CN101358410A - Method of preparing polypropylene multi-layer nonwoven fabrics for medical treatment - Google Patents

Method of preparing polypropylene multi-layer nonwoven fabrics for medical treatment Download PDF

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CN101358410A
CN101358410A CNA2007101376873A CN200710137687A CN101358410A CN 101358410 A CN101358410 A CN 101358410A CN A2007101376873 A CNA2007101376873 A CN A2007101376873A CN 200710137687 A CN200710137687 A CN 200710137687A CN 101358410 A CN101358410 A CN 101358410A
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agent
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nonwoven fabric
water
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CN101358410B (en
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黄宇昌
金明镐
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Toray Polytech Nantong Co Ltd
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Toray Polytech Nantong Co Ltd
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Abstract

The invention relates to a preparation method of medical polypropylene multi-layer non-woven cloth, which comprises the following steps: a first spun-bonded overlay, a second spun-bonded overlay and a third melt-blown overlay are formed to form a spun-bonded/melt-blown/spun-bonded overlay; the three overlays are thermally bonded by a glazing machine to be endowed with stable shape; the non-woven cloth endowed with stable shape is soaked into the solution mixed with oil resistance agent and antistatic agent and dried, receives heat treatment, and is endowed with water resistance, oil resistance and antistatic properties. The polypropylene multi-layer non-woven cloth improves the permeability effect of water resistance agent, oil resistance agent and antistatic agent, is very economic, has no harm to the human body and environment pollution, no fire, explosion and other danger when being stored and used.

Description

The manufacture method of polypropylene multi-layer nonwoven fabrics for medical treatment
Technical field
The present invention relates to polypropylene multi-layer nonwoven fabrics for medical treatment and manufacture method thereof.In more detail, relate to as operating coat, sterilizing cloth, the patient with operation non-woven fabric compounded materials of biological barrier such as operation cloth in the available medical team of medical field, with the material manufacturing of superfine fiber high-density filter cloth the microbial barrier effect is arranged, anti-water, anti-oil, resisting alcoholic is excellent and isolate blood and body fluid fully, anti-charging property and gas permeability excellence and wearing feeling is good, medical team is undergone surgery under the comfortable condition of health, prevent polypropylene multi-layer nonwoven fabrics for medical treatment and manufacture method thereof in hospital infection.
Background technology
Generally, the biological barrier nonwoven fabric suppresses the infiltration of bacterium and other pollution sources, can use on disposable medical products such as surgery cloth, disposable garment.Such as, giving the nonwoven fabric of anti-water, resisting alcoholic such as operating coat etc. on the elasticity lace nonwoven fabric uses as disposable product, but obscure as nonwoven fabric insufficient strength because of staple fibre this moment, interior hydraulic pressure is low, when therefore using for a long time in the many fields of water, patient's body fluid or various pollution sources are exposed easily.And the spun-bonded non-woven fabrics of being made up of the polypropylene filament uses as the employee's of hospital the vest or the valance of patient with operation, thereby has reduced economy and cost burden.But the space is big between the fiber of formation spun-bonded non-woven fabrics, thereby reduces the effect that intercepts germ or other pollutants such as bacterium or patient's body fluid.And, the WATER RESISTANCE that the polypropylene filament spun-bonded non-woven fabrics is excellent because of its hydrophobicity has, but and have chemical attraction between oil and the alcohol etc., thereby the disinfectant that is used in the hospital easily, alcohol etc. get wet, be exposed to pollution sources.In addition, synthetic fiber are because of having the static that the long-time savings of electrical insulating property characteristic and other material frictions etc. produce, thereby because of discharge, attraction, the repulsion of static, the modern electronics Medical Devices of high price are extremely responsive and may cause various obstacles such as permanent damage.These static are produced by the friction between the material, contact, so can not prevent static itself.Therefore, in order to prevent so static obstacle of synthetic fiber, should eliminate, neutralization, leak charge.Prevent the adjustment of the method general using humiture of static obstacle, corona discharge etc.The fiber that is activating agent as anti-charged method principal component carries out surface treatment with anti-live agent.Modes such as dipping, spraying are adopted in this surface treatment.Anti-live agent is divided into hygroscopic agent and surfactant substantially, and hygroscopic agent damage treatment facility because of using the hygroscopic anti-live agent of tool in numerous kinds of surfactants, thereby hinders the hydrophobic polyacrylic WATER RESISTANCE of tool, hydraulic pressure in also hindering.When so utilizing anti-water, oil resistance agent processing resin, except anti-water, oil-resistant characteristic, also require complex functions such as anti-charging property.This importance of handling design is come on the scene gradually.Employed softener, anti-live agent are according to selecting obviously to reduce WATER RESISTANCE.Absorptive anti-live agent of apparatus or softener add man-hour, obviously reduce WATER RESISTANCE, increase use amount and also are difficult for improving anti-water, grease resistance.Therefore, in order to improve anti-water effect, according to WATER RESISTANCE performance, cross-linking method and give in the Compound Machining of other functions and during with other medicaments, need not reduce the technological design of water repelling property.
From these viewpoints, when adding isopropyl alcohol, improve permeability when giving fluorine on the hydrophobic polypropylene nonwoven fabric and be water repellent agent, seldom reduce WATER RESISTANCE, therefore utilize the method usually, but keeping or use raw material, when especially adhering to through drying machine for heat in addition needs reclaim the device that evaporates etc.Therefore, requirement is at the countermeasure and the solution thereof of human body harmful's property, fire outburst, environmental pollution.
Summary of the invention
Therefore, the object of the invention is tool biological barrier characteristic is provided and suppresses the stable polypropylene multi-layer nonwoven fabrics for medical treatment of bacterium and other pollution sources infiltration.
Another object of the present invention is to provide and use superfine fiber high-density filter cloth material to make, microbial barrier effectively not only, and anti-water, anti-oil, resisting alcoholic are excellent, intercept blood and body fluid fully, anti-charging property and gas permeability excellence and wearing feeling is good, medical team is undergone surgery under the comfortable condition of health, thereby prevent infected polypropylene multi-layer nonwoven fabrics for medical treatment in hospital.
Another object of the present invention is to provide prevention human body harmful property, the environmental pollution of the medical polypropylene spun-bonded non-woven fabrics that has both anti-water, anti-oil, resisting alcoholic and anti-charging property, and the method that is easy to make.
To achieve these goals, polypropylene multi-layer nonwoven fabrics of the present invention is characterised in that, comprise the first spun-bonded non-woven fabrics stratum reticulare and the second spun-bonded non-woven fabrics stratum reticulare formed continuously by the polypropylene filament, and the 3rd melt spraying non-woven fabrics stratum reticulare that is inserted in the fine porous layer of an above hydrophobicity that prevents the bacterium intrusion between the above-mentioned first spun-bonded non-woven fabrics stratum reticulare and the second spun-bonded non-woven fabrics stratum reticulare and breathe freely, above-mentioned first and second spun-bonded non-woven fabrics stratum reticulare is that melt index MFR is 20~80g/10 minute a polypropylene, and above-mentioned the 3rd melt spraying non-woven fabrics stratum reticulare is that melt index is 800~1300g/10 minute a polypropylene.
According to the present invention, during as first and second spun-bonded non-woven fabrics stratum reticulare of above-mentioned formation, main material use melt index is 20~80g/10 minute a polypropylene foil.If melt index is lower than 20g/10 minute, melting viscosity is too high, and the result reduces at a high speed and makes a property, and on the contrary, melting viscosity is during greater than 80g/10 minute, and melting viscosity is crossed low and reduced spinnability, thereby can not carry out stable production.
And when forming the 3rd melt spraying non-woven fabrics stratum reticulare, main material use melt index is 800~1300g/10 minute a polypropylene foil.If melt index is lower than 800g/10 minute, melting viscosity too high and can not high speed spinning, extension, thereby can not form superfine fibre, can not bring into play the effect that intercepts bacterium or pollutant thus.On the contrary, melt index is during greater than 1300g/10 minute, and melting viscosity is low excessively, thereby the pressure in the extruder is low, has reduced spinnability.
According to a further aspect in the invention, above-mentioned first, second and third stratum reticulare is that masterbatch sheet by the highly enriched phthalocyanine blue dyestuff that drops into 1~5 weight % respectively forms.
Be the complementary color of the blood redness that flows out from the patient with operation affected part according to the blueness of the phthalocyanine blue dyestuff of the invention described above, when performing the operation for a long time, can eliminate the residual shape of blood and eliminate the fatigue of medical team.During insufficient investment 1 weight %, can not work.When drop into surpassing 5 weight %, in the time of high speed spinning foreign matter is arranged and reduce and make a property.
According to a further aspect in the invention, the basis weight of above-mentioned spunbond layer is respectively 10g/m at least 2, preferably about 10g/m 2~30g/m 2The weight of spunbond layer is lower than 10g/m respectively 2The time, can not protect the meltblown layer of central authorities, and intensity is low can not give morphological stability again.On the other hand, spunbond layer surpasses 30g/m respectively 2The time, the overall weight of central meltblown layer that drop into to intercept bacterium or other pollutants is overweight and sense of touch is hard, reduces wearing feeling.The basis weight of middle meltblown layer should be at least 5g/m 2, be lower than 5g/m 2Shi Buneng intercepts various bacteriums or polluter fully.
In order to realize other purposes of the present invention, the manufacture method of polypropylene multi-layer nonwoven fabrics for medical treatment is characterised in that and comprises the steps:
Melt index MFR is polypropylene foil main material fusion in extruder of 20~80g/10 minute, mixes, carry out melt spinning, cooling and extension process and form after the filament by spinning head, on the porous platform conveyer belt that moves continuously, form first, second spunbond web layer; With melt index MFR is that 800~1300g/10 minute polypropylene foil uses as main material, fusion in extruder, mix, by the spinning head melt spinning, extend in side nozzle spray silk, and form the 3rd with the polymer of concentrating at a high speed that adds the hot-air spinning with 1~5 μ m glass-coated microwire and melt and spray stratum reticulare, and lamination is the step of spunbond/meltblown/spunbonded layer;
Give the step of morphological stability with above-mentioned three stratum reticulares of calender heat bonding; And
The nonwoven fabric of giving above-mentioned morphological stability is immersed in the solution that has mixed oil resistance agent and anti-live agent, and carries out dry heat to handle and give the step of anti-water, anti-oil and anti-charging property.
According to other aspects of the invention, it is characterized in that, with respect to the weight of nonwoven fabric, oil resistance agent is coated in weight on the nonwoven fabric with solids content 0.4~5.0 weight % that is as the criterion, and anti-live agent is coated in weight on the nonwoven fabric with solids content 0.1~2.0 weight % that is as the criterion.
According to a further aspect in the invention, it is characterized in that oil resistance agent is an acrylic acid perfluoro alkyl ethyl copolymer, anti-live agent is an anionic sulphonate.
According to a further aspect in the invention, it is characterized in that, mixed in the solution of oil resistance agent and anti-live agent and also contained α-phenyl-ω-hydroxyl poly(ethylene oxide) compound.
According to a further aspect in the invention, it is characterized in that spinning head is made up of 3~6 casees (Beam), thereby constitute spunbond/meltblown/spunbonded three-decker, adding up in the spunbond layer both sides is 2 layers~4 layers structure, and central meltblown layer is 2 layers~4 a layers structure.
According to a further aspect in the invention, it is characterized in that nonwoven fabric weight is 40~70g/m 2, thickness is 0.1~0.7mm, spunbond rate is 10~30%.
According to a further aspect in the invention, the nonwoven fabric of making according to said method is used the sterilizing cloth use of Medical Devices such as valance, operation tool as protective clothing, operation cloth and the patient of medical team.
As the medical nonwoven fabric of the present invention of above-mentioned composition is that the inside that the polypropylene melt spraying super-fine-fiber is set between polypropelene fine silk spinning bonded non-woven fabrics net is the net of fiber shape, forms the multi-layer nonwoven fabrics of spunbond/meltblown/spunbonded three-decker after the compression.Both sides spunbond layer protection meltblown layer, and suitable intensity is provided, the stratum reticulare that melts and sprays of central authorities intercepts bacterium or other pollutants.And, during multi-layer nonwoven fabrics constructed in accordance, the mutual thermal of each nonwoven layer and form single Fabric composites.General thermal is with the calender of nonwoven layer by heating, the meltblown layer of partial melting inside, and be combined into composite.Therefore, when inabundant fusion of meltblown layer and fusion, reduce the interlayer adhesion of Fabric composites.And when correctly not adjusting the thermal condition, thermal zone superheated can produce the aperture that destroys inner meltblown layer biological barrier characteristics.Therefore, the actual thermal condition of using should satisfy the biological barrier characteristics as adhesion between sustaining layer.
And as mentioned above, polypropylene spun-bonded/meltblown/spunbonded multi-layer nonwoven fabrics that tradition is made has a water resisting property because of its hydrophobicity, but nonreactive oil, resisting alcoholic and anti-charging property, thus improper medical supplies use as hospital.The present invention is in order to address this problem, and carries out anti-water, anti-oil processing as above-mentioned.Anti-water, anti-oil processing are because the polypropylene fibre surface does not have repulsive force to alcohol and oil component, so change fiber surface character in order to repel mutually.Anti-water, oil resistance agent should not hinder other existing characteristics attached to after the polypropylene spunbond fibers surface, such as intensity, percentage elongation, interior hydraulic pressure, gas permeability etc.In order to give anti-charging property, use the raw material that changes character when making nonwoven fabric, or on nonwoven fabric, carry out the processing second time.When changing raw polymer, according to the high temperature of polymer fabrication processes, the activating agent of use and other additives, polymer monomers are decomposed easily.The anti-live agent that is dispersed in polymer inside exposes from the teeth outwards, and the performance effect need consume for a long time, thereby reduced effect.Therefore, anti-oil adds and adds anti-live agent man-hour and solve problem.The aqueous anti-live agent that uses has hydrophily product and hydrophobicity product.When using the hydrophilic surfactant active, hinder the WATER RESISTANCE of hydrophobic polypropylene, the damage treating apparatus.Therefore, use the hydrophobicity anti-live agent, can solve the problem of only obstruction WATER RESISTANCE of polypropylene and interior hydraulic pressure, thereby make the polypropylene multi-layer nonwoven fabrics of WATER RESISTANCE and anti-charging property excellence.At this moment, use above-mentioned anti-water, oil resistance agent, anti-live agent to add man-hour, be difficult for being penetrated in the hydrophobic polypropylene non-woven fabric, therefore use bleeding agent, but the isopropyl alcohol that in the past uses exists as above-mentioned problem.To this, the present invention's use as implied above α-phenyl-ω-hydroxyl poly(ethylene oxide) compound is as bleeding agent, thereby improve the osmotic effect of anti-water, oil resistance agent and anti-live agent, good economy performance is provided thus, no human body harmfulness and environmental pollution, keeping be dangerous little action effect such as fire outburst when using.
When being applicable to medical aspect as the nonwoven fabric of the present invention of above-mentioned manufacturing, the complete liquid barrier of superfine fibre meltblown layer, thereby do not have infect dangerous, protect patient and surgical team effectively.Between patient skin and operation cloth, form the air-isolation layer and the tool heat insulation effect, thereby can obtain technology and function matches, alleviate surgical team's burden, obviously save the polypropylene spun-bonded non-woven fabrics of the unnecessary energy and washing expense simultaneously.
Description of drawings
Fig. 1 is the cross-section photograph of medical polypropylene multi-layer compound nonwoven cloth constructed in accordance.
Fig. 2 is that schematic diagram is according to the manufacturing installation of medical polypropylene filament multi-layer composite nonwoven fabrics of the present invention and the ideograph of manufacturing technique thereof.
The specific embodiment
Followingly with reference to the accompanying drawings illustrate in greater detail the present invention.
Fig. 1 is a polypropylene multi-layer nonwoven fabrics of the present invention, the cross-section photograph of promptly spunbond/meltblown/spunbonded, and Fig. 2 is the summary ideograph according to the manufacturing equipment of polypropylene multi-layer nonwoven fabrics for medical treatment of the present invention and manufacturing technique thereof.
With 10 li storages of raw material bin spunbond with acrylic resin be transplanted on measure first, second stratum reticulare manufacturing with spunbond unit A and B partly the raw material measurement mechanism 11,11 of each raw material ', by a certain amount of be fed to extruder 12,12 '.And, have color masterbatch also to be fed to other raw material measurement mechanisms respectively, and by a certain amount of be fed to extruder 12,12 '.Main material and color masterbatch melting mixing in extruder is arranged during by the multi-holed jet spinning, just becomes the glass-coated microwire of 20~30 μ m.The polymer of spinning is cooled, solidifies by the cooling air of honeycomb shape quenching chamber 14,14 ' injection, is extended according to upper air with at platform conveyer belt bottom inhaled air pressure, is stacked on the platform conveyer belt that moves continuously by constant weight.First and second stratum reticulare basis weight separately is at least about 10g/m 2, 10g/m preferably 2To 30g/m 2The weight of first and second stratum reticulare is lower than 10g/m respectively 2The time, can not protect the meltblown layer of central authorities, and intensity is low can not give morphological stability again.On the other hand, the weight of first and second stratum reticulare surpasses 30g/m respectively 2The time, the overall weight of central meltblown layer that drop into to intercept bacterium or other pollutants is too high and sense of touch is hard, reduces wearing feeling.The stratum reticulare that melts and sprays with the polypropylene superfine fiber composition is set between the spun-bonded non-woven fabrics stratum reticulare, forms the multi-layer nonwoven fabrics of three-decker after the compression.Outside spunbond layer provides suitable intensity in order to protect nonwoven fabric.Central authorities' meltblown layer intercepts bacterium or other pollutants.That is, be stored at melting and spraying of another raw material bin (omitting diagram) and be transplanted on measurement the 3rd stratum reticulare manufacturing raw material measurement mechanism 11 that melts and sprays unit C part material with main material ", by a certain amount of extruder 12 that is fed to ".And, have color masterbatch also to be transplanted on other raw material measurement mechanisms, by a certain amount of extruder 12 that is fed to ".Main material and masterbatch melting mixing in extruder, by the multi-holed jet spinning, and the concentrated heated air (being generally gas) of high speed of running into nozzle discharge from the side.This high-velocity heated gas extends through the polymer of minute aperture spinning, and the polymer of extension forms the meltblown layer of 1~5 μ m superfine fibre.This 3rd melts and sprays the stratum reticulare basis weight and is at least 5g/m 2Be lower than 5g/m 2The time, thin thickness and can not intercept various bacteriums or pollutant fully.For first, second and third stratum reticulare such as Fig. 1 are arranged, with as the device of Fig. 2 arrangement operate and form spunbond/sandwich construction composite of melting and spraying/melting and spraying.In order to give mechanical characteristic and morphological stability to stratum reticulare, with heat and pressure combination.At this moment calender one side is that bonding rate is 10~30% knurling rolls, and opposite side is ganoid straight plate.Calender pressure at this time is 50~100dyne/cm, and temperature is 130~170 ℃.When making the fabric of form like this, the mutual thermal of each nonwoven layer and form single Fabric composites.Generally, thermal is with the calender of nonwoven layer by heating, optionally the meltblown layer of fused inner and be combined into the nonwoven layer of composite.The fusion of meltblown layer and fusing when insufficient weakens the adhesion of composite interlayer.And, when the thermal condition is incorrect, thermal zone superheated, thus can produce the aperture that destroys inner meltblown layer biological barrier characteristics.Therefore, the actual thermal condition of using should satisfy the biological barrier characteristics as adhesion between sustaining layer, and determines bonding rate and temperature, pressure.The basis weight of multi-layer nonwoven fabrics is 30~80gsm, preferably 40~70gsm.When basis weight was lower than 30gsm, morphological stability and intensity were low, reduced the barriering effect of pollution sources.When being higher than 80gsm, the flexibility and (drape) property of dangling are bad, not only reduce gas permeability, and economic impacts are not good.
In order to give as the anti-water of the product of above-mentioned production, anti-alcohol, grease resistance and anti-charging property, coating oil resistance agent and anti-live agent.Anti-water processing is different with the waterproof processing of broad sense.Anti-water processing is to make fiber molecule directly in conjunction with hydrophobic group with lyophobic dust covering fabric fiber or according to chemical reaction, and prevents the processing of water-wet.Attached to fiber surface, freely pass through in the space between chamber and the chamber by so the space of gases such as air or steam between fiber with filminess for water repellent agent.So not wet water is that the WATER RESISTANCE (hydrophobicity) according to water repellent agent realizes.Because of fiber and fiber, there is the space between chamber and the chamber, when WATER RESISTANCE well also was applied to pressure in the water again, water was penetrated into fibrous inside and seepage, and these waterproof processing with broad sense are different.The contact angle of fibrous material and water is cotton: 59 °, wool: 81 °, artificial silk: 38 °, nylon: 64 °, terylene: 67 °, acrylonitrile: 53 °, and polypropylene: 90 °.When contact angle is 180 °, be complete non-wetted state, when contact angle is 0 °, complete wetting.Add man-hour as the hydrophilic fiber fabric of cotton or artificial silk actual, the reason that WATER RESISTANCE reduces is that the contact angle of first being processed fiber itself is little.Polypropylene is that contact angle is big as mentioned above without the also excellent reason of processing WATER RESISTANCE.
The aeration that anti-water processing does not hinder the nonwoven fabric lining with the necessary condition of resin, form the big hydrophobic layer of contact angle on the fiber surface, the water that touches is become droplet, lyophobic dust answers firm attachment on fiber, can process medicament and usefulness with other, and the tool sense of touch is improved effect or not damaged, do not produce phenomenons such as foul smell, intensity reduction, flavescence, do not influence dyefastness, do not have hard silk and change, be difficult for being acted upon by temperature changes etc.
The water repellent agent that fiber product uses is classified as follows, be divided into solvent system and water system according to working fluid dilution medium difference, be divided into provisional water repellent agent and permanent water repellent agent according to water repelling property, be divided into thermoplasticity and thermosetting according to anti-water property of thin film, and influence classification such as sense of touch according to the main component and the water repellent agent of water repellent agent.The kind of anti-water processing agent and its typical structure have Methyl Hydrogen Polysiloxane Fluid (methyl hydrogen polysiloxane) resinae, contain the copolymer fluorine class of perfluoroalkyl, wax class such as paraffin, zirconates class such as aliphatic acid zirconates, ethylene unit class such as octadecyl ethylene urea, methylol amide class such as N-methylol stearmide, pyridine salt such as stearyl amidomethyl pyridinium chloride thing (stearamido methylpyridinium chloride), metallic soap class such as aluminum stearate etc.The factor that influences processing effect is resin concentration, condition of cure and catalyst type etc.Generally under the condition of using catalyst, use heat treatment on fiber surface, to form resin film, thereby obtain excellent WATER RESISTANCE.
Kind time-like by structure division water repellent agent has following kind:
Paraffin: C nH 2n+1
Fatty acid amide: C nH 2n+1CONHCH 2OH
Alkyl ethylidene unit:
The resin system water repellent agent:
Figure A20071013768700132
Fluorine is a water repellent agent:
Figure A20071013768700133
Wherein, paraffin is water repellent agent with the longest history, and fatty acid amide, ethylidene unit have been introduced reactive group in order to improve durability, and their WATER RESISTANCE is identical with paraffin, according to the alkyl performance performance of residual chain.Silicon is that water repellent agent is a kind of silicones of silicone oil, and methyl is arranged in the outside on the fiber, seemingly has a water resisting property with paraffin class.Silicones also comprises dimethyl silicone polymer and its modified product, and they generally use as the soft-touch agent of fabric, also mixes a part for the sense of touch of improving silicone oil system and uses.Fluorine is that water repellent agent is the copolymer of perfluoroalkyl acrylate, and they have than silicon is low etc. the characteristics of WATER RESISTANCE, the atypia of water repellent agent excellence, and key is to possess grease resistance in addition.Because of the present invention needs anti-alcohol, grease resistance, used acrylic acid perfluoro alkyl ethyl based copolymer (solids content 30%) product of fluorochemical as oil resistance agent.With emulsion state processing fiber, the mode of forming when making emulsion and mixing is divided into monomer substantially and mixes and mixed with polymers with resin in processing.Recently, generally use mix monomer to heat-treat the method for reaction.
Carry out on fibrous material after the water repellent agent processing, in order to improve durability, the bonding force that improves fiber and water repellent agent is very important.The power that works between fiber and water repellent agent can be divided into molecular separating force (Fan Dewaersi (Van Der Waals) power) and chemical bond.Molecular separating force be when fluorine be water repellent agent processing on fiber, and the reason of performance water repellent agent, the ester group (perfluoroalkyl) that contains fluorine and fiber be the WATER RESISTANCE of only having by the vertical direction location, the core acrylic acid residue of fluororesin helps the adhesion with fiber.The former is called anti-water base, and the latter is called bonding base.And carbon fluorine chain is compared hydrocarbon chain and is had very high surface-activity and obviously reduce surface free energy.Therefore, obtain excellent anti-water, anti-oily effect.That is usefulness-CF, 3Or-CF 2When covering fiber surface, its surface contact angle is than usefulness-CH 3Or-CH 2The surface that covers is bigger.Anti-water, grease resistance method for expressing as the surface of solids utilize wetting critical surface tension (γ c, dyn/cm) (below use γ cExpression).The fluorine of having represented the processing fiber of one of basic structure below is anti-water, oil resistance agent.
Figure A20071013768700141
This structure is that cyanogen fluoroalkane tethers utilizes hydrocarbon system main polymer chain (being polypropylene acid type main polymer chain) to get involved the form that ester bond gets here.Said structure is made emulsion polymers, γ with the emulsifying agent emulsion polymerization cBe 10.4dyn/cm, with polyethylene γ cBe 31, polyvinyl chloride γ cWhen being 39 comparisons, obviously low.When representing fluoroalkyl with Rf, the Rf end is-CF 3, the most difficult wetting and have stronger anti-water, grease resistance.At this moment-CF 3γ cBe 6.0dyn/cm.So substantially, making fluorine with acrylic copolymer (being generally the β polyacrylate) as the center as side chain with perfluoroalkyl is anti-water, oil resistance agent, in order to strengthen these performances, can consider check with this body structure of polymer, copolymer is selected, make the check of the relevant polymer Tg composition of film, according to strengthening as the adhesion of the bonding force reinforcement of the plastic links of main chain, assistant, additive, crosslinking agent, effectively cross-linking reaction is utilized method etc.
When utilizing anti-water, oil resistance agent processing resin, except anti-water, oil-resistant characteristic, also require complex functions such as anti-charging property.This importance of handling design is come on the scene gradually.WATER RESISTANCE is lowered according to the softener, the anti-live agent that at this time use.Utilize absorptive anti-live agent of tool or softener to add man-hour, obviously reduce WATER RESISTANCE.Increase use amount again and also be difficult for improving anti-water, grease resistance.Therefore, in order to improve anti-water processing effect, according to WATER RESISTANCE performance, cross-linking method and give in the Compound Machining of other functions and during with other medicaments, need not reduce the technological design of water repelling property.Because water repellent agent partly has water imbibition, should confirm before therefore using.And for the uniformity at resin padding mangles (padder mangle) liquid level, liquid should be without interruption a certain amount of.The alcohols such as isopropyl alcohol that use as bleeding agent improve permeability when the processing fluorine is water repellent agent on the hydrophobic polypropylene nonwoven fabric, WATER RESISTANCE is influenced little and general selected use.But, for keeping raw material or use, especially adhere to for heat, need retracting device in addition because of reasons such as evaporations during by drying machine.Also need to solve human body harmful's property, fire outburst, environmental pollution problems.So, above-mentioned bleeding agent uses the α-phenyl-ω-hydroxyl poly(ethylene oxide) compound of no potential danger, improve the osmotic effect of anti-water, oil resistance agent and anti-live agent, good economy performance, no human body harmfulness and environmental pollution, when keeping is used, danger such as no fire outburst, thereby the stability that realization is produced.
Anti-live agent because of the tool hydrophobicity as medical better.At this moment, when anti-live agent uses general surfactant or hygroscopic agent, because of losing the intrinsic WATER RESISTANCE of polypropylene, and possess water imbibition, treating apparatus is got rusty etc., will damage treating apparatus.Anti-live agent mainly is divided into anionic species, cationic, nonionic class and both sexes class.Wherein anionic species, the general use of nonionic class are preventing in the charged processing.Generally, cationic and both sexes class are few as the situation that spinning, weaving emulsion composition use, but use as the anti-live agent of final tool product flexibility.
Have as anionic species:
Sulfonate type: RSO 3Na,
Sulfuric acid type: ROSO 3Na, ROSO 3NH (CH 2CH 2OH) 3Na, RO (CH 2CH 2O) SO 3Na,
The phosphate ester salt type:
Figure A20071013768700161
Deng.
The phosphate ester salt type has excellent anti-charging property, therefore mixes use separately or with other medicaments.There are much relations the position of carbon number, sulfuric acid, phosphoric acid and the hydrophilic group of the fatty group in the charging preventive property of the product of generally, sulfuric ester salinization, phosphate salinization and the anti-live agent molecular structure etc.
Have as cationic:
Amine salt type: RNH 2CH 3COOH,
Quaternary: (RCONHC 3H 6N (CH 3) 2CH 2CH 2OH) X (X=NO 3, ClO 4) etc.Because of preventing charging property, also using on after-processing technology with property, excellent the passing through of flexibility.But, molecule contain that nitrogen can cause since oxidation painted, because the salt obstacle of salt bleaching, have the problem of pollutions, adsorbing metal ions etc. and should note use.
The nonionic class generally absorption affinity to fiber is little, and slickness is good and synthetic fiber are had uniform wettability.
Polyoxyethylene fatty acid ester type: R-COO (CH 2CH 2O) nH
Polyoxyethylene alkyl ether type: RO (CH 2CH 2O) nH
Alkylphenol polyoxyethylene type and polyoxyethylene alkyl amine type etc. use as the weaving emulsion of synthetic fiber usually.
On the other hand, the zwitterionic classes that contains CATION, two kinds of polarity of anion with molecule has performance and the sense of touch excellence and the few characteristic of chlorine obstacle of two kinds of ionic species, be divided into betaine (betaine) type and imidazoline type, the general betaine types that use more.The flexibility of durability anti-live agent or excellent heat resistance, the hard silk of nothing changes, and does not reduce dyefastness, and can also use resin finishing agent or anti-water, oil resistance agent, requires to continue dustless.Durability anti-live agent major part is bibulous cationic macromolecular compound or electrolyte macromolecular compound, such as, polyacrylic acid derivative, polyvinylamine derivative, polyamide derivative and amphion resinoid etc.Wherein be typically the polyacrylic acid derivative of tool zwitterionic classes side chain, handle poly-(Beta-methyl acryloxy) ethyl diethylmethyl sulfate methyl ammonium (Poly-β-methacryloxy ethyldiethylmethylAmmonium Metasulfate) on the fiber afterwards, carry out after the post processing with anion active agent, form the method for compound (complex) on the fiber, handle the method for disperseing this synthetic with tween, the polyamine and crosslinking agent and the usefulness that contain poly(ethylene oxide), and the processing fiber forms three-dimensional twine structure according to heat treatment on fiber surface.
As mentioned above; in order to prevent that medical team's clothes and patient that medical team and patient use in inside-hospital infection from using the coverlet class; main purpose for the pollution sources protection; carry out anti-oil, the processing of anti-water; for the electrostatic protection Medical Devices; the attached purpose of sense comfortable and easy to wear is prevented charged processing, and can not absorb water.Therefore, the anti-live agent that uses has in the present invention used hydrophobic anion class sulfonate product (solids content 20%).In the solution of pressing certain ratio mixing oil resistance agent and anti-live agent (bath) lining immersion non-woven fabrics and evenly coating, utilize air drier to carry out drying, obtained the nonwoven fabric of anti-oil and anti-charging property after the heat fixation.
With respect to the weight of nonwoven fabric, oil resistance agent is as the criterion with solids content and handles by 0.4~5.0 weight %, and anti-live agent is as the criterion with solids content and handles by 0.1~2.0 weight %.With respect to the weight of nonwoven fabric, the solids content of oil resistance agent and anti-live agent is respectively when surpassing 5.0 weight %, 2.0 weight %, and nonwoven surface is really up to the mark, even it is also very small to increase the effect of use amount grease resistance and anti-charging property.On the other hand, oil resistance agent with respect to the weight of nonwoven fabric with the solids content less than 0.4 weight % that is as the criterion, when anti-live agent is as the criterion less than 0.1 weight % with respect to the weight of nonwoven fabric with solids content, its effect can not be brought into play respectively, thereby grease resistance of the present invention and anti-charging property can not be embodied.
And, be easy to be penetrated into nonwoven fabric inside in order to make medicament, use α-phenyl-ω-hydroxyl poly(ethylene oxide) compound as bleeding agent, and be as the criterion with solids content and handled 0.1~2.0 weight % with respect to the weight of nonwoven fabric.Bleeding agent less than 0.1 weight % or when surpassing 2.0 weight %, nonwoven fabric is not easy infiltration in tank liquor, or too much reduces the grease resistance performance.The nonwoven fabric that is immersed in tank liquor need be adjusted mangle (pick-up) rate because of padding mangles pressure, and suitable pick-up rate is adjusted pressure remains on the nonwoven fabric above-mentioned solids content.At the air drier inner drying nonwoven fabric that moves continuously, when bringing into play the effect of anti-oil and anti-live agent, the temperature range of air drier is 130~150 ℃.Drying is insufficient during 130 ℃ of less thaies, thereby can not embody grease resistance, and temperature is crossed low and reduced productivity.On the other hand, improve temperature when surpassing 150 ℃ and polyacrylic fusing point, cause the non-woven fabric net thermal change, in drying machine, melting or the surface changes and becomes very hard the closer to 160 ℃.At this moment because of inner meltblown layer is melting the effect that loses as Obstruct membrane, can not satisfy the flexibility of operation dress and fabric (drap) class and wearing feeling is poor.
Following embodiment and comparative example are to illustrate in greater detail the present invention, but do not limit the scope of the invention.Various characteristics pH-value determination pH in embodiment and the comparative example and estimate following carrying out.
[evaluation method]
(1) tensile strength: utilize the Instron sensing equipment, according to ASTM D1682-64 method, the clamping spacing is 10cm, and anti-Zhang Sudu is the anti-amplitude 5cm of opening under the 500mm/min condition, the test film of spacing 20cm, and calculate peak load.
(2) the anti-percentage elongation of opening: the percentage elongation in the time of anti-the opening of maximum measured by the method for (1).
(3) weight per unit area (weight: g/m 2): measure according to ASTM D 3776-1985 method.
(4) interior hydraulic pressure (mmH 2O): according to low hydrostatic(al) process (the hydraulic pressure 60cm H of FTMS-191A-5514 2O) measure.
(5) gas permeability (cm 3/ cm 2S): measure according to ASTM D 737.
(6) anti-charging property:
1) frictional electrification is pressed: according to KS K 0555-1983 B method, and 20 ± 2 ℃ of temperature, humidity 40 ± 2%RH, 400RPM analyzes with cotton.
2) sheet resistance: testing equipment TOA, SME-8311 D1=1.96cmD2=2.41cm, rated voltage 500VOLT, 60 seconds, 20 ± 2 ℃ of temperature, humidity 40 ± 2%RH measures according to ASTM D 257 methods, and prevents charging property according to the standard determination as following table 1.
Table 1
Sheet resistance (ω/cm) Electrification phenomenon Judge
10 13< 10 13~10 12 10 12~10 10 10 9~10 6 10 6~10 3 The savings electrostatic charge reduce gradually after charged reduce immediately after charged charged hardly not charged fully Bad bad good
(7) anti-water, grease resistance (grade): the oil test liquid (oil testliquid) that has utilized market sale.The nonwoven fabric test portion is placed on the horizontal surface after smooth.Begin on test portion at least by 2 cun spacing drops 5 times from inferior grade liquid, after miter angle observed for 10 seconds, four are considered as when being shown as sphere or hemispherical by test in five globules, after high-grade liquid such as above-mentioned the test, and the highest ranking that record passes through.
(8) bacterium sees through inhibiting rate: will test test portion and press after the diameter 48mm intercepting, and put into one of filter paper in the Petri dish of sterilization.Bacterial strain concentration is adjusted into 3.0~8.0x10 5After/the ml, test drop 0.5ml experimental liquid on the test portion, and disperse to be placed on above the steel disk in order to be easy to.At this moment absorb bacterium liquid under filter paper being placed on the test test portion.Used ATCC 6538 staphylococcus aureuses (staphylococcus aureus) bacterial strain at this.At 37 ℃, after RH90% cultivated 24 hours, measure the bacterial population above the filter paper.
Embodiment 1
Spunbond main material of the present invention is that characteristic is 35g/10 minute a polypropylene of melt index (MFR), in order to embody blueness, drops into the masterbatch sheet 3 weight % of highly enriched phthalocyanine blue dyestuff.Melting mixing main material and masterbatch sheet in extruder after spinning head formation filament, with the cooler cooling, suck air with the conveyer belt bottom and extend, and form first spunbond web layer and second spunbond web layer respectively on the continuous platform conveyer belt that moves.Melting and spraying characteristic is 1000g/10 minute polypropylene of melt index (MFR), the same blue masterbatch tablet that used with spunbond layer.Melting mixing main material and masterbatch sheet in extruder by the spinning head spinning of porous, and extend polymer, and the polymer that is extended forms by 1~5 μ m glass-coated microwire and melts and sprays stratum reticulare.The 3rd to melt and spray stratum reticulare be double-layer structure, and two-layer basis weight is 8g/m 2First, second stratum reticulare is at least three-decker, and it is 50g/m that formation comprises the gross weight that melts and sprays stratum reticulare 2Spunbond/meltblown/spunbonded multi-layer nonwoven fabrics net.So the net that forms is 158 ℃ at knurling rolls, and straight plate is 156 ℃, and pressure is to carry out hot compression under the calender condition of 78dyne/cm to give morphological stability.The bonding rate of knurling rolls is 11%.In order to give grease resistance and to prevent charging property on spunbond/meltblown/spunbonded multi-layer nonwoven fabrics, acrylic acid perfluoro alkyl ethyl analog copolymer (solids content 30%) oil resistance agent and p-methyl benzenesulfonic acid sodium salt (solids content 20%) anti-live agent are blended in 940 weight parts waters by 40 weight portions, 10 weight portions and α-phenyl-ω-hydroxyl poly(ethylene oxide) compound (solids content 30%) 10 weight portions respectively, be immersed in the tank liquor without interruption, the solids content standard is oil resistance agent 1.2 weight %, the OPU of anti-live agent 0.2 weight % (rate oils).Nonwoven fabric is handled 36sec/m in 135 ℃ of air driers that move continuously, made the medical polypropylene non-woven fabric of anti-water, anti-oil and anti-charging property excellence.Above-mentioned each production and processing conditions are shown in table 2, and physical property is shown in table 3.
Embodiment 2
Removing the nonwoven fabric overall weight is 60g/m 2, the temperature of air drier is beyond 145 ℃, and is identical with embodiment 1.Condition and physical property are shown in table 2, table 3.
Comparative example 1
Remove as bleeding agent and use isopropyl alcohol 40 weight portions, make beyond water 910 weight portions, identical with embodiment 1.Condition, physical property are shown in table 2, table 3.
Comparative example 2
Remove as bleeding agent and use α-phenyl-ω-hydroxyl poly(ethylene oxide) compound (solids content 30%) 1 weight portion, make water 949 weight portions, and the bleeding agent solids content becomes beyond the 0.03% standard adhesive rate, identical with embodiment 1.Condition, physical property are shown in table 2, table 3.
Comparative example 3
Remove as bleeding agent and use α-phenyl-ω-hydroxyl poly(ethylene oxide) compound (solids content 30%) 70 weight portions, make water 880 weight portions, and the bleeding agent solids content becomes beyond the 2.1% standard adhesive rate, identical with embodiment 1.Condition, physical property are shown in table 2, table 3.
Comparative example 4
Identical with the use and the working condition of embodiment 1 nonwoven fabric main raw material, do not resist oil, prevent charged processing.Condition, physical property are shown in table 2, table 3.
Table 2 nonwoven production and processing conditions
Figure A20071013768700221
( *1) acrylic acid perfluoro alkyl ethyl analog copolymer oil resistance agent
( *2) paratoluenesulfonic acid sodium salt salt anti-live agent
( *3) α-phenyl-ω-hydroxyl poly(ethylene oxide) compound bleeding agent
( *4) isopropyl alcohol
The physical property of table 3 processing back nonwoven fabric
Figure A20071013768700231
◎: good, △: general, X: bad
Industrial applicability
As mentioned above, polypropylene multi-layer nonwoven fabrics for medical treatment of the present invention forms the multi-layer nonwoven fabrics of spun-bonded/melt-blown/spunbond three-decker, and the spunbond layer protection meltblown layer of both sides also provides suitable intensity. The meltblown layer of central authorities intercepts bacterium or other pollutants. Use α-phenyl-ω-hydroxyl PEO compound as bleeding agent, improved the osmotic effect of anti-water, oil resistance agent and anti-live agent, good economy performance simultaneously, without human body harmfulness and environmental pollution, keeping, when using without danger such as fire outbursts. When being applicable to medical aspect, the complete liquid barrier of superfine fibre meltblown layer, protection patient and surgical team are dangerous without infecting. Form the air layer of isolation between patient skin and the operation cloth and the tool heat insulation effect. Alleviate surgical team's burden thereby the technology of providing and function match, save simultaneously the polypropylene spun-bonded non-woven fabrics of the unnecessary energy and washing expense.
Description of reference numerals
10: raw material bin (silo)
11,11 ', 11 ": raw material measurement mechanism (dosing unit)
12,12 ', 12 ": extruder (extruder)
13,13 ', 13 ": Spinning pumps (spin pump) and manifold (spin beam)
14,14 ': quenching chamber (quenching chamber)
15,15 ': center-aisle (intermedeate channel)
16,16 ', 16 ": induced-draught fan (suction blower)
17: reticular zone (screen belt)
18: calender (calender)
19: winder (winder)

Claims (7)

1. the manufacture method of polypropylene multi-layer nonwoven fabrics for medical treatment is characterized in that comprising the steps:
Melt index MFR is polypropylene foil main material fusion in extruder of 20~80g/10 minute, mixes, carry out melt spinning, cooling and extension process and form after the filament by spinning head, on the porous platform conveyer belt that moves continuously, form first, second spunbond web layer; With melt index MFR is that 800~1300g/10 minute polypropylene foil uses as main material, fusion in extruder, mix, by the spinning head melt spinning, extend in side nozzle spray silk, and form the 3rd with the polymer of concentrating at a high speed that adds the hot-air spinning with 1~5 μ m glass-coated microwire and melt and spray stratum reticulare, and lamination is the step of spunbond/meltblown/spunbonded layer;
Give the step of morphological stability with above-mentioned three stratum reticulares of calender heat bonding; And
The nonwoven fabric of giving above-mentioned morphological stability is immersed in the solution that has mixed oil resistance agent and anti-live agent, and carries out dry heat to handle and give the step of anti-water, anti-oil and anti-charging property.
2. according to the manufacture method of claim 1, it is characterized in that, weight with respect to nonwoven fabric, described oil resistance agent is coated in weight on the nonwoven fabric with solids content 0.4~5.0 weight % that is as the criterion, and described anti-live agent is coated in weight on the nonwoven fabric with solids content 0.1~2.0 weight % that is as the criterion.
3. according to the manufacture method of claim 1, it is characterized in that described oil resistance agent is an acrylic acid perfluoro alkyl ethyl copolymer, described anti-live agent is an anionic sulphonate.
4. according to the manufacture method of claim 1, it is characterized in that, also contain α-phenyl-ω-hydroxyl poly(ethylene oxide) compound in the described solution that has mixed oil resistance agent and anti-live agent.
5. according to the manufacture method of claim 1, it is characterized in that spinning head is made up of 3~6 casees, thereby constitute spunbond/meltblown/spunbonded three-decker, adding up in the spunbond layer both sides is 2 layers~4 layers structure, and central meltblown layer is 2 layers~4 a layers structure.
6. according to the manufacture method of claim 1, it is characterized in that nonwoven fabric weight is 40~70g/m 2, thickness is 0.1~0.7mm, spunbond rate is 10~30%.
7. according to the manufacture method of claim 1, wherein the nonwoven fabric of manufacturing uses the sterilizing cloth of valance, Medical Devices to use as protective clothing, operation cloth and the patient of medical team.
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