CN1412355A - Double wave length fluorescent composite fibre, its production method and application - Google Patents
Double wave length fluorescent composite fibre, its production method and application Download PDFInfo
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- CN1412355A CN1412355A CN 02137637 CN02137637A CN1412355A CN 1412355 A CN1412355 A CN 1412355A CN 02137637 CN02137637 CN 02137637 CN 02137637 A CN02137637 A CN 02137637A CN 1412355 A CN1412355 A CN 1412355A
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Abstract
The double-wavelength fluorescent composition fibre is a fibre which is formed from long-wavelength fluorescent mixture and short-wavelength fluorescent mixture and has skin-core type or side-by-side type structure, the exciting wavelength of the described long-wavelength fluorescent compound is 365 nm and the exciting wavelength of the short-wavelength fluorescent compound is 254 nm. Said composite fibre possesses good safety as compared with monowavelength fluorescent fibre, according to the different requirement it can be formed into series antifalse identifications with different colours, and is a high-effective antifalse material with good stability. Said invention also provides its preparation method.
Description
Technical field:
The present invention relates to the material field, be specifically related to a kind of double wave length fluorescent composite fibre and manufacture method thereof and application.
Background technology:
Along with expanding economy, commodity market prosperity, fake and inferior commodities frequently occur, and are full of every field, become the public hazards in the whole world.These fake product behaviors not only bring loss to national economy, upset national financial order, even bring about great losses for people's lives and properties.Survey report according to federation of French manufacturer shows that counterfeit and fake product has accounted for the 5-6% of quantum of world trade, hundred million dollars of about 1000-1200, and the economic loss that China's year personation counterfeit or inferior quality goods cause reaches 3,000 hundred million RMB.Therefore with contemporary advanced, greatly develop anti-counterfeiting technology, actively take false proof means to prevent and hit the forgery behavior, in current economic develop rapidly, seem very urgent.
The false proof means that current manufacturer uses adopt the fluorescence series of products mostly, as fluorescent ink, fluorescent fiber.Fluorescent ink is on the make simpler, generally adds fluorescent chemicals in printing ink, makes the printing trade mark then.This trade mark is under the ultra violet lamp of specific wavelength, and the fluorescent chemicals brilliance that can glimmer in the printing ink uses the fluorescent chemicals of different colours can send the light of different colours.But the manufacturing of this kind method is simple, the imitation of easily being given away secrets.Fluorescent fiber is the antifalse fiber that grew up in recent years, and its manufacturing technique is comparatively complicated, and it is earlier with fluorescent chemicals and fiber-forming polymer blend, obtain the fluorescence master batch, fluorescence master batch and high polymer mix, and obtain fluorescent mixture, get through spinning, coiling, stretching again.Fluorescent fiber is mainly used in anti-fake certificate, bill, trade mark, garment decoration and other can discern the field.For example Japan, Germany make cheque paper with it, just fluorescent fiber are cut into the fubril of certain-length, it are added in the paper then can make cheque paper.Fiber in the paper be can't see, but fiber will present a kind of color under the ultraviolet ray irradiation.In the latest domestic version RMB fluorescent fiber is arranged also, form but above-mentioned fluorescent fiber all is single wavelength fluorescent compound.Along with progress of science and technology, these false proof measures also are easy to give away secrets.Simultaneously, this kind fluorescent fiber is subjected to back processing conditions and surrounding environment influence, the less stable of fluorescence property.Summary of the invention:
Technical problem to be solved by this invention provides a kind of double wave length fluorescent composite fibre with efficient anti-fake effect.
Double wave length fluorescent composite fibre disclosed by the invention is the fiber with core-skin type or parallel type structure that is composited by long wavelength's fluorescent mixture and short wavelength's fluorescent mixture, wherein the excitation wavelength of the fluorescent chemicals in long wavelength's fluorescent mixture is 365nm, and the excitation wavelength of the short wavelength's fluorescent chemicals in short wavelength's fluorescent mixture is 254nm.
Length of the present invention or short wavelength's fluorescent mixture are made up of fluorescence master batch and high polymer, and wherein fluorescent chemicals content is 1-10%; Described fluorescence master batch is that 45-91.5% high polymer, 5-40% fluorescent chemicals, 0-2% coupling agent and 0-3% dispersant are formed by percentage by weight.
Described high polymer is selected from TPO, polyesters and polyamide-based.
Described fluorescent chemicals is the fluorescent material of inorganic or organic class, and its excitation wavelength is 254nm or 365nm.
Described coupling agent is titanate ester (as NDZ-101), silanes (as KH-550, A-151) and aluminium esters of gallic acid (as DL-411).
Described dispersant is low molecular weight polyethylene wax, EVA.
The compound ratio of long wavelength's fluorescent mixture and short wavelength's fluorescent mixture is 30-70: 70-30 (w/w) in the fluorescent fiber of the present invention.
Skin-core structure of the present invention as shown in Figure 1, the fluorescent mixture of its center core layer 1 and cortex 2 can be respectively long or short wavelength's fluorescent mixture, or the fluorescent mixture of identical wavelength different colours.Described parallel type structure as shown in Figure 2, wherein left-half 3 and right half part 4 can be respectively long wavelength or short wavelength's fluorescent mixtures, or the fluorescent mixture of identical wavelength different colours.
Another technical problem to be solved by this invention is the manufacture method that discloses above-mentioned double wave length fluorescent composite fibre.
The preparation of double wave length fluorescent composite fibre of the present invention comprises the following steps:
(1) fluorescence master batch preparation: long wavelength and short wavelength's fluorescent chemicals is made long wavelength's fluorescence master batch and short wavelength's fluorescence master batch with high polymer, coupling agent, dispersant blend respectively by prescription.Fluorescent chemicals content is≤40% in the master batch;
(2) spinning material preparation: according to fluorescent chemicals content in the fluorescence master batch, sneak into fiber-forming polymer in proportion, obtain fluorescent mixture, making fluorescent chemicals content in high polymer is 1-10%, and high polymer is identical with the fiber-forming polymer of sneaking in the master batch;
(3) spinning: spinning equipment is the twin-screw spinning machine, and spinning pack has core-skin type and parallel type; During spinning at first with long wavelength's fluorescent mixture and melt extruded, the metering in 2 screw rods respectively of short wavelength's fluorescent mixture, enter same spinning pack again, two kinds of melts are respectively walked the road of each in spinning pack, until the spinneret orifice place converges and extrudes spinneret orifice, spin fiber; Fiber passes through upper oil-pan, by reeling behind draw-off godet, the last draw-off godet down; If adopting the parallel type spinning pack to spin the double wave length fluorescent fiber is parallel type; Adopting the core-skin type spinning pack to spin the double wave length fluorescent fiber is core-skin type.Spinning temperature is 200-285 ℃, and winding speed is 600-1500m/min; The compound ratio of long wavelength's fluorescent mixture and short wavelength's fluorescent mixture is 30-70: 70-30 (w/w) in core-skin type or the parallel type fluorescent fiber.
A technical problem more to be solved by this invention is to disclose the application of above-mentioned double wave length fluorescent composite fibre in the preparation anti-fake product.
Double wave length fluorescent composite fibre of the present invention can be used for the false proof of certificate, bill, trade mark, clothes, decoration and other field.
Double wave length fluorescent composite fibre disclosed by the invention contains the fluorescent chemicals of two kinds of wavelength, long wavelength 365nm, short wavelength 254nm in fiber.Present a kind of color under the 365nm wavelength ultraviolet light that do not coexist of fiber color according to fluorescent chemicals, present another kind of color under 254nm wavelength ultraviolet light, fluorescent chemicals and the color that can Gong select for use be as shown in table 1 below.
Table 1 fluorescent chemicals
Wavelength model coloured light
SW1-SO is organic red
Long JGUV-R is inorganic red
JGUV-B indigo plant
The JGUV-O orange
Ripple JGUV-Y Huang
JGUV-G is green
The JGUV-P purple
JGUV-W is white
Short JGUVS-R is red
JGUVS-B indigo plant
Ripple JGUVS-G is green
Double wave length fluorescent composite fibre disclosed by the invention is compared with existing single wavelength fluorescent fiber has following many-sided remarkable advantage:
1, double wave length fluorescent fibre manufacture complexity is not if having specific twin-screw spinning equipment and assembly then can't copy.Simultaneously, the also general spinning complexity of composite spinning technology.If do not grasp composite spinning technology, also can't forge, so this fluorescent fiber security is better.
2, long wavelength's fluorescent chemicals and short wavelength's fluorescent chemicals are respectively in cortex and sandwich layer; Or a left side is half of and right half of, and it is very nearly the same to make fluorescent fiber mechanical property and general fibre, fibre strength 〉=2.5CN/dtex, monfil dawn number 〉=1.2dtex.
3, the double wave length fluorescent fiber can with the another kind of color of glimmering under the 254nm wavelength ultraviolet ray irradiation, have efficient antiforge function with a kind of color of glimmering under the 365nm wavelength ultraviolet ray irradiation.
4, can produce a series of different fluorescent composite fibres by permutation and combination, also can produce the fluorescent fiber of co-wavelength different colours, reach the purpose of false proof seriation.
5, fluorescent chemicals is carried out surface treatment, and it is better with the high polymer compatibility in fiber to add auxiliary agent, coupling agent, fluorescent chemicals, fluorescent chemicals is difficult for being separated out from fiber surface.
Description of drawings:
Fig. 1 sheath core fiber structural representation
Wherein 1 is sandwich layer, and 2 is cortex
Fig. 2 bilateral fibre structural representation
Wherein 3 is left-half, and 4 is right half part
The specific embodiment:
The preparation of embodiment 1 sheath core fiber
High polymer is a polypropylene, and fluorescent material is SWI-SO, coupling agent: NDZ-101, dispersant: EVA.
1, the preparation of master batch is kneaded 1 part of fluorescent chemicals SWI-SO and 9 parts of polypropylene by high-speed kneader, extruded by screw extruder fusion, blend again, and granulation obtains long wavelength's fluorescence master batch.1 part of coupling agent is dissolved in 4 parts of alcohol solvents, will contains ethanolic solution and 1 part of fluorescent chemicals JGUVS-B high-speed stirred of 0.03 part of coupling agent again, coupling agent fully coats JGUVS-B, at last with alcohol solvent volatilization and pulverizing.This JGUVS-R of 1 part and 9 parts of polypropylene and 0.03 part of dispersant (EVA) are kneaded by high-speed kneader again, extruded by screw extruder fusion, blend, granulation obtains short wavelength's fluorescence master batch.Two kinds of fluorescence master batches mix with polypropylene respectively, and it is 4% blend that proportioning becomes content.
2, the fluorescence blend of two kinds of different wave lengths by two screw rod fusions respectively, be metered into the core-skin spinning pack, before core-skin spinning pack spinnerets, converge, spray by spinneret orifice, through oiling, coiling obtains the dual wavelength core-skin composite fiber, the cortex of this fiber is long wavelength's fluorescent mixture, and sandwich layer is that short wavelength's fluorescenceization is mixed thing.Spinning temperature 230-250 ℃, spinning speed 800m/min, 3.5 times of draw ratios, 70/100 ℃ of draft temperature.The length wavelength fluorescent compound ratio of this dual wavelength core-skin composite fiber is 1: 1.The compound ratio of core-skin is 50: 50.
The preparation of embodiment 2 bilateral fibres
High polymer: polypropylene, fluorescent chemicals: SWI-SO, JGUVS-B, coupling agent: NDZ-101, dispersant: EVA.
The preparation of fluorescence master batch mixes 1 part of fluorescent chemicals SWI-SO and 9 parts of polypropylene by high-speed kneader, extruded by screw extruder fusion, blend again, and granulation obtains long wavelength's fluorescence master batch.1 part of coupling agent is dissolved in 4 parts of alcohol solvents, will contains ethanolic solution and 1 part of fluorescent chemicals JGUVS-B high-speed stirred of 0.03 part of coupling agent again, coupling agent fully coats JGUVS-B, at last with alcohol solvent volatilization and pulverizing.This JGUVS-B of 1 part, 9 parts of polypropylene and 0.03 part of dispersant (EVA) are kneaded by high-speed kneader again, extruded by screw extruder fusion, blend, granulation obtains short wavelength's fluorescence master batch.Two kinds of fluorescence master batches mix with polypropylene respectively, and it is 4% long wavelength's fluorescence blend and 6% short wavelength's fluorescence blend that proportioning becomes content.
The fluorescence blend of two kinds of different wave lengths by two screw rod fusions respectively, be metered into spinning pack arranged side by side, before spinnerets, converge, by spinneret orifice ejection, through oiling, reel again, obtain the dual wavelength parallel composite fiber.Spinning temperature 230-250 ℃, spinning speed 600m/min, 3.5 times of draw ratios, 70/100 ℃ of draft temperature.The length wavelength fluorescent compound ratio of this dual wavelength parallel composite fiber is 4: 6.The arranged side by side compound ratio of this dual wavelength parallel composite fiber: 50: 50.
The preparation of embodiment 3 sheath core fibers
High polymer: polypropylene, fluorescent chemicals: JGUV-R, JGUVS-B, coupling agent: NDZ-101, dispersant: low molecular weight polyethylene wax
1 part of coupling agent is dissolved in 4 parts of alcohol solvents, will contains ethanolic solution and 1 part of fluorescent chemicals JGUVS-B high-speed stirred of 0.03 part of coupling agent again, coupling agent fully coats JGUVS-B, at last with alcohol solvent volatilization and pulverizing.This JGUVS-B of 1 part and 9 parts of polypropylene and 0.02 part of dispersant (low molecular weight polyethylene wax) are kneaded by high-speed kneader again, extruded by screw extruder fusion, blend, granulation obtains short wavelength's fluorescence master batch.With make long wavelength's fluorescence master batch with quadrat method.The content of fluorescent chemicals all is 10% in the master batch.
Two kinds of fluorescence master batches mix with polypropylene respectively, and it is 4% long wavelength's fluorescence blend and 6% short wavelength's fluorescence blend that proportioning becomes content.
The fluorescence blend of two kinds of different wave lengths by two screw rod fusions respectively, be metered into spinning pack arranged side by side, before spinnerets, converge, spray by spinneret orifice, again through oiling, reel, obtain the dual wavelength core-skin composite fiber, the cortex of this fiber is long wavelength's fluorescent mixture, and sandwich layer is short wavelength's fluorescent mixture.270 ℃ of spinning temperatures, spinning speed 600m/min, 3.5 times of draw ratios, 70/100 ℃ of draft temperature.The length wavelength fluorescent compound ratio of this dual wavelength core-skin composite fiber is 4: 6; The compound ratio of core-skin is 50: 50.
Claims (9)
1, a kind of double wave length fluorescent composite fibre, it is characterized in that this composite fibre is the fiber with core-skin type or parallel type structure that is composited by long wavelength's fluorescent mixture and short wavelength's fluorescent mixture, wherein the excitation wavelength of the fluorescent chemicals in long wavelength's fluorescent mixture is 365nm, and the excitation wavelength of the short wavelength's fluorescent chemicals in short wavelength's fluorescent mixture is 254nm.
2, a kind of double wave length fluorescent composite fibre as claimed in claim 1 is characterized in that wherein said long wavelength or short wavelength's fluorescent mixture be made up of fluorescence master batch and high polymer, and wherein fluorescent chemicals content is 1-10%; The fluorescence master batch is that 45-91.5% high polymer, 5-40% fluorescent chemicals, 0-2% coupling agent and 0-3% dispersant are formed by percentage by weight.
3, a kind of double wave length fluorescent composite fibre as claimed in claim 2 is characterized in that wherein said high polymer is selected from TPO, polyesters and polyamide-based; Described coupling agent is selected from titanate ester, silanes and aluminium esters of gallic acid; Described dispersant is selected from low molecular weight polyethylene wax and EVA.
4, a kind of double wave length fluorescent composite fibre as claimed in claim 2 is characterized in that wherein said fluorescent chemicals is the fluorescent chemicals of inorganic or organic class, and its excitation wavelength is 254nm or 365nm.
5, a kind of double wave length fluorescent composite fibre as claimed in claim 1 is characterized in that the compound ratio of long wavelength's fluorescent mixture and short wavelength's fluorescent mixture is 30-70: 70-30w/w in the wherein said composite fluorescence fiber.
6, a kind of double wave length fluorescent composite fibre as claimed in claim 1, the fluorescent mixture that it is characterized in that wherein said skin-core structure center core layer and cortex can be respectively long wavelength or short wavelength's a fluorescent mixture.
7, a kind of double wave length fluorescent composite fibre as claimed in claim 1 is characterized in that left-half and right half part can be respectively long or short wavelength's fluorescent mixtures in the wherein said parallel type structure.
8, a kind of preparation method of double wave length fluorescent composite fibre as claimed in claim 1 is characterized in that the preparation of this double wave length fluorescent composite fibre comprises the following steps:
(1) fluorescence master batch preparation: long wavelength and short wavelength's fluorescent chemicals is made long wavelength's fluorescence master batch and short wavelength's fluorescence master batch with high polymer, coupling agent, dispersant blend respectively by prescription; Fluorescent chemicals content is≤40% in the master batch;
(2) spinning material preparation: according to fluorescent chemicals content in the fluorescence master batch, sneak into fiber-forming polymer in proportion, obtain fluorescent mixture, making fluorescent chemicals content in high polymer is 1-10%, and high polymer is identical with the fiber-forming polymer of sneaking in the master batch;
(3) spinning: spinning equipment is the twin-screw spinning machine, and spinning pack has core-skin type and parallel type; During spinning at first with long wavelength's fluorescent mixture and melt extruded, the metering in two screw rods respectively of short wavelength's fluorescent mixture, enter same spinning pack again, two kinds of melts are respectively walked the road of each in spinning pack, until the spinneret orifice place converges and extrudes spinneret orifice, spin fiber; Fiber passes through upper oil-pan, by reeling behind draw-off godet, the last draw-off godet down; If adopting the parallel type filament spinning component to spin the double wave length fluorescent fiber is parallel type; Adopting the spun dual wavelength fiber of core-skin type assembly is core-skin type; Spinning temperature is 200-285 ℃, and winding speed is 600-1500m/min; Draw ratio 2.5-4 times, draft temperature 50-85/100-150 ℃; The compound ratio of long wavelength's fluorescent mixture and short wavelength's fluorescent mixture is 30-70: 70-30w/w in core-skin or the parallel type fluorescent fiber.
9, the application of a kind of double wave length fluorescent composite fibre as claimed in claim 1 in the preparation anti-fake product is characterized in that this composite fibre can be used for the false proof of certificate, bill, trade mark, clothes, decoration and other field.
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Cited By (14)
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| WO2008034381A1 (en) * | 2006-08-30 | 2008-03-27 | Xianlin Sun | A fluorescent anti-fake fiber and an anti-fake material whose vision character change caused by excited light angle change |
| CN100410429C (en) * | 2003-12-10 | 2008-08-13 | 同济大学 | Electrostatic spinning apparatus with multi-spraying heads for preparing coaxial composite continuous nanometer/micron fibre |
| WO2009105970A1 (en) | 2008-02-29 | 2009-09-03 | Sun Xianlin | Fluorescent anti-counterfeiting fiber and anti-counterfeiting material with vision character changing according to changing of exciting light angle |
| CN101578400B (en) * | 2006-12-27 | 2011-08-10 | 韩国造币公社 | Functional fiber for preventing forgery |
| CN102153285A (en) * | 2010-12-03 | 2011-08-17 | 中国科学院上海光学精密机械研究所 | Method for preparing co-doped mesoporous aluminum phosphate glass capable of realizing double-wavelength fluorescent output |
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| CN103668557A (en) * | 2013-11-18 | 2014-03-26 | 浙江三星特种纺织有限公司 | Photosensitive sheath core coating yarn and preparation method thereof |
| CN104824891A (en) * | 2015-05-20 | 2015-08-12 | 海安县兄弟合成纤维有限公司 | Thermal-sensitive composite fabric |
| CN105734704A (en) * | 2015-12-25 | 2016-07-06 | 上海印钞有限公司 | Colorful fluorescent fiber |
| CN106674710A (en) * | 2016-12-13 | 2017-05-17 | 福建鑫邦新材料科技有限公司 | EVA (Ethylene Vinyl Acetate) master batch as well as preparation method and application thereof |
| CN108708220A (en) * | 2018-05-20 | 2018-10-26 | 复旦大学 | A kind of anti-fake hand-made paper of double wave length fluorescent and its production method |
| CN110709540A (en) * | 2017-05-02 | 2020-01-17 | 犯罪科学技术公司 | Use of 4-boron-3 a,4 a-diaza-s-indene for producing fluorescent fibers |
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- 2002-10-25 CN CN 02137637 patent/CN1216188C/en not_active Expired - Fee Related
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| CN100410429C (en) * | 2003-12-10 | 2008-08-13 | 同济大学 | Electrostatic spinning apparatus with multi-spraying heads for preparing coaxial composite continuous nanometer/micron fibre |
| WO2008034381A1 (en) * | 2006-08-30 | 2008-03-27 | Xianlin Sun | A fluorescent anti-fake fiber and an anti-fake material whose vision character change caused by excited light angle change |
| CN101578400B (en) * | 2006-12-27 | 2011-08-10 | 韩国造币公社 | Functional fiber for preventing forgery |
| WO2009105970A1 (en) | 2008-02-29 | 2009-09-03 | Sun Xianlin | Fluorescent anti-counterfeiting fiber and anti-counterfeiting material with vision character changing according to changing of exciting light angle |
| CN101519857B (en) * | 2008-02-29 | 2011-08-24 | 上海柯斯造纸防伪技术有限公司 | Anti-counterfeiting fiber with fluorescence fiber color changing with the change of optic angle of exciting light and anti-counterfeiting material |
| CN102482802B (en) * | 2009-09-08 | 2015-03-25 | 联邦印刷有限公司 | Biluminescent colored fibers |
| CN102482802A (en) * | 2009-09-08 | 2012-05-30 | 联邦印刷有限公司 | Biluminescent colored fibers |
| CN102153285A (en) * | 2010-12-03 | 2011-08-17 | 中国科学院上海光学精密机械研究所 | Method for preparing co-doped mesoporous aluminum phosphate glass capable of realizing double-wavelength fluorescent output |
| CN103668557A (en) * | 2013-11-18 | 2014-03-26 | 浙江三星特种纺织有限公司 | Photosensitive sheath core coating yarn and preparation method thereof |
| CN104824891A (en) * | 2015-05-20 | 2015-08-12 | 海安县兄弟合成纤维有限公司 | Thermal-sensitive composite fabric |
| CN105734704A (en) * | 2015-12-25 | 2016-07-06 | 上海印钞有限公司 | Colorful fluorescent fiber |
| CN106674710A (en) * | 2016-12-13 | 2017-05-17 | 福建鑫邦新材料科技有限公司 | EVA (Ethylene Vinyl Acetate) master batch as well as preparation method and application thereof |
| CN110709540A (en) * | 2017-05-02 | 2020-01-17 | 犯罪科学技术公司 | Use of 4-boron-3 a,4 a-diaza-s-indene for producing fluorescent fibers |
| US11649563B2 (en) | 2017-05-02 | 2023-05-16 | Crime Science Technology | Use of 4-bora-3a,4a-diaza-s-indacenes for the production of fluorescent fibres |
| CN108708220A (en) * | 2018-05-20 | 2018-10-26 | 复旦大学 | A kind of anti-fake hand-made paper of double wave length fluorescent and its production method |
| CN111074363A (en) * | 2019-12-30 | 2020-04-28 | 常熟涤纶有限公司 | Superfine polyester fluorescent fiber with high adsorption function and preparation method thereof |
| CN111088552A (en) * | 2019-12-30 | 2020-05-01 | 常熟涤纶有限公司 | Cationic dyeable polyester fiber and preparation method thereof |
| CN111074363B (en) * | 2019-12-30 | 2022-04-15 | 常熟涤纶有限公司 | Superfine polyester fluorescent fiber with high adsorption function and preparation method thereof |
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