CN1089314A - Multi-function electromagnetic radiation shielding fibre and manufacture method thereof - Google Patents
Multi-function electromagnetic radiation shielding fibre and manufacture method thereof Download PDFInfo
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- CN1089314A CN1089314A CN 92114675 CN92114675A CN1089314A CN 1089314 A CN1089314 A CN 1089314A CN 92114675 CN92114675 CN 92114675 CN 92114675 A CN92114675 A CN 92114675A CN 1089314 A CN1089314 A CN 1089314A
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Abstract
The present invention relates to a kind of electromagnetic radiation shielding fibre and manufacturing technology thereof.It is characterized in that fibre-forming polymer (A) and (B) and its functional additive separately, X-alpha ray shield material and conductive materials and ultra-violet absorber, and improve the auxiliary agent of compatibility between the two, mix respectively evenly, making the core-skin weight ratio through melting mixing and composite spinning is 3: 7～2: 8 composite fibre.It has X-ray, radio and ultraviolet radiation function of shielding, and have can spin preferably and taking and the shielding durability.The manufactured goods of fiber of the present invention can be widely used in the electronic product particularly preceding personnel's of computer or television screen and X-ray CT machine body and mind protection on every side.
Description
The present invention relates to a kind of electromagnetic radiation shielding fibre and manufacture method thereof.
Along with more and more widely the application in industrial and agricultural production and people's daily life of electronic and electrical equipment or product, the caused phase mutual interference of electromagnetic radiation, accident that people produce for these electric products, even disaster is more and more paid attention to research; To by caused electronic product user of service of electromagnetic radiation or staff's body and mind discomfort on every side, and the pollution of working environment is also more and more paid close attention to and is solved.The scheme of researching and solving has two kinds substantially, and a kind of is the shielding that strengthens radiation source itself, as using conductive plastics as electronic product shell, or uses x ray protection glass etc. before the fluorescent screen of television set, with the minimizing radiation; Another kind of then be the body protection of strengthening the user of service, this point is particularly important to the electronic product user.Electromagnetic radiation shielding fibre just belongs to the latter's scope.
In the existing shielding fiber manufacturing technology, fiber generally only has a certain wave band shielding electromagnetic waves function, opens clear 61-102411 as the spy and has reported the barium sulfate of a kind of 40-80% of containing average grain diameter below 1 μ m, the viscose of making through wet spinning technology.It has 0.01-100A ° of electromagnetic radiation, i.e. X-alpha ray shield function preferably.Numerous results of study show, being 10-10 than resistance
-3The fabric that the fiber process of Ω cm becomes has good 1mm-500m ripple, i.e. the function of shielding of radio radiation, and this fiber is a metallized fiber.Its manufacture method is to adopt methods such as ion plating, chemistry (dipping) or vacuum moulding machine to form metal or the conductive metallic compound layer of one 0.05～1 μ m at fiber surface.When the weight of metal level be fibre weight 10～50% the time, the ratio resistance that can make fiber is by 10
13Ω cm drops to 10
-3～10
-4Ω cm, but owing to after fiber surface covers metal level, can influence the flexibility and the feel of fiber, the reduction wearability, and also metal cladding can come off after fiber is washed and uses gradually, and cause the deterioration of fiber shielding properties.For improving this defective, developed again in fiber surface plating alloy and the method that adopts special fiber base material, open shown in the clear 61-132667 as the spy.But these methods have all strengthened the difficulty of producing of radio radiation shielding fiber to some extent, and the preparation technology of this metallized fiber is become increasingly complex, and cost also improves thereupon.It is comparatively simple that the spy opens disclosed technology among the clear 55-3470: it is when the core composition carries out the core-skin composite spinning silk with fusing point than the thermal viscosity skin composition of low at least 30 ℃ of core composition, make fiber surface adhere to metal dust or metal forming, make metalized fibers being higher than the skin congruent melting point and being lower than to heat-treat under the temperature of 30 ℃ of core congruent melting points again during adhesion or after adhering to, but its shielding properties of fiber that obviously adopts this technology to make is unfavorable, also be unsettled, wearability is poor too.
Need be pointed out that further that more the research that has confirms, electromagnetic radiation around the electronic product is not single wave band sometimes, thereby the ELECTROMAGNETIC RADIATION SHIELDING function that shielding fiber only has an a certain wave band is not enough.As once the assembling of being engaged in high-pressure electronic equipment, the health status of testing, vacuumizing the woman worker being investigated, there are the electromagnetic field of different frequency and the X-ray of doses equivalent rates in these woman workers' the working environment simultaneously, the result shows, most illnesss be because x-ray irradiation, yet the higher nervous function disorder of incidence since microwave cause.As seen, when microwave and X-ray existed simultaneously, it injured into degree and superposes.To X-ray and ultraviolet research, also shown this injury synergistic effect.There is data to show, just has radio radiation, x-ray radiation and ultraviolet radiation before present widely used graphoscope and the television receiver fluorescent screen simultaneously.But in existing invention, fiber and manufacturing technology thereof with multiband ELECTROMAGNETIC RADIATION SHIELDING function still are not reported.
The purpose of this invention is to provide a kind of have simultaneously radio radiation, x-ray radiation and ultraviolet radiation function of shielding, and have preferably spinnability and take performance, and in use function of shielding does not have the fiber of obvious reduction and manufacturing technology comparatively simple and with low cost thereof.
The objective of the invention is following realization: the homogeneous mixture by fibre-forming polymer (A) and X-alpha ray shield material is sandwich layer, homogeneous mixture by fibre-forming polymer (B) and conductive materials and ultraviolet screener material is a cortex, all add the auxiliary agent that can improve compatibility between functional additive and fibre-forming polymer in sandwich layer and the cortex, and fibre-forming polymer (A) and (B) between have cohesiveness, cortex and sandwich layer weight ratio at fiber are 3: 7～2: 8 o'clock, make multi-function electromagnetic radiation shielding fibre through composite spinning technology.
The manufacture method of this multi-functional shielding fiber is: first used additives carries out preliminary treatment to functional additive, to increase the compatibility between itself and fibre-forming polymer; Use twin-screw mixer machine melting mixing, make between functional additive and fibre-forming polymer and evenly mix; Adopt the short silk of core-skin composite spinning silk technology spinning composite fibre; Spinning is after the wet method multistage drafting; Fiber curls through preheating and handles after the drawing-off; Be cut into the length that needs after the drying typing.
Said composite spinning is meant the fusion method spinning.Its process conditions are: be higher than fibre-forming polymer (A) or (B) in higher melt person's 20～150 ℃ of melt temperatures, particularly under 30～100 ℃ the spinning temperature, melt pressure is 50～80 * 10
5Pa, winding speed is 300～600 meters/minute, adopts the compound melt spinning equipment of conventional core-skin, produces the undrawn yarn of fiber of the present invention.
Undrawn yarn is behind boundling, and under 70～130 ℃, through secondary or the wet method drawing-off more than the secondary after totally 3～10 times, curling through 80～100 ℃ of preheatings obtains the fiber that crispation number is 3～8/cm, cuts into the length that needs behind the dryness finalization.
Fiber of the present invention is or/and the fiber of making by the inventive method or technology, can be by tradition or unorthodox method spinning, weave, or directly make nonwoven, and further manufactured goods are processed into various screening clothings or shielding articles for use as required.
Fibre-forming polymer of the present invention (A) and polymer (B), can be general fibre-forming polymers such as high density polyethylene (HDPE), polypropylene, polyamide and polyester, polymer (A) and polymer (B) both can be same substances, also can be to have fusible non-same substance, this will go design according to purposes.
What X-alpha ray shield material of the present invention was meant metallic element atoms such as containing lead, bismuth, gadolinium and barium has the good X-radiation absorption and a material of dissipation role, as lead oxide, lead octoate, lead acetate, bismuth oxide, bismuth chloride, bismuth hydroxide, bismuthic oxide, gadolinium oxide, gadolinium carbonate, gadolinium hydroxide, Digadolinium trisulfate and barium sulfate etc.The average diameter of these shielding material particles should be selected between 0.1～20 μ m, and particle diameter is excessive or too smallly all can influence its even dispersion in fibre-forming polymer.In addition, particle diameter is too small, may emit gas when spinning because of containing a large amount of absorption micromolecule, influences spinnability; And particle diameter is excessive, then might block filter screen in spinning, influences normally carrying out of spinning process.What also should specify is, in order to guarantee the shield effectiveness of X-ray, has good spinnability and taking simultaneously again, and the described content of dosing material should be controlled at 20～80%(and account for the sandwich layer percentage by weight, down with), particularly 30～70%.
Conductive materials of the present invention is meant the filament or the micro mist of metals such as copper, aluminium, nickel and titanium, and the specification of filament is, diameter is 5～20 μ m, and length is 0.05～1mm; And the average grain diameter when using metal fine powder should be selected between 0.1～20 μ m in order to avoid cause and disperse irregular or the obstruction spinnerets.What is more important, the content of conductive materials (account for the cortex percentage by weight, down with) should be higher than 10%, so that it has electric conductivity preferably, and is lower than 40%, with what keep fiber intensity should be arranged.
The ultraviolet radiation absorption material is meant that UV-0, UV-9, UV-531, UV-328, UV-327 and UV-326 etc. can effectively absorb 200～380 nanometer ultraviolet rays, prevent that it from seeing through the material powder of fabric, when its content is that 2～5%(accounts for the cortex percentage by weight, down with) time more suitable, content is then to realize the purpose of shielding ultraviolet rays of the present invention at 2～3% o'clock better.
The present invention is for obtaining high-quality shielding fiber, special even mixing of paying attention between functional additive and fibre-forming polymer, on prescription, added the auxiliary agent that can improve compatibility, as titanate esters series coupling agent, at least a, wherein best in silane series coupling agent and the glycerine high-grade aliphatic ester etc. with the titanate esters effect that contains long chain hydrocarbon groups, the addition of auxiliary agent is that the 1-2% of substance weight is advisable; On manufacture method, realize through melting mixing by the twin-screw mixer machine.The concrete practice is, at first auxiliary agent is joined in the powder of functional additive, high-speed stirred in closed container, mix, then the fibre-forming polymer pelletizing is joined in the said mixture, after further mixing, be higher than 20-100 ℃ of fibre-forming polymer fusing point, be preferably under the 30-80 ℃ of condition and melt extrude once, make pelletizing, use for spinning dry back.
Processed behind the also special fiber of paying attention in the spinning technique of the present invention is as the design of multistage wet method drawing-off and appropriate drafting multiple; Fiber crimp temperature and the design of crispation number purpose etc.These technological designs all will help improving or improving the processing characteristics (as intensity, elongation, embrace and power etc.) of fiber and the wearability of this fibre (as feel, breathe freely, comfortableness, antistatic behaviour etc.), and this will apply the tangible effect that brings to product of the present invention actual.
Because fiber of the present invention has spinnability preferably, so it can the explained hereafter identical or close with conventional spinning process go out woven cloth, knitted cloth and nonwoven etc., and further is processed into protective clothing and protective articles etc.Because having, this fiber and goods thereof shield radio radiation simultaneously again, the function of x-ray radiation and ultraviolet radiation (also having antistatic and dustproof), and has a taking preferably, and in use function of shielding does not have obvious reduction, so will be around the electronic product, the desirable protective articles of place staff such as before the computer display or before the television screen and before the X-ray CT machine particularly.In addition, process of the present invention is comparatively simple, is suitable for large-scale production, and expense is also cheap, is convenient to the popularization and application of product.
With embodiment the present invention is described more specifically below.
Embodiment 1 in average grain diameter is 1 micron 69 parts in barium sulfate powder, add 1 part of isopropyl three isostearic acid titanate esters after, put into airtight super mixer, stirred 20 minutes with 1400 rev/mins; Add melt index then and be 30 parts of 32 polypropylene; High-speed stirred once more, melting mixing is once made pelletizing under 240 ℃ of temperature on the Φ 30 twin-screw mixer machines, pelletizing after vacuumize as the core composition.
In average grain diameter is 20 microns 10 parts of aluminium powders, add 0.1 part of isopropyl three isostearic acid titanate esters, after the high-speed mixing, add 2 parts of 88 parts of above-mentioned polypropylene and UV-531 again, behind the mixing, mixing pelletizing and the drying made is as the skin composition.
The pump of adjusting the core composition is 51.2g/min for amount, and the pump of skin composition is 12.8g/min, melt pressure 60 * 10 for amount
5Pa, 250 ℃ of spinning temperatures, 400 meters/minute of winding speeds are spun into the core-skin composite fiber undrawn yarn.
Above-mentioned undrawn yarn boundling becomes 1,800,000 special tow, 3 times and 1.8 times of 70 ℃ and the drawing-offs of 100 ℃ of following continuous quadratic wet methods, and draft speed 45～60m/min, behind the dryness finalization that curls, cutting short-forming fiber.
The tensile break strength of gained fiber is 1.6CN/dtex, and extension at break is 23%, and fiber is 18.5 Ω CM than resistance.
This fiber can be processed into plain, drillipg and canvas and non-weaving cloth etc. with approximate conventional processing conditions.480g/M after tested
28kev(1.542A ° of drillipg (18/2 strands on warp thread, 18/2 strands of weft yarns)) X-alpha ray shield rate is 58.0%; The radio radiation that maskable is 22～43 decibels; 200～380 nanometer ultraviolet ray shielding rates are 99.5%.
Embodiment 2; with embodiment one identical step and condition under; bismuth oxide with 10 microns of average grain diameters; behind 39 parts in powder and the 0.8 part of hard ester acyl group of the isopropyl-methylpropenyl titanate esters mixing, being that 26 polyethylene is mixing with 60.2 parts of melt index again makes dry pelletizing as the core composition.
In average grain diameter is 10 microns 25 parts of copper powders, add 0.5 part of isopropyl three iso stearate titanate esters, then with 2 parts of 72.5 parts of above-mentioned polyethylene and UV-327, mixingly make dry pelletizing as the skin composition.
Adjust core and become wheel cylinder to be 63g/min for amount, skin becomes wheel cylinder to be 27g/min for amount, and pressure is 55 * 10
5Pa, 230 ℃ of spinning temperatures, winding speed under 400 meters/minute the condition, are spun into the core-skin composite fiber undrawn yarn.
After 5.6 times of boundling and twice wet method drawing-offs, curl, dryness finalization, cut-out obtain finished fiber.
The tensile break strength of gained fiber is 2.1CN/dtex, and extension at break is 28%, and fiber is 0.6 Ω CM than resistance.
It is 300～1000g/M that this fiber be can be made into surface density
2Non-weaving cloth and surface density be 550～660g/M
2Woven cloth.Test 557g/M
2The 8KevX-alpha ray shield rate of canvas is 60.3%; 45～50 decibels of maskable radio radiations, rate of ultraviolet shield are 99.8%.
Embodiment 3 is under the step and condition of embodiment one, 20 parts of gadolinium oxides and isopropyl two 0.2 part of different hard acid titanate esters and the intrinsic viscosity that with average grain diameter is 18 microns is after 0.69 polyethylene terephthalate is mixed, to make dry pelletizing as the core composition at 280 ℃ of melting mixings.
In average grain diameter is 0.8 micron 40 parts of copper powders; add 1 part of the hard ester acyl group of isopropyl diallyl titanate esters; after mixing, with molecular weight be 56 parts of 15000 polycaprolactams and uv-92 part, 250 ℃ of following melting mixings are made dry pelletizing as the skin composition.
Become wheel cylinder to be 56g/min for amount at core, skin becomes wheel cylinder for amount 24g/min, 60 * 10
5Under the melt pressure of Pa, temperature is 300 ℃, 515 meters/minute of winding speeds, and the spinning core-skin composite fiber is cut to finished fiber.
The tensile break strength of gained fiber is 2.6CN/dtex, and extension at break is 19%, and fiber is 6.2 * 10 than resistance
-2Ω cm.
The surface density made from this fiber is 1000g/M
2The 8kevX-alpha ray shield rate of non-weaving cloth be 43%, 52～60 decibels of maskable radio radiations, rate of ultraviolet shield is 99.3%.
Claims (6)
1, a kind of electromagnetic wave shielding composite fibre, it makes sandwich layer by fibre-forming polymer (A) and functional additive thereof, makes cortex by fibre-forming polymer (B) and functional additive thereof, makes through melting mixing, composite spinning technology, it is characterized in that:
(1) functional additive in the fibre-forming polymer (A) is an X-alpha ray shield material;
(2) functional additive in the fibre-forming polymer (B) is conductive materials and ultra-violet absorber;
(3) also be added with the auxiliary agent that can improve functional additive and add compatibility between main body separately;
(4) weight ratio of cortex and sandwich layer is 3: 7～2: 8;
(5) fibre-forming polymer (A) and (B) between have caking property.
2, according to the fiber of claim 1, it is characterized in that:
(1) average grain diameter of x-alpha ray shield material is 0.1～20 μ m; Content (account for the sandwich layer percentage by weight, down with) is 20～80%, particularly 30～70%;
(2) conductive materials can be a. wire, and specification is diameter 5～20 μ m, and length is 0.05～1mm; B. (account for the cortex percentage by weight, down with) is 10～40% or/and the content of metal fine powder for metal particle, average grain diameter 0.1～20 μ m, filament; Ultraviolet radiation absorption agent content (account for the cortex percentage by weight, down with) is 2～5%, particularly 2～3%;
(3) described auxiliary agent is 1～2% of a functional additive weight.
3, fiber according to claim 2 is characterized in that described auxiliary agent is a titanate esters series coupling agent.
4, according to the manufacture method of the described fiber of claim 1, it is characterized in that:
(1) first used additives carries out preliminary treatment to functional additive, to increase the compatibility between itself and fibre-forming polymer;
(2) use twin-screw mixer machine melting mixing, functional additive is fully mixed with fibre-forming polymer;
(3) adopt core-skin composite spinning silk method spinning composite short fiber;
(4) spinning is after the wet method multistage drafting;
(5) fiber curl to be handled through preheating after the drawing-off;
(6) after the drying typing, cutting into as required needs length.
5,, it is characterized in that process conditions are according to the manufacture method of the described fiber of claim 1:
(1) spinning temperature be higher than fibre-forming polymer (A) or (B) in 20～150 ℃ of higher melt temperature persons, particularly 30～100 ℃;
(2) melt pressure of melt spinning is 50～80 * 10
5Pa;
(3) the melt spinning winding speed is 300～600 meters/minute;
(4) the wet method drawing temperature is 70～130 ℃;
(5) the multistage drafting general times is 3～10 times;
(6) curling preheat temperature is 80～100 ℃;
(7) curling number is 3～8/centimetre.
6,, it is characterized in that described fiber being spinned, weaving by tradition or unorthodox method or directly make nonwoven, and further manufactured goods are processed into various screening clothings or shielding articles for use as required according to claim 1,2,4,5 described fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92114675 CN1038953C (en) | 1992-12-29 | 1992-12-29 | Multi-function electromagnetic radiation shielding fibre and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92114675 CN1038953C (en) | 1992-12-29 | 1992-12-29 | Multi-function electromagnetic radiation shielding fibre and its producing method |
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| Publication Number | Publication Date |
|---|---|
| CN1089314A true CN1089314A (en) | 1994-07-13 |
| CN1038953C CN1038953C (en) | 1998-07-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92114675 Expired - Fee Related CN1038953C (en) | 1992-12-29 | 1992-12-29 | Multi-function electromagnetic radiation shielding fibre and its producing method |
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| CN101949095A (en) * | 2010-09-02 | 2011-01-19 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN1796623B (en) * | 2004-12-31 | 2011-06-01 | 株式会社晓星 | Composite fiber with excellent conductivity and method for manufacturing same |
| CN102516726A (en) * | 2011-12-12 | 2012-06-27 | 费近峰 | PBT conductive plastics |
| CN102634931A (en) * | 2012-03-12 | 2012-08-15 | 马素德 | Production method of absorptive radiation-proof nonwoven fabrics |
| CN102704023A (en) * | 2012-05-24 | 2012-10-03 | 山东海龙股份有限公司 | Cellulose fiber for preventing X-ray radiation and preparation method thereof |
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| CN107502975A (en) * | 2017-08-31 | 2017-12-22 | 江苏中杰澳新材料有限公司 | Texturized terylene electrically conductive filament, manufacture method and its application |
| CN109957855A (en) * | 2019-03-19 | 2019-07-02 | 上海格普新材料科技有限公司 | A kind of fiber and preparation method thereof with anti-ultraviolet function |
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-
1992
- 1992-12-29 CN CN 92114675 patent/CN1038953C/en not_active Expired - Fee Related
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| CN1314845C (en) * | 2005-05-26 | 2007-05-09 | 天津工业大学 | Microwave shielding fiber and fabricating method |
| CN101949095A (en) * | 2010-09-02 | 2011-01-19 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN101949095B (en) * | 2010-09-02 | 2013-09-11 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN102516726A (en) * | 2011-12-12 | 2012-06-27 | 费近峰 | PBT conductive plastics |
| CN102634931A (en) * | 2012-03-12 | 2012-08-15 | 马素德 | Production method of absorptive radiation-proof nonwoven fabrics |
| WO2013170544A1 (en) * | 2012-05-14 | 2013-11-21 | Mao Yingjun | Warming and heat storage fiber, and preparation method and textile thereof |
| CN102704023B (en) * | 2012-05-24 | 2014-04-16 | 恒天海龙股份有限公司 | Cellulose fiber for preventing X-ray radiation and preparation method thereof |
| CN102704023A (en) * | 2012-05-24 | 2012-10-03 | 山东海龙股份有限公司 | Cellulose fiber for preventing X-ray radiation and preparation method thereof |
| CN105624821A (en) * | 2016-04-08 | 2016-06-01 | 上海全宇生物科技遂平有限公司 | Barium sulfate/polyvinyl alcohol composite fiber and preparation method thereof and non-woven fabric |
| CN105624821B (en) * | 2016-04-08 | 2017-08-25 | 上海全宇生物科技遂平有限公司 | A kind of barium sulfate/polyvinyl alcohol composite fiber and preparation method thereof, non-woven cloth |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
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|---|---|
| CN1038953C (en) | 1998-07-01 |
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