CN102691129A - Antibacterial polyster fiber as well as production method and application thereof - Google Patents
Antibacterial polyster fiber as well as production method and application thereof Download PDFInfo
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- CN102691129A CN102691129A CN2012101925034A CN201210192503A CN102691129A CN 102691129 A CN102691129 A CN 102691129A CN 2012101925034 A CN2012101925034 A CN 2012101925034A CN 201210192503 A CN201210192503 A CN 201210192503A CN 102691129 A CN102691129 A CN 102691129A
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- antibacterial
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- polyester fiber
- antibiotic
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- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 56
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 229920001225 polyester resin Polymers 0.000 claims abstract description 19
- 238000002074 melt spinning Methods 0.000 claims abstract description 13
- 241000222122 Candida albicans Species 0.000 claims abstract description 6
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 6
- 229940095731 candida albicans Drugs 0.000 claims abstract description 6
- 230000003115 biocidal effect Effects 0.000 claims description 80
- 229920000728 polyester Polymers 0.000 claims description 66
- 230000002421 anti-septic effect Effects 0.000 claims description 60
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 38
- 239000004332 silver Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 30
- 230000008878 coupling Effects 0.000 claims description 28
- 238000010168 coupling process Methods 0.000 claims description 28
- 238000005859 coupling reaction Methods 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 22
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- 239000004599 antimicrobial Substances 0.000 claims description 18
- 239000004645 polyester resin Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- -1 aluminic acid ester Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 150000004756 silanes Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000008239 natural water Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 235000012222 talc Nutrition 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 241000305071 Enterobacterales Species 0.000 claims description 3
- 239000004593 Epoxy Chemical group 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Chemical group 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 12
- 238000005406 washing Methods 0.000 abstract description 11
- 206010040880 Skin irritation Diseases 0.000 abstract description 4
- 230000036556 skin irritation Effects 0.000 abstract description 4
- 231100000475 skin irritation Toxicity 0.000 abstract description 4
- 241000588724 Escherichia coli Species 0.000 abstract description 3
- 239000004594 Masterbatch (MB) Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 32
- 239000004744 fabric Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 230000000845 anti-microbial effect Effects 0.000 description 15
- 230000002401 inhibitory effect Effects 0.000 description 14
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 229920004934 Dacron® Polymers 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000005180 public health Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 238000010171 animal model Methods 0.000 description 2
- 229940064004 antiseptic throat preparations Drugs 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100223920 Caenorhabditis elegans rha-1 gene Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000003094 microcapsule Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- Artificial Filaments (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an antibacterial polyster fiber as well as a production method and application thereof. The method comprises the following steps: mixing antibacterial components and the like with polyster resin; carrying out melt extrusion to prepare antibacterial masterbatch; and carrying out melt spinning on the antibacterial masterbatch and the polyster resin so as to produce the antibacterial polyster fiber. The antibacterial polyster fiber provided by the invention is long in spinning period and good in spinning performance; the antibacterial rates of the antibacterial polyster fiber on E.coli, staphylococcus aureus and Candida albicans are larger than or equal to 99%; the antibacterial polyster fiber is good in washing resistance and has no skin irritation; the antibacterial rate of the antibacterial polyster fiber is still larger than 98% after washing 30 times. So that, the antibacterial polyster fiber produced by utilizing the existing equipment has extremely good application prospect.
Description
[technical field]
The invention belongs to textile technology field.More specifically, the present invention relates to a kind of polyster fibre product, also relate to the production method of said antibiotic polyester fiber, also relate to the purposes of said antibiotic polyester fiber with antibacterial functions.
[background technology]
Nature exists microorganisms such as various bacteriums, fungi, and these microorganisms are the ramp breeding under suitable environmental condition, and spreads disease through contact, influences the healthy of people.All kinds of textiless are good existence media of these microorganisms, and it is worn by the mankind and goes round, and also becomes the important propagation pollution sources of disease.
Fiber can adhere to a lot of microorganisms, if humiture is suitable, these microorganisms will breed rapidly, and human body is produced all harm.Therefore, in recent years, along with the progressively raising of human health consciousness, the antibiotic property of textiles also more and more receives people's attention.Fiber and textiles with antibacterial action also become the focus of more and more being paid close attention to by people.
Anti-bacterial fibre belongs to functional fibre; Functional fibre can have three kinds of production methods, and first method is a chemical modification method, promptly adopts chemical technology; Antibacterial functions group is grafted on the fiber base material reactive group; For the material that does not possess reactive group, introduce reactive group, make fiber possess the condition of chemical modification.This method is because relate to certain chemical reaction, so processing mode is complicated, and difficulty is very big.The method is seldom adopted by the people.
Second method is a physical modification method, i.e. different phase blend at fiberizing adds the antibacterial functions material, for example can when the spinning material polymerization, add; Also can, spinning blend add when extruding; Can also functional material be joined in the spinning solution for wet spinning.Physical modification is easy to operate because of it, and technical difficulty is low, and applicability is wide, has become the main method that functional fibre is made at present.
The third method is a finishing method, is the physical modification that after perhaps processing fabric behind the fiberizing, carries out, and adopts face coat method, RESIN FINISH method or microcapsule method to carry out usually.The finishing method function additive generally all is distributed in fiber and fabric face, so its durability is that people are devoted for years in one of difficult point that solves always.Fiber or fabric are made into the clothes series products, need constantly washing, reuse; Be easy to when washing, come off and be bonded to its surperficial functional material through the back arrangement; It is functional and reduce, and almost loses all functions when serious, no longer has anti-microbial property like anti-bacterial fibre.Its functional increase along with washing times and service time descends.The advantage of this method is that operation is very simple, and influence factor is less, and shortcoming is exactly that durability does not guarantee.Be difficult to satisfy fabric whole wear all have in the cycle functional.Therefore only by some low sides or disposable product favor.
For example; CN 01113772, denomination of invention " nano Polyester short fibre and manufacturing approach thereof " disclose the method for being made the antibacterial dacron short fiber by the powder of nano level specific antibiotic, sterilizing function and mixed with resin, extruding spinning; This invention is in polyester resin, to add 30% nanometer very to ice stone ore stone; And so high inorganic particle adds in the spinning material, and spinnability receives serious threat, is difficult to through normal spinning technique.CN 200510012956, denomination of invention " High-speed blended fiber-spinning process of nano composite antibacterial dacron poy " disclose employing 20-60 nano silver-carrying, zinc, silicon-base oxide compound antibacterial powder system and have made dacron master grain; Again master batch is added to the addition of 3-7% and carry out melt spinning in the spinning polyester resin, make antibiotic polyester fiber.This method is directly added the composite antibiosis powder to and is made dacron master grain in the polyester resin; And antimicrobial powder is difficult to the dispersion that reaches good in polyester resin; Disperse irregular powder body material in spinning, can increase spinning pressure, stop up spinnerets, influence the spinnability of fiber; And the inhomogeneous dispersion of antiseptic also can further have influence on the anti-microbial property of fiber.CN200510027688, denomination of invention " a kind of antibacterial humidity-guide polyester fiber and production method thereof and application " and CN 200910184329, denomination of invention " a kind of uvioresistant, antibiotic, " disclosed all is that basic zirconium phosphate carries aluminium powder and makes the terylene antibacterial matrices to lead wet type polyster fibre and production method thereof and application; This method shortcoming is that antimicrobial powder is difficult in polyster fibre, evenly disperse equally, is prone to cause spinnability variation and fiber anti-microbial property not to ensure.
The inventor is summing up on the basis of prior art, and through lot of experiments, the preferred antiseptic system of suitable spinning has been accomplished the present invention.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of polyster fibre with antibacterial functions.
Another object of the present invention provides the production method of said antibiotic polyester fiber.
Another object of the present invention provides the purposes of said antibiotic polyester fiber.
[technical scheme]
The present invention realizes through following technical proposals.
The present invention relates to a kind of production method of antibiotic polyester fiber.
The step of this production method is following:
The preparation of A, antibacterial matrices
In mixer; Use the 0.015-2 weight portion to prevent that the variable color finishing agent carries silver-colored zinc antiseptic to 1-20 weight portion zeolite and 1-20 weight portion basic zirconium phosphate carrying silver antimicrobials carries out the anti-variable color processing in surface; Then add 0.3-1 weight portion coupling dispersant and proceed to handle, obtain a kind of mixture that contains antiseptic; Then, described mixture is mixed with 75-90 weight portion polyester resin, re-use the double screw extruder group and under the condition of heating-up temperature 240-265 ℃, engine speed 200-230 rev/min and feeding 18-24Hz, melt extrude, obtain a kind of antibacterial matrices;
The preparation of B, antibiotic polyester fiber
Take by weighing the 2-10 weight portion in steps A) preparation antibacterial matrices and 90-98 weight portion polyester resin, the employing melt spinning method carry out spinning, obtain described antibiotic polyester fiber;
Described coupling dispersant is that one or more are selected from silane series, aluminic acid ester series, titanate esters is serial or the coupling dispersant of the compound coupling dispersant of bimetallic;
Described anti-variable color finishing agent is one or more anti-variable color finishing agents that are selected from BTA, methylbenzotrazole, methylbenzotrazole potassium, natural water talcum, synthetic hydrotalcite, magnesium aluminium oxide calcine or alumina silicate.
A preferred embodiment of the invention, said silane series coupling dispersant is a following formula: compound:
R
nSiX
(4-n)
In the formula:
n=1~3；
R is methyl, vinyl, amino, epoxy radicals, sulfydryl or acryloyl-oxy propyl group functional group;
X is alkoxyl, aryloxy group, acyl group or chloro group.
According to another kind of preferred implementation of the present invention, said aluminic acid ester series is selected from distearyl acyl-oxygen isopropyl aluminic acid ester, aluminic acid trimethyl, aluminic acid three isopropyl esters or aluminic acid three benzyl esters.
According to another kind of preferred implementation of the present invention, said titanate esters series is following formula: compound:
ROO
(4-n)Ti(OX-R'Y)
n
In the formula:
N=2 or 3;
RO is hydrolyzable short chain alkoxy-functional;
OX is carboxyl, alkoxyl, sulfonic group or phosphorus base group.
According to another kind of preferred implementation of the present invention, said bimetallic composite coupler is aluminium titanium composite coupler or aluminium zirconium composite coupler.
According to another kind of preferred implementation of the present invention, it is under the condition of mixer rotating speed 2800-3000rpm, to carry out the anti-variable color in surface to handle 10-30 minute that the anti-variable color in described surface is handled.
According to another kind of preferred implementation of the present invention, the processing of described coupling dispersant is under the condition of mixer rotating speed 500-600rpm, to handle 3-5 minute.
According to another kind of preferred implementation of the present invention, the mixed processing of said polyester resin is under the condition of mixer rotating speed 500-600rpm, to handle 3-5 minute.
The invention still further relates to the antibiotic polyester fiber that adopts said method to produce.
The invention still further relates to the purposes of said antibiotic polyester fiber in Chinese People's Anti-Japanese Military and Political College enterobacteria, staphylococcus aureus and Candida albicans.
Below the present invention will be described in more detail.
The present invention relates to a kind of production method of antibiotic polyester fiber.
The step of this production method is following:
The preparation of A, antibacterial matrices
In mixer; Use the 0.015-2 weight portion to prevent that the variable color finishing agent carries silver-colored zinc antiseptic to 1-20 weight portion zeolite and 1-20 weight portion basic zirconium phosphate carrying silver antimicrobials carries out the anti-variable color processing in surface; Then add 0.3-1 weight portion coupling dispersant and proceed to handle, obtain a kind of mixture that contains antiseptic; Then, described mixture is mixed with 75-90 weight portion polyester resin, re-use the double screw extruder group and under the condition of heating-up temperature 240-265 ℃, engine speed 200-230 rev/min and feeding 18-24Hz, melt extrude, obtain a kind of antibacterial matrices.
At first, in mixer, use the 0.015-2 weight portion to prevent that the variable color finishing agent carries silver-colored zinc antiseptic to 1-20 weight portion zeolite and 1-20 weight portion basic zirconium phosphate carrying silver antimicrobials carries out the anti-variable color processing in surface.The purpose of mixing is to let anti-variable color finishing agent coat its antiseptic, thereby prevents antiseptic generation oxidation stain effectively, influences its fiber antibacterial effect, changes its appearance of fabrics.
It is a kind of in the carry silver-colored zinc 4A zeolite of its antiseptic gross weight silver content 0.2 ~ 0.45% with zinc content 1 ~ 4% that described zeolite carries silver-colored zinc antiseptic.In this antiseptic, different silver-colored zinc content not only influence the anti-microbial property of its product, but also influence the discoloration of its product.Preferably, the silver content that described zeolite carries silver-colored zinc antiseptic is 0.28 ~ 0.35%, and zinc content is 1.8 ~ 3.2%.The zeolite that the present invention uses carry silver-colored zinc antiseptic can be the Beijing Chonygao Nano Science and Technology Co., Ltd with trade name An Dimei antiseptic AM product sold, perhaps can be the product of the commodity antiseptic FS-ZN by name that sells of company of section of Haier.
Described basic zirconium phosphate carrying silver antimicrobials is that a kind of bedded zirconium phosphate in its antiseptic gross weight silver content 1-3% carries silver products.In this antiseptic, different silver contents influences the anti-microbial property and the discoloration of product significantly.Preferably, the silver content of said basic zirconium phosphate carrying silver antimicrobials is 1.6 ~ 2.4%.It can be the sell goods of Beijing Chonygao Nano Science and Technology Co., Ltd with trade name An Dimei AMR antiseptic that the basic zirconium phosphate carrying silver antimicrobials zeolite that the present invention uses carries silver-colored zinc antiseptic, perhaps can profit river, Shanghai nanometer company also can be that the trade mark that Japanese SR company sells is the product of zeomic with commodity antiseptic RHA-1 product sold by name.
The part by weight that said zeolite carries silver-colored zinc antiseptic and said basic zirconium phosphate carrying silver antimicrobials is 4 ~ 15:6 ~ 14 preferably; More preferably be 8 ~ 10:10 ~ 12.
The inventor discovers; Compare with single antiseptic; When said zeolite carries silver-colored zinc antiseptic and is used in combination according to above-mentioned weight ratio with said basic zirconium phosphate carrying silver antimicrobials; Its product has very significantly antibacterial effect and anti-variable color synergistic effect, particularly referring to the content of effect assessment 1 in this specification technical scheme.
According to the present invention; Described anti-variable color handles to should be appreciated that it is a kind ofly can prevent that silver and airborne sulfide effect from generating silver sulfide; And in its surperficial chemical substance that produces black or yellow rete; Every have this character, and the material that can not influence anti-microbial property and fibre property again may be used to the present invention.
Preferably one or more are selected from the anti-variable color finishing agent of BTA, methylbenzotrazole, methylbenzotrazole potassium, natural water talcum, synthetic hydrotalcite, magnesium aluminium oxide calcine or alumina silicate to described anti-variable color finishing agent.More preferably be one or more anti-variable color finishing agents that are selected from BTA, methylbenzotrazole, natural water talcum or alumina silicate.
These anti-variable color finishing agents all are product solds in the market, and for example BTA is CAS95-14-7; Methylbenzotrazole is CAS 21412-99; Magnesium aluminium oxide calcine molecular formula is [Mg
0.7Al
0.6O
1.15]; Synthetic hydrotalcite is [Mg
45Al
0.5(OH)
13CO
3.3.5H
2O].
When the amount that said zeolite carries silver-colored zinc antiseptic and said basic zirconium phosphate carrying silver antimicrobials is the 1-20 weight portion,, has small xanthochromia and produce if the amount of anti-variable color finishing agent prevents then that less than 0.015 weight portion color changeable effect is undesirable; If the amount of anti-variable color finishing agent then can influence the processing and the anti-microbial property of product, especially the spinning process performance greater than 2 weight portions; Therefore, the amount of anti-variable color finishing agent is that 0.015 ~ 2 weight portion is suitable.
Described mixer is a product sold in the market, and for example creating that good mechanical Co., Ltd produces, model by the Zhangjagang City is the high-speed mixer of SHR-5A/10A.
It is under following condition, to carry out that described anti-variable color is handled: the rotating speed of institute's use mixer is generally 2800-3000rpm, and the anti-variable color processing time is 10-30min, this coating that is beneficial to antiseptic, the raising discoloration-resisting of being mixed with.Preferably, the rotating speed of said mixer is 2850 ~ 2950rpm, anti-variable color processing time 16 ~ 25min, and at this moment surperficial covered effect is best, and discoloration-resisting is significantly increased.
After anti-variable color is handled, then add 0.3-1 weight portion coupling dispersant and proceed to handle, obtain a kind of mixture that contains antiseptic.
According to the present invention, described coupling dispersant should be appreciated that it is that a kind of can to improve its antiseptic dispersed, reduces the bath surface viscosity, reduces the material of extruder moment of torsion, extrusion pressure.
Said coupling dispersant one or more be selected from silane series, aluminic acid ester series, titanate esters is serial or the coupling dispersant of the compound coupling dispersant of bimetallic.
Said silane series coupling dispersant is a following formula: compound:
R
nSiX
(4-n)
In the formula:
n=1~3；
R is methyl, vinyl, amino, epoxy radicals, sulfydryl or acryloyl-oxy propyl group functional group;
X is alkoxyl, aryloxy group, acyl group or chloro group.
The organo-functional group that the R group is non-hydrolysis, can combine with high molecular polymer, X is a hydrolyzable groups, preferably methoxyl group and ethyoxyl.
Said silane series coupling dispersant for example is gamma-aminopropyl-triethoxy-silane (CAS919-30-2 particularly; EINECS 213-048-4), VTES (CAS 78-08-0), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (CAS73069-29-2), they are product sold on the market.
Described aluminic acid ester series can be (C
3H
7O)
xAl (OCOR)
m(OCOR)
n(OAB)
yFormula compound, for example distearyl acyl-oxygen isopropyl aluminic acid ester, aluminic acid trimethyl, aluminic acid three isopropyl esters, the aluminic acid three benzyl esters of the sale of Foochow novel fine materials Co., Ltd of section of unit.
Said titanate esters series is following formula: compound:
ROO
(4-n)Ti(OX-R'Y)
n
In the formula:
N=2 or 3;
RO is hydrolyzable short chain alkoxy-functional;
OX is carboxyl, alkoxyl, sulfonic group or phosphorus base group.
The hydrolyzable short chain alkoxy-functional of RO can react with the inorganic matter surface hydroxyl, thereby reaches the purpose of chemical coupling.
Said titanate esters series is isopropyl three stearic acid titanate esters (CAS61417-49-0), tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanate esters (CAS 65460-52-8) or isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters (CAS67691-13-8) specifically.
Described bimetallic composite coupler is aluminium titanium composite coupler and/or aluminium zirconium composite coupler, particularly the aluminium titanium composite coupler OL-AT1618 that sells of Shanxi-Prov Inst of Chemical Industry for example; The aluminium zirconium composite coupler HY-031 that Hangzhou Jesse's card chemical industry Co., Ltd sells.
The condition of using the coupling dispersant to handle is following:
The processing of described coupling dispersant is under the condition of mixer rotating speed 500-600rpm, to handle 3-5 minute.This processing time can guarantee that the material surface treatment is more abundant; If the processing time is less than 5 minutes, then the material surface treatment is insufficient; If the processing time more than 5 minutes, then possibly grume take place reunite because of the material frictional heat, cause treatment effect not good on the contrary.
Then; The antiseptic that the anti-variable color in surface is handled mixes with 75-90 weight portion polyester resin with the coupling mixture of dispersing agents; Re-use the double screw extruder group and under the condition of heating-up temperature 240-265 ℃, engine speed 200-230 rev/min and feeding 18-24Hz, melt extrude, obtain a kind of antibacterial matrices.
Described polyester resin is PET (PETG) resin that can be used for spinning; Its inherent viscosity is 0.64-0.66g/dL, the for example spinning grade polyester section of China Petrochemical Industry's Yizheng Fiber Optical plant company sale, the spinning grade polyester section that PetroChina Company Limited.'s Liao Yang petrochemical company is sold.
The antiseptic that the anti-variable color in said surface is handled is mixing under the following condition with polyester resin: under the condition of mixer rotating speed 500-600rpm, mixed 3-5 minute, this incorporation time can guarantee that mixing of materials is more abundant; Be less than this time, then these mixing of materials are inhomogeneous; Being longer than this time then also maybe be because of the material frictional heat, and the generation grume is reunited, and causes batch mixing inhomogeneous on the contrary, influences production technology and product quality.
Double screw extruder used in the present invention is a product sold in the market, for example the TE-65 type parallel dual-screw extruding machine produced of the inferior chemical equipment in sets of Nanjing section Co., Ltd.
The preparation of B, antibiotic polyester fiber
Take by weighing the 2-10 weight portion in steps A) preparation antibacterial matrices and 90-98 weight portion polyester resin, the employing melt spinning method carry out spinning, obtain described antibiotic polyester fiber.
Melt spinning method is with a kind of polymer heating and melting, extrudes through spinneret orifice then, and cooling curing in air and form a kind of filament, the polymer that can be used for melt spinning must be can be melt into viscous state and the polymer that do not take place significantly to decompose.
The antibiotic polyester fiber spinning technique that the present invention adopts is consistent with the polyster fibre spinning technique of prior art, therefore in present specification, repeats no more.
The invention still further relates to the antibiotic polyester fiber that adopts said method to produce.
The antibiotic polyester fiber that adopts the inventive method to produce be a kind of be the nuclear core with the polyester resin, the fiber that its polyester resin outside is coated by antiseptic.The anti-microbial property of antibiotic polyester fiber of the present invention is excellent, and antibacterial effect is lasting, can be along with reason performances such as washing weaken.In addition, this anti-bacterial fibre outward appearance is better, does not have the xanthochromia phenomenon.The most important thing is; It is good that antiseptic superfine powder of the present invention has in use passed through coating and surface treatment and matrix resin compatibility, and dispersive property is also fine in resin; The anti-biotic material that makes like this shows good spinning property when spinning; Draping cycle and replacing filament spinning component cycle are compared with other similar spinning level antibacterial matrices (for example general basic zirconium phosphate carries silver-colored antibacterial matrices on the market), and the cycle is all long, thereby effectively reduces equipment loss.
Adopt the inventive method to produce antibiotic polyester fiber, the spinning cycle is long.The press filtration value of antibacterial matrices of the present invention (DF value) is less than 2.0 * 105Pa ㎝
2/ g; Assembly cycle>=15 day are changed in draping cycle>=1 slice/12 hours.And take antibacterial matrices system that general basic zirconium phosphate on the market carries silver to prepare spinning cycle >=1 slice of antibiotic polyester fiber/8 hours, change assembly cycle >=6 day.This shows that the spinning property of antibacterial matrices of the present invention is very good.
The invention still further relates to the purposes of said antibiotic polyester fiber in Chinese People's Anti-Japanese Military and Political College enterobacteria, staphylococcus aureus and Candida albicans.
1, anti-microbial property is excellent
According to AATCC100-2004 " performance evaluation of textile material antibiotic finish " standard testing; After the antibiotic polyester fiber that adopts the inventive method to produce is made into fabric; To antibiotic rate >=99% of Escherichia coli, staphylococcus aureus and Candida albicans, its result lists in table 1.
Table 1: the antibacterial tests result of antibiotic polyester fiber of the present invention
Two kinds of antiseptic zeolites that the present invention selects for use carry silver-colored zinc antiseptic and the basic zirconium phosphate carrying silver antimicrobials has synergistic function,
The antibacterial effect of antiseptic adopts the minimal inhibitory concentration method to judge, and minimal inhibitory concentration is measured according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.1.7.3.
At first test the minimal inhibitory concentration (MIC) of one-component.Each antiseptic uses ethanol-water solution (by volume 1:1) to dilute as solvent respectively, is diluted to concentration 10000ppm, tests the minimal inhibitory concentration of its one-component again, and these result of the tests are listed in the table 2.
Table 2 antiseptic one-component is to the minimal inhibitory concentration (MIC) of bacterium
Then, two kinds of antiseptics are mixed obtaining a kind of mixed liquor again by the 1:1 proportioning, and each component concentrations also all is 10000ppm in the mixed liquor, the same employing tested the minimal inhibitory concentration method, tests the minimal inhibitory concentration of composite component.
(fractional inhibitory concentration FIC) estimates the antibiotic synergistic function of two kinds of composite components of antiseptic with reference to the antibiotic synergy classification Mlc index method that adopts usually in this test.
The computing formula of FIC index is:
The FIC index that people calculate according to above-mentioned formula can be judged the interaction between the first and second composite components.When FIC≤0.5, first and second liang of components show as synergy, and when 0.5<FIC≤1, first and second liang of components then show as superposition, and when 1<FIC<2, it is uncorrelated that first and second liang of components show as, and when FIC>=2, first and second liang of components show as antagonism.MIC and FIC result that zeolite of the present invention carries silver-colored zinc antiseptic and basic zirconium phosphate carrying silver antimicrobials two composite components list in the table 3.
Table 3: the composite composition of antiseptic of the present invention is to the minimal inhibitory concentration (MIC) of bacterium
And the classification Mlc index (FIC) between composite composition
Common a kind of material can be regarded as it to the minimal inhibitory concentration of bacterium less than 800ppm and have anti-microbial property, and for example the minimal inhibitory concentration of regulation must be less than 800ppm among the industry standard HG/T3794-2005 " inorganic antiseptic-performance and evaluation ".Minimal inhibitory concentration (MIC) result by the single antibacterial components of table 2 can find out that the minimal inhibitory concentration of the selected antiseptic component of the present invention all is far smaller than 800ppm, so all showed good bacteriostatic activity.The result of table 3 shows, compares with the effect of single antiseptic component, and the minimal inhibitory concentration of composite back antiseptic system composition all reduces more.Judge the interaction between two kinds of antiseptic compositions according to classification Mlc index method; As far as two kinds of bacteriums; The FIC index of selected two kinds of antiseptics is all less than 0.5, and the selected composite parts of this explanation the present invention all has synergistic function, and synergistic effect is very good.
2, antibiotic persistence
The antibiotic polyester fiber fabric that adopts the inventive method to produce has permanent antibiotic property, and wash durability is excellent, compares with the antibiotic polyester fiber of afterfinish method preparation, and resistance to water obviously improves, wash 30 times after its antibiotic rate still greater than 98%.General adopt washable 30 times of antibiotic polyester fiber that afterfinish method makes or fabric after antibiotic rate be difficult to remain on more than 90%.
This test is with reference to the washing procedure of FZ/T 73023-2006 " antibiosis knitting article appendix C antibiotic fabric sample decantation test method ", and its result of the test is listed in the table 4.
Table 4: the terylene antibiotic fabric that distinct methods is produced is washed the antibacterial effect after 30 times
Result by table 4 can find out that not only antibacterial effect is excellent for the antibacterial dacron of process the present invention preparation, and washability is very good, and through 30 washings, anti-microbial property still can remain on more than 99%.Be far superior to the fabric of conventional afterfinish method preparation, can find out from last table, the fabric of finishing method preparation is after 30 washings.Anti-microbial property descends very serious.
3, security
Test method according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.3.3 regulation is carried out the skin irritation test to the antibiotic polyester fiber fabric of being produced by the inventive method:
Experimental animal is the NZw of 2.13-2.69kg.
Its result of the test is listed in the table 5.
Table 5: the skin irritation test result of antibiotic polyester fiber fabric
The result of the test that table 5 is listed shows that the antibiotic polyester fiber fabric that adopts the inventive method production is to the skin nonirritant.
[beneficial effect]
The invention has the beneficial effects as follows:
Adopt the inventive method to produce antibiotic polyester fiber, the spinning cycle is long, and spinning property is very good.The press filtration value of antibacterial matrices of the present invention (DF value) is less than 2.0 * 10
5Pa ㎝
2/ g; Assembly cycle>=15 day are changed in draping cycle>=1 slice/12 hours.And the antibacterial matrices system that adopts prior art prepares draping cycle >=1 slice of antibiotic polyester fiber/8 hours, changes assembly cycle >=6 day.
After the antibiotic polyester fiber that adopts the inventive method to produce is made into fabric, to antibiotic rate >=99% of Escherichia coli, staphylococcus aureus and Candida albicans.
The antibiotic polyester fiber fabric that adopts the inventive method to produce has permanent antibiotic property, and wash durability is excellent, and resistance to water obviously improves, wash 30 times after its antibiotic rate still greater than 98%.General adopt washable 30 times of antibiotic polyester fiber that afterfinish method makes or fabric after antibiotic rate be difficult to remain on more than 90%.
The antibiotic polyester fiber fabric that adopts the inventive method production is to the skin nonirritant.
[specific embodiment]
Can understand the present invention better through following embodiment.
Embodiment 1: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
The basic zirconium phosphate carrying silver antimicrobials of the silver content 2.8% of this profit river, Shanghai company production of 10 weight portions; The silver content 0.2% that 10 weight portion Beijing lofty nanometer Co., Ltd produces and the zeolite of zinc content 3.5% carry silver-colored zinc antiseptic and are added to the Zhangjagang City and create good mechanical Co., Ltd and produce in the SHR-10A type mixer; Add 0.2 weight portion discoloration inhibitor natural water talcum again, under the condition of mixer rotating speed 3000rpm, handle 15min; Then add 2 weight portion coupling dispersant VTESs, under the condition of rotating speed 500rpm, mix 5min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice that described mixture and 80 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry are sold is to mix 4min under the condition of 500rpm at rotating speed; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 260 ℃; The temperature in SECTOR-SEVEN, eight districts is 250 ℃; Head temperature is 245 ℃, and feeding is 20Hz, and engine speed is 220rpm.
The preparation of B, antibiotic polyester fiber
With 4 weight portion above-mentioned steps A) in the PET resin sold of the antibacterial matrices 96 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry that are added to of preparation, adopt melt spinning method to carry out spinning, obtain a kind of polyster fibre with antibacterial functions.
Embodiment 2: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
The basic zirconium phosphate carrying silver antimicrobials of the silver content 3.0% of profit river, 5 weight portion Shanghai company production; The silver content 0.3% that 15 companies of section of weight portion Haier produce and the zeolite of zinc content 2.0% carry silver-colored zinc antiseptic and are added to the Zhangjagang City and create good mechanical Co., Ltd and produce in the SHR-10A type mixer, add 0.015 weight portion discoloration inhibitor magnesium aluminium oxide calcine [Mg again
0.7Al
0.6O
1.15], under the condition of mixer rotating speed 2800rpm, handle 10min; Then add 0.3 weight portion coupling dispersant distearyl acyl-oxygen isopropyl aluminic acid ester, under the condition of rotating speed 500rpm, mix 3min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice that described mixture and 90 weight portion PetroChina Company Limited. Liao Yang petrochemical company are sold is to mix 3min under the condition of 600rpm at rotating speed; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 255 ℃; The temperature in SECTOR-SEVEN, eight districts is 245 ℃; Head temperature is 240 ℃, and feeding is 20Hz, and engine speed is 210rpm.
The preparation of B, antibiotic polyester fiber
With 10 weight portion above-mentioned steps A) antibacterial matrices of preparation joins in the PET resin that 90 weight portion PetroChina Company Limited. Liao Yang petrochemical company sell, and adopts melt spinning method to carry out spinning, obtains a kind of polyster fibre with antibacterial functions.
Embodiment 3: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
The basic zirconium phosphate carrying silver antimicrobials of the silver content 3.0% of the synthetic commodity of producing in 15 weight portions Japan East Asia zeomic by name; The silver content 0.3% that 5 weight portion Beijing lofty nanometer Co., Ltd produces and the zeolite of zinc content 2.0% carry silver-colored zinc antiseptic and are added to the Zhangjagang City and create good mechanical Co., Ltd and produce in the SHR-10A type mixer; Add 0.6 weight portion discoloration inhibitor, 1 weight portion alumina silicate and 1 weight portion natural water talcum again, under the condition of mixer rotating speed 3000rpm, handle 30min; Then add the compound coupling dispersant of 0.6 weight portion aluminium titanium, under the condition of rotating speed 600rpm, mix 4min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice with described mixture and the sale of 75 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry mixes 5min under the condition of rotating speed 600rpm; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 265 ℃; The temperature in SECTOR-SEVEN, eight districts is 255 ℃; Head temperature is 245 ℃, and feeding is 20Hz, and engine speed is 230rpm.
The preparation of B, antibiotic polyester fiber
The antibacterial matrices of 2 weight portion above-mentioned steps A preparation is joined in the PET resin of 98 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry sale, adopt melt spinning method to carry out spinning, obtain a kind of polyster fibre with antibacterial functions.
The antibiotic polyester fiber of embodiment 1-3 preparation carries out following antibacterial tests.
1, anti-microbial property:
According to AATCC100-2004 " performance evaluation of textile material antibiotic finish " standard testing, its result lists in table 4:
Table 4: the antibacterial tests result of antibiotic polyester fiber
2, antibiotic persistence:
List in table 5 with reference to test The anti-bacterial result behind the washing procedure of FZ/T 73023-2006 " antibiosis knitting article appendix C antibiotic fabric sample decantation test method " the washing anti-bacterial fibre 30 times.
Table 5 antibiotic polyester fiber is washed the antibacterial effect after 30 times
3, security:
Skin irritation test method according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.3.3 regulation is carried out.
Experimental animal is the NZw of 2.13-2.69kg.
These tests have proved that fully the antibiotic polyester fiber that embodiment 1,2,3 produces is to the skin nonirritant.
Embodiment 4: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
Producing the trade mark to the lofty nanometer of 1 weight portion Co., Ltd is the basic zirconium phosphate carrying silver antimicrobials of the silver content 2.8% of AMR; It is that the zeolite of silver content 0.2% and the zinc content 3.5% of AM carries silver-colored zinc antiseptic and is added to the Zhangjagang City and creates good mechanical Co., Ltd and produce in the SHR-10A type mixer that 20 weight portion Beijing lofty nanometer company produces the trade mark; Add 2 weight portion discoloration inhibitor BTAs (CAS 95-14-7) again, under the condition of mixer rotating speed 3000rpm, handle 15min; Then add 0.8 weight portion coupling dispersant gamma-aminopropyl-triethoxy-silane, under the condition of rotating speed 500rpm, mix 5min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice that described mixture and 85 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry are sold is to mix 4min under the condition of 500rpm at rotating speed; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 260 ℃; The temperature in SECTOR-SEVEN, eight districts is 250 ℃; Head temperature is 245 ℃, and feeding is 20Hz, and engine speed is 220rpm.
The preparation of B, antibiotic polyester fiber
With 6 weight portion above-mentioned steps A) in the PET resin sold of the antibacterial matrices 94 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry that are added to of preparation, adopt melt spinning method to carry out spinning, obtain a kind of polyster fibre with antibacterial functions.
Embodiment 5: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
The basic zirconium phosphate carrying silver antimicrobials of the silver content 3.0% of profit river, 20 weight portion Shanghai company production; The silver content 0.3% that 1 company of section of weight portion Haier produces and the zeolite of zinc content 2.0% carry silver-colored zinc antiseptic and are added to the Zhangjagang City and create good mechanical Co., Ltd and produce in the SHR-10A type mixer; Add 1 weight portion discoloration inhibitor methylbenzotrazole potassium again, under the condition of mixer rotating speed 2800rpm, handle 10min; Then add 0.5 weight portion coupling dispersant DL-411, under the condition of rotating speed 500rpm, mix 3min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice that described mixture and 82 weight portion PetroChina Company Limited. Liao Yang petrochemical company are sold is to mix 3min under the condition of 600rpm at rotating speed; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 255 ℃; The temperature in SECTOR-SEVEN, eight districts is 245 ℃; Head temperature is 240 ℃, and feeding is 20Hz, and engine speed is 210rpm.
The preparation of B, antibiotic polyester fiber
The antibacterial matrices of 8 weight portion above-mentioned steps A preparation is joined in the PET resin of 92 weight portion PetroChina Company Limited. Liao Yang petrochemical company sale, adopt melt spinning method to carry out spinning, obtain a kind of polyster fibre with antibacterial functions.
Embodiment 6: produce antibiotic polyester fiber
Implementation step is following:
The preparation of A, antibacterial matrices
The basic zirconium phosphate carrying silver antimicrobials of the silver content 3.0% of 15 weight portions Japan SR company production; It is that the zeolite of silver content 0.3% and the zinc content 2.0% of AM carries silver-colored zinc antiseptic and is added to the Zhangjagang City and creates good mechanical Co., Ltd and produce in the SHR-10A type mixer that 5 weight portion Beijing lofty nanometer company produces the trade mark; Add 0.6 weight portion discoloration inhibitor methylbenzotrazole (CAS 21412-99) again, under the condition of mixer rotating speed 3000rpm, handle 30min; Then add 0.6 weight portion isopropyl, three stearic acid titanate esters, under the condition of rotating speed 600rpm, mix 4min, obtain a kind of mixture that contains antiseptic; At last, the PET polyester slice with described mixture and the sale of 75 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry mixes 5min under the condition of rotating speed 600rpm; Mixing of materials is even, emits material, is added in the inferior TE-65 type double screw extruder group of producing of Nanjing section under following condition, to carry out granulation; Obtain a kind of antibacterial matrices: the temperature in first district is 240 ℃, and the temperature in second district, three districts is 250 ℃, and the temperature in the 4th district, five districts, six districts is 265 ℃; The temperature in SECTOR-SEVEN, eight districts is 255 ℃; Head temperature is 245 ℃, and feeding is 20Hz, and engine speed is 230rpm.
The preparation of B, antibiotic polyester fiber
The antibacterial matrices of 2 weight portion above-mentioned steps A preparation is joined in the PET resin of 98 Yizheng Fiber Optical plant companies of weight portion China Petrochemical Industry sale, adopt melt spinning method to carry out spinning, obtain a kind of polyster fibre with antibacterial functions.
Claims (10)
1. the production method of an antibiotic polyester fiber is characterized in that the step of this production method is following:
The preparation of A, antibacterial matrices
In mixer; Use the 0.015-2 weight portion to prevent that the variable color finishing agent carries silver-colored zinc antiseptic to 1-20 weight portion zeolite and 1-20 weight portion basic zirconium phosphate carrying silver antimicrobials carries out the anti-variable color processing in surface; Then add 0.3-1 weight portion coupling dispersant and proceed to handle, obtain a kind of mixture that contains antiseptic; Then, described mixture is mixed with 75-90 weight portion polyester resin, re-use the double screw extruder group and under the condition of heating-up temperature 240-265 ℃, engine speed 200-230 rev/min and feeding 18-24Hz, melt extrude, obtain a kind of antibacterial matrices;
The preparation of B, antibiotic polyester fiber
Take by weighing antibacterial matrices and the 90-98 weight portion polyester resin of 2-10 weight portion, adopt melt spinning method to carry out spinning, obtain described antibiotic polyester fiber in the steps A preparation;
Described coupling dispersant is that one or more are selected from silane series, aluminic acid ester series, titanate esters is serial or the coupling dispersant of the compound coupling dispersant of bimetallic;
Described anti-variable color finishing agent is one or more anti-variable color finishing agents that are selected from BTA, methylbenzotrazole, methylbenzotrazole potassium, natural water talcum, synthetic hydrotalcite, magnesium aluminium oxide calcine or alumina silicate.
2. production method according to claim 1 is characterized in that said silane series coupling dispersant is a following formula: compound:
R
nSiX
(4-n)
In the formula:
n=1~3；
R is methyl, vinyl, amino, epoxy radicals, sulfydryl or acryloyl-oxy propyl group functional group;
X is alkoxyl, aryloxy group, acyl group or chloro group.
3. production method according to claim 1 is characterized in that said aluminic acid ester series is selected from distearyl acyl-oxygen isopropyl aluminic acid ester, aluminic acid trimethyl, aluminic acid three isopropyl esters or aluminic acid three benzyl esters.
4. production method according to claim 1 is characterized in that said titanate esters series is following formula: compound:
ROO
(4-n)Ti(OX-R'Y)
n
In the formula:
N=2 or 3;
RO is hydrolyzable short chain alkoxy-functional;
OX is carboxyl, alkoxyl, sulfonic group or phosphorus base group.
5. production method according to claim 1 is characterized in that said bimetallic composite coupler is aluminium titanium composite coupler or aluminium zirconium composite coupler.
6. production method according to claim 1 is characterized in that it is under the condition of mixer rotating speed 2800-3000rpm, to carry out the anti-variable color in surface to handle 10-30 minute that the anti-variable color in described surface is handled.
7. production method according to claim 1, the processing that it is characterized in that described coupling dispersant are under the condition of mixer rotating speed 500-600rpm, to handle 3-5 minute.
8. production method according to claim 1, the mixed processing that it is characterized in that said polyester resin are under the condition of mixer rotating speed 500-600rpm, to handle 3-5 minute.
9. the antibiotic polyester fiber of producing according to the said method of each claim among the claim 1-8.
10. according to the purposes of the said antibiotic polyester fiber of claim 9 in Chinese People's Anti-Japanese Military and Political College enterobacteria, staphylococcus aureus and Candida albicans.
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