon number 1～18, A is the alkylidene of carbon number 2～5, and the quantity n of the repetitive of polyalkylene glycol chain is 1～22.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010170631 | 2010-07-29 | ||
| JP2010-170631 | 2010-07-29 | ||
| PCT/JP2011/066518 WO2012014762A1 (en) | 2010-07-29 | 2011-07-21 | Method for producing antibacterial fibers, antibacterial fibers and antibacterial processing agent for fibers |
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| JP (1) | JP5140208B2 (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103696145A (en) * | 2013-12-10 | 2014-04-02 | 吴江市品信纺织科技有限公司 | Sweat-absorbent non-woven fabric |
| CN103829676A (en) * | 2014-04-01 | 2014-06-04 | 上海婉静纺织科技有限公司 | Antimicrobic sleeping bag and making method thereof |
| CN105821654A (en) * | 2016-05-05 | 2016-08-03 | 东华大学 | Durable cotton fabric antifungal finishing method based on click chemistry |
| CN109749129A (en) * | 2019-01-15 | 2019-05-14 | 株洲时代新材料科技股份有限公司 | A kind of multi-functional silane coupling agent and its preparation method and application |
| CN114144554A (en) * | 2019-07-12 | 2022-03-04 | 松本油脂制药株式会社 | Antistatic agent for fiber and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103566371B (en) * | 2012-08-01 | 2015-09-09 | 南京神奇科技开发有限公司 | Antimicrobial physical method |
| JP5646572B2 (en) * | 2012-10-16 | 2014-12-24 | 日本蚕毛染色株式会社 | Modified fiber and method for producing the same |
| CN103436167B (en) * | 2013-08-22 | 2015-12-02 | 齐鲁工业大学 | A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method |
| CN103436169B (en) * | 2013-08-22 | 2015-10-28 | 齐鲁工业大学 | A kind of germ resistance gelatin hide finishes and preparation method containing polysiloxane and quaternary ammonium salt |
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| JPH10110383A (en) * | 1996-09-30 | 1998-04-28 | Fuji Spinning Co Ltd | Cellulosic fiber product having oil and fat absorbability and antibacterial property, and its production |
| CN101331263A (en) * | 2006-09-21 | 2008-12-24 | 爱乐康株式会社 | Antimicrobial fiber and its production method, and antimicrobial fiber product comprising the antimicrobial fiber, its production method and regeneration method |
| CN101418517A (en) * | 2008-11-10 | 2009-04-29 | 江南大学 | Method for preparing quaternary ammonium salt sol for antibacterial textile |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103696145A (en) * | 2013-12-10 | 2014-04-02 | 吴江市品信纺织科技有限公司 | Sweat-absorbent non-woven fabric |
| CN103829676A (en) * | 2014-04-01 | 2014-06-04 | 上海婉静纺织科技有限公司 | Antimicrobic sleeping bag and making method thereof |
| CN105821654A (en) * | 2016-05-05 | 2016-08-03 | 东华大学 | Durable cotton fabric antifungal finishing method based on click chemistry |
| CN109749129A (en) * | 2019-01-15 | 2019-05-14 | 株洲时代新材料科技股份有限公司 | A kind of multi-functional silane coupling agent and its preparation method and application |
| CN109749129B (en) * | 2019-01-15 | 2021-07-06 | 株洲时代新材料科技股份有限公司 | Multifunctional silane coupling agent and preparation method and application thereof |
| CN114144554A (en) * | 2019-07-12 | 2022-03-04 | 松本油脂制药株式会社 | Antistatic agent for fiber and use thereof |
| CN114144554B (en) * | 2019-07-12 | 2023-08-25 | 松本油脂制药株式会社 | Antistatic processing agent for fiber and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5140208B2 (en) | 2013-02-06 |
| WO2012014762A1 (en) | 2012-02-02 |
| JPWO2012014762A1 (en) | 2013-09-12 |
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