CN1080780C - Easily fibrillable fibre - Google Patents
Easily fibrillable fibre Download PDFInfo
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- CN1080780C CN1080780C CN96195692A CN96195692A CN1080780C CN 1080780 C CN1080780 C CN 1080780C CN 96195692 A CN96195692 A CN 96195692A CN 96195692 A CN96195692 A CN 96195692A CN 1080780 C CN1080780 C CN 1080780C
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Abstract
The present invention relates to a fiber with a sea-island phase separation structure, wherein the sea component comprises vinyl alcohol base polymers with high orientability and high degree of crystallization, and the island component comprises water-insoluble cellulose polymers with excellent absorption rate of alkaline solutions, good heat resistance and good hot melt resistance; the dimension of the island is 0.03 to 10 mu m, and the intensity is 3 g/d or larger than 3 g/d when mechanical stresses act on the wet fiber in water, the fiber is easy to split into original fibers with 0.05 to 8 mu m of the diameter. The present invention also has favorable absorption rate of alkaline solutions, very high heat resistance and high hot melt resistance besides having the original fibers with good hydrophilicity, high strength, collection performance for large granules and very good enhancement performance, and any component in the fiber during the before-fibrillation period can not be dissolved; both of the pulping technology and the pulping solution do not result in blistering or environmental pollution, and the original fiber is specifically suitable for diaphragms of alkaline cells, enhancement fibers of cement stone plates, enhancement fibers of friction materials, etc.
Description
Background of invention
Invention field
The present invention relates to comprise the fiber of the easily fibrillable of polymer based on vinyl alcohol (below be abbreviated as " PVA ") and cellulosic polymer; More specifically, the present invention relates to fiber and fibrillation, therefore be characterised in that independent effect or its combination by chemical solution expansive force or mechanical stress can easily make described fiber become ultra-fine fibrillation, be preferred for wet or do barrier film in no latitude supatex fabric, the alkaline battery, be used for the fortifying fibre of friction material and be used for the increase fiber of cement products.
Prior art
The supatex fabric that contains the PVA fiber is commonly used for the barrier film of alkaline manganese battery by force because of alkali resistance.Along with the development of electronic information communication system, need carry out considerable improvement to the performance of battery in recent years, production and the processing aspect from pollution-free battery also needs mercury-free battery simultaneously.In addition, owing to need more high performance mercury-free battery, required more significant isolating power as the barrier film that is used for battery.Therefore, the PVA fiber of having prepared thinner dawn number is used for the barrier film of alkaline manganese battery, but the PVA fiber that 0.3 dawn was arranged that present market obtains.The PVA fiber of the thin dawn number of preparation simply, its as the barrier film of alkaline manganese battery very important performance---the absorptivity (being the absorption (weight) of the KOH aqueous solution) of alkaline solution is unsatisfactory.
For overcoming these problems, the barrier film that has used PVA fiber that comprises thin dawn number and the polynoise fiber that bigger alkaline solution absorptivity is arranged to make as a kind of mixture of cellulose fibre, described polynoise fiber can fibril changes into ultra-fine fibrillation by pulling an oar easily.Yet shortcoming is that polynoise fiber can cause public hazards in process of production.In addition, polynoise fiber has the core of so poor beatability so that fiber to become thick core in the gained fibrillation.Therefore, be difficult to obtain enough carefully be dispersed to such degree so that the also dispersed fibrillation of core.But thereby need fibril to change into ultra-fine fibrillation and higher alkaline solution absorptivity is arranged and higher alkali-proof PVA fiber.
Usually, as the various fortifying fibres that are used for the friction material of automotive brake and clutch disc, according to the capture performance of inorganic particle, heat resistance, refractoriness, enhancing etc. and opinion is used asbestos usually.Yet, since the health of asbestos possibility harm humans, the use of strict control asbestos.Thereby, replace asbestos with expensive aramid fibre fibrillation in recent years.Yet the cost of aramid fibre is high thereby only use with limited mode.Therefore, in fact use strengthen the property not enough lower cost materials such as natural pulp.So, need such fiber, but its cost is lower than aromatic polyamides and fibrillation, so that this fiber can obtain granule capturing performance, heat resistance, refractoriness and the combination of strengthening the property.
Asbestos are commonly used for the fortifying fibre of cement products such as slabstone, but are subjected to the control of strictness because of its application of aforesaid reason.The PVA fiber in cement because of bigger alkali resistance being arranged as the substitute of asbestos, but because the fiber size of PVA fiber is bigger than asbestos, low with the wet strength of this fibre-reinforced slabstone.For replenishing intensity, the fibrillation of this fiber and natural pulp etc. should be used in combination.But, then can save PVA fiber and natural pulp and be used in combination required common complicated work if there is the PVA fiber of any fibrillation.
In addition, for producing ultra-fine synthetic fiber, carried out the phenomenon of phase separation that a large amount of effort attempts to utilize polymer blend.For example, JP-B-10617/1974, JP-B-17609/1976, JP-A-56925/1973, JP-A-6203/1974 have described sea-island fiber respectively, comprise acrylonitrile polymer as the graft copolymer of sea component and PVA and acrylonitrile or methylmethacrylate polymer as the island component, can pass through beating method fibrillation.But these technology belong to the improvement technology of polyacrylonitrile as the so-called polyacrylonitrile fibre of sea component that comprise.The absorptivity of alkaline solution is good owing to the alkali resistance difference of polyacrylonitrile fibre, so this fiber need can not be used to fabulous application of these performances or the stable on heating application of needs.
JP-B-31376/1972 also discloses a kind of PVA fiber of easily fibrillable, comprise fully saponified PVA as sea component and partly-hydrolysed PVA as the island component, but this fiber has following defective: partly-hydrolysed water-solubility PVA is dissolved in the water that is used for fibrillation in pulping process, causes seriously bubbling during the making beating.
Summary of the invention
Therefore, be starved of a kind of like this PVA fiber, comprise the PVA that contains hydroxyl identical in the relatively large wood pulp with as sea component, lower because of the caused foaming degree of the dissolubility of fibre fractionation during pulling an oar, the ability of the fibrillation of being easy to, bigger alkaline solution absorptivity and/or higher heat resistance and refractoriness are arranged, and higher intensity is arranged.Yet, do not produce such fiber as yet.
In this case, the inventor finishes the present invention after deliberation at last.
The present invention relates to a kind of fiber of easily fibrillable of sea-island structure, comprise PVA (A) and water-insoluble cellulosic polymer (B), wherein A and B form sea component and the island component in the fiber cross section respectively, are characterised in that size average out to 0.03 μ m to the 10 μ m and the TENSILE STRENGTH on described island is 3g/d or bigger.
Detailed Description Of The Invention
In fiber of the present invention, PVA is a sea component.Reach purpose of the present invention and it is highly important that described sea component---be that continuous phase comprises such PVA: its strand can be easy to orientation and crystallization, can easily produce high-intensity fibrillation by it, it has higher alkali resistance and higher heat resistance, contains relatively large hydrophily hydroxyl with it in the mode identical with wood pulp.
PVA as referred to herein does not have particular restriction, as long as this PVA contains 70mol% or more vinyl alcohol units, comprise with ratio and monomer such as ethene, itaconic acid, vinylamine, acrylamide, new vinyl acetate acid, maleic anhydride that is lower than 30mol% and the vinyl alcohol that contains the vinyl compound copolymerization of sulfonic acid.Any vinyl alcohol from the saponification vinyl esters satisfies, and does not have particular restriction, as long as its saponification degree is 80mol% or bigger.But, be orientation and crystallization, the content of therein ethylene alcohol unit is preferably 95mol% or bigger, more preferably 98mol% or bigger, also more preferably 99mol% or bigger, most preferably 99.8mol% or bigger.
The degree of polymerization of PVA does not have particular restriction.Yet, be producing the higher fibrillation of intensity, the degree of polymerization is preferably 500 or higher, and more preferably 1500 or higher.For improving hot water resistance, in the postreaction after fiber production, PVA can be in molecule or carry out acetalation between this molecule and aldehyde compound (typically for example formaldehyde); Perhaps available crosslinking agent makes PVA crosslinked.
In fiber of the present invention, the water-insoluble cellulosic polymer is a described island component.The water-insoluble cellulosic polymer comprises cellulose itself, cellulose acetate such as cellulose diacetate and cellulose triacetate, celluloid and low water-insoluble cellulose such as methylcellulose, ethyl cellulose, hyetellose and the carboxymethyl cellulose that replaces is arranged.Wherein, cellulose is preferred, because fiber have higher alkaline solution absorptivity, low water-swellable, hydrophily and heat resistance and heat-resisting fusibleness; Cellulose acetate is preferred because its compatibility with PVA is low, the water absorptivity is low, heat-resisting and heat-resistingly melt, easily fibrillable particularly.The shortcoming of starch is that higher solubility is arranged is amorphous, so starch does not belong to water-insoluble cellulosic polymer class of the present invention.For example, make and be saponified into cellulosic cellulose acetate by reaction behind the fiber and can meet the demands; Particularly when the cellulose acetate as water-insoluble cellulosic polymer raw material was saponified into cellulose after polymer is made fiber, the fiber of gained was easy to fibrillation.Therefore, the most preferably this polymer according to the present invention.In case dissolved, cellulosic polymer had both become amorphous, so be difficult to make this polymer directional and crystallization so that polymer has higher intensity.For effectively utilizing the special performance of this polymer, promptly higher alkaline solution absorptivity, lower water-swellable with and heat resistance and heat-resisting fusibleness, importantly should make cellulosic polymer with the island component---the component form of promptly disperseing exists.
Preferably, the ratio on sea/island---the weight ratio that is the PVA/ cellulosic polymer is 95/5 to 50/50.Be lower than 5% cellulosic polymer as the island component, then fiber is difficult to fibrillation.Be lower than 50% sea component PVA, then cellulosic polymer partly forms sea component, thereby PVA can not form any tangible matrix phase, is difficult to produce the fibrillation of higher-strength.The weight ratio of PVA/ cellulosic polymer more preferably 90/10 to 52/48, also more preferably 80/20 to 55/45, most preferably 75/25 to 60/40.
The average-size on island is 0.03 μ m to 10 μ m.By the present invention, described island size is as giving a definition.Fiber of the present invention is made the ultra-thin section of fiber cross section then through making fiber give the technology of resistance to water.With osmium tetroxide dyeing, be amplified to 20000 to 60000 times with transmission electron microscope.On the cross-sectional picture of amplifying, determine the area on each island, the equivalent diameter of each circle of the same area in calculating and these islands.The island dimension definitions be the island equivalent diameter add and average.If average diameter is less than 0.03 μ m, then size too little so that this fiber in island is difficult to fibrillation; If the island size is greater than 10 μ m, then the gained fibrillation too big (in other words, fibrillation is too thick) so that this fibrillation can not play fibriilar basic role, this fibrillation also easily gives rise to trouble in the fiber production process in addition, and is unfavorable to disposal ability.The island is preferably dimensioned to be 0.1 to 6 μ m, more preferably 0.5 to 3 μ m.In fiber of the present invention, the shape of cross section on island is preferably non-circular or erose, because the sea component area that contacts with the island component is big so that fissile part increases, and produces the more fiber of easily fibrillable.
In addition, in fiber of the present invention, can have three-phase, wherein PVA is scattered in (in other words, the island is scattered in the island) in the island that comprises cellulosic polymer with satisfying condition.In the fiber of this three-phase structure, the island itself divides mutually, and this is effective to producing thinner fibrillation.
The fiber of easily fibrillable of the present invention should have 3g/d or higher TENSILE STRENGTH (hereinafter abbreviating " intensity " sometimes as).If intensity is lower than 3g/d, then fiber can not be used for application such as battery diaphragm, the fortifying fibre of friction material and the fortifying fibre of cement slabstone of desired strength.In addition, in general the fiber that intensity is lower is difficult to fibrillation, and this is disadvantageous.Described intensity is preferably 4g/d or higher, more preferably 5g/d or higher, also more preferably 7g/d or higher.According to the present invention, press the intensity that JIS L1015 measures fiber.It is 3g/d or higher fiber that following method produces intensity.
Fiber of the present invention preferably has 30 minutes or lower beatability.Term among the present invention " beatability " means the stirring and the beating time of following measurement: make fiber sample (4g) place the atmosphere of 20 ℃ and relative humidity 65%, sample is cut into the section of 2-mm, 20 ℃ water (400cc) are added in the section of chopping, and these broken section packed into by Matsushita Electric Industry, Co.Ltd. in the blender that (National MX-X40) makes, stir and the making beating certain hour with 11000rpm, take out the aqueous dispersion sample of making beating solution then, measure the drainage time of this solution by the following stated method, drainage time reaches required stirring in 60 seconds and beating time is called beatability.Term " drainage time " means by the 350-order metallic filter of opening graduated cylinder lower end, the end that is installed in diameter 63mm and filters aqueous dispersion (750cc) required time that contains the fibriilar making beating solution of 0.5 gram.
Making beating property is higher than 30 minutes, then fiber sometimes can not fibrillation when reality is used or fiber fibrillation inadequately consequently fiber may not be suitable for the target purposes.Much less in addition the fiber of fibrillation poor ability also may pass through some method fibrillation, comprise and prolong beating time or use harsher conditions of beating, but the fibrillation of Chan Shenging is under such state so that fibrillation tangles mutually or fibrillation further is cut into shorter section by this way, so this fiber is not suitable for the target purposes.Drainage time is 75 seconds or fiber for more time after more preferably pulling an oar 5 minutes, has the fiber of drainage time like this to be produced by the following stated method.Term " pull an oar after 5 minutes drainage time " means in making beating under the condition identical with above-mentioned measurement beatability and contains the fibriilar aqueous dispersion of 0.5g (750cc) is equipped with metallic filter by above-mentioned bottom graduated cylinder required time after 5 minutes.
Fiber preparation method of the present invention is described below.At first, importantly above-mentioned PVA (A) and water-insoluble cellulosic polymer (B) are dissolved in the common solvent.This organic solvent commonly used comprises the mixture of methyl-sulfoxide (below be abbreviated as " DMSO "), dimethylacetylamide and dimethyl formamide and slaine such as zinc chloride, if described cellulosic polymer is cellulose acetate or celluloid.With an organic solvent can help the gel spinning of PVA to produce the higher fiber of intensity.
Two kinds of polymer dissolution extremely final A/B weight ratio in organic solvent commonly used is 95/5 to 50/50.The gained spinning solution needs not to be complete transparent and uniform solution, depends on the compatibility between PVA and described cellulosic polymer.For producing sea-island fiber, PVA wherein of the present invention is a sea component, and cellulosic polymer is the island component, and its average-size is 0.03 μ m to 10 μ m, and spinning solution is preferably the solution of sea-island phase separation structure, and wherein PVA is the sea, and cellulosic polymer is the island.Yet, do not require that in the spinning solution stage island is of a size of 0.03 to 10 μ m, because the situation that is separated is because of existing solvent or changing according to condition of cure.The factor of decision sea-island structure comprises compatibility, composition ratio and the polymer concentration of two kinds of polymer, the type of organic solvent and the temperature of spinning solution, importantly, machinability such as spinnability and performance such as easily fibrillable, intensity and resistance to water are adapted by suitably controlling these factors.For wet spinning, the viscosity of spinning solution is suitably for 10 to 400 pools; For dry-jet wet spinning, viscosity is suitably for 50 to 2000 pools.This viscosity is far below the viscosity of melt-spun method, and it can be used as the factor that can form non-circular or irregularly shaped island.
The water that is commonly used for the PVA spin solvent can not use, because water can not dissolve the water-insoluble cellulosic polymer.Be intensity and the stainability of improving viscose rayon, a kind of known method comprises the PVA aqueous solution is added in the viscose solution, this solution is spun into the aqueous solution that comprises saltcake and sulfuric acid.The fiber of producing by this method comprise PVA as island component and regenerated cellulose as sea component, but thereby this fiber with regard to intensity and fibril voltinism, be different from fiber of the present invention.Can be sea component even increase content so that the PVA of PVA in the method, but see that as fibril voltinism and intensity aspect the gained fiber is also very different than the present invention fiber from performance.
For fiber production method of the present invention, more very important be with PVA and cellulosic polymer with given ratio solvent spinning solution with the preparation sea-island structure in common solvent, cellulosic polymer can be the island component thereby PVA can be sea component.
Then, for wet spinning or dry-jet wet spinning, make the spinning solution of preparation like this enter coagulating bath by spinning plate.Even do not have to carry out spinning under the situation of fibers melt, so this method is suitable for the spinning of porous spinning filament plate because coagulating bath can narrow down in the spinneret orifice spacing with wet spinning that spinning plate directly contacts yet.On the other hand, between coagulating bath and spinning plate, there is the dry-jet wet spinning of air gap to be applicable to high speed spinning, because the polymer solution of discharging is bigger at the draw ratio of air gap part.By the present invention, can and use and suitably select wet spinning or dry-jet wet spinning according to purpose.
By the present invention, solidify solvent and do not have particular restriction, but thereby preferred PVA at low temperatures can produce the organic solvent that microlite is induced even gelling therein, comprises that as alcohols methyl alcohol and ethanol, ketone comprise the solvent of acetone and methyl ethyl ketone and spinning solution and the mixture of these solvents.It is not preferred easily inducing the non-homogeneous solvent that solidifies such as the saltcake aqueous solution.
The gelatine silk that evenly solidifies is transported to wet stretching, extracts and washs, oils, dry and dried drawing process, delivers to dry heat treatment technology again as needs, and preparation sea-island fiber, wherein sea component PVA is directed and crystallization.
The silk that forms in the coagulating bath is imported extraction bath to remove the solvent of contained spinning solution in the silk, and, final extraction bath comprises alcohol, ketone and water three components, alcohol is 9/1 to 1/9 with the weight ratio of ketone, by total restatement water content of described three components is 1 to 30wt%, can produce the fiber of extraordinary easily fibrillable effectively, can satisfy drainage time is 75 seconds or desired properties for more time.Alcohol in final extraction bath comprises for example methyl alcohol, ethanol, propyl alcohol and butanols.And described ketone comprises for example methyl isopropyl Ketone, methyl n-butyl ketone and methyl iso-butyl ketone (MIBK); From producing the angle of better easily fibrillable, preferred boiling point is higher than ketone such as the methyl n-butyl ketone and the methyl iso-butyl ketone (MIBK) of water.If alcohol exceeds 9/1 to 1/9 scope with the weight ratio of ketone, then gained making beating property may be not fine.If water content is lower than 1wt%, then making beating property is not fine yet; If water content is higher than 30wt%, the then mutual clinkering of fiber, thereby the intensity of infringement fiber etc.But the reason of using this final extraction bath of being made up of described three components to improve the fibril voltinism is not still clearly explained.
Described island size is plunged into the commercial sea-island phase separation structure and solidification stages gelling performance and the balance decision between the performance of being separated by spinning solution state as mentioned above.Island size under the spinning solution state is big more, solidification stages gel speed is low more and the speed that is separated is big more, and then the island size of gained fiber may be big more.The factor of the decision solidification stages gelling performance and the performance that is separated comprises the composition of coagulating bath and temperature, the time of staying therein, discharge from spinning plate before the temperature of spinning solution and shear rate etc.Therefore, usually by control decision spinning solution state down with in the factor of the island of solidification stages size, can produce the fiber of the present invention that average island is of a size of 0.03 μ m to 10 μ m.
Can change the performance of gained fiber like this by chemical reaction.PVA immersed as the fiber of the present invention of island component as sea component and cellulose acetate in 50 ℃ the 1N caustic soda and to make the cellulose acetate saponification in 30 minutes, produce that PVA exists as sea component and the fiber that has the cellulose of higher alkaline solution absorptivity, heat resistance and heat-resisting fusibleness to exist as the island component.With regard to having mentioned, this fiber is most preferred in the fiber type of the present invention.For improving the hot water resistance of this fiber, this fiber is immersed in aldehyde such as formaldehyde and the mixed aqueous solution of acid as sulfuric acid, the amorphous fraction that makes PVA is in molecule or intermolecular acetalization.
In addition, according to the present invention, with water-insoluble cellulosic polymer (B) with dissolve in amine oxide solvent or its aqueous solution and the polymer (C) that is different from polymer (B) are dissolved in amine oxide solvent or its aqueous solution with 95/5 to 5/95 B/C weight ratio, preparation sea-island solution that is separated, wherein B is that sea component and C are the island component, or wherein B is that island component and C are sea component.Then, this solution that spins as spinning solution by wet spinning or dry-jet wet spinning enters coagulating bath, can produce the easily fibrillable fiber of sea-island structure.Described polymer (C) except that PVA, comprise acrylate based polyalcohol such as polymethyl methacrylate and PMA, acrylonitrile based polymer such as polyacrylonitrile and acrylonitrile and cinnamic copolymer, vinyl esters based polyalcohol such as polyvinyl acetate, based on polymer such as polyethylene glycol, starch and the derivative polymer thereof of aklylene glycol and be different from polymer (B) based on cellulosic polymer; From easily fibrillable, high strength and alkali resistance aspect, preferred especially in the case above-mentioned PVA (A).
When using amine oxide solvent as the solvent of spinning solution in the methods of the invention, the cellulose of gained fiber has mutually than the high intensity of fiber that comprises the plain polymer of traditional fibre, therefore this fiber easily fibrillable.The weight ratio of polymer (C) and water-insoluble cellulosic polymer (B) can be in 95/5 to 5/95 scope, is 95/5 to 50/50 wide ranges than the weight ratio of PVA (A) and water-insoluble cellulosic polymer (B).Exceed 95/5 to 5/95 scope, can not produce the fiber of desired easily fibrillable.In addition, use the method, arbitrary island component that all can be of described polymer (C) and water-insoluble cellulosic polymer (B).
Used amine oxide solvent comprises N-methylmorpholine-N oxide (being abbreviated as " N-MMO "), dimethylethanolamine-N-oxide, the high piperidines of dimethyl-N-oxide, dimethyl benzyl amine-N-oxide, N in this method, N, N-Trimethylamine-N-oxide etc.This solvent can be the aqueous solution that contains 50wt% or how above-mentioned these solvents.Especially, from cellulosic solubility and security aspect, most preferably satisfy the N-MMO monohydrate of relational expression (N-MMO/ (N-MMO+ water)=87%).
Use this method, melt amine oxide solvent down, to wherein adding entry, add polymer (C) and water-insoluble cellulosic polymer (B) again, under 90 to 100 ℃ of stirrings, mix the preparation spinning solution as needs at 80 to 110 ℃.Polymer concentration in this spinning solution is preferably 5 to 30wt%; The viscosity of spinning solution for dry-jet wet spinning be suitably for 100 to 50000 the pool, and for wet spinning viscosity be 10 to 1000 the pool.The gained spinning solution is discharged from spinning head, by the air gap, introduces then (dry-jet wet spinning) in the coagulating bath, or enters directly that (wet spinning) makes it to solidify in the coagulating bath.Make water (as long as polymer (C) is an insoluble polymer), organic solvent such as methyl alcohol and acetone, saltcake and ammonium sulfate solution as coagulating bath.After this coagulating bath, make fiber by the product that method same as described above will be solidified.
In addition, in purpose scope of the present invention, the fiber that the present invention contains PVA and cellulosic polymer can contain inorganic pigment, organic pigment, dyestuff, prevents to damage stable on heating reagent, pH regulator agent, crosslinking agent, oil agent etc., they can add in each production phase, as before spinning solution stage, solidification stages, extraction stages, the next-door neighbour's drying, before next-door neighbour's stretching, after the hot-stretch, after the heat treatment and after the afterreaction.
Make fibrillation by the fiber that independent effect or its compound action of chemical solution expansive force or mechanical stress will so be produced.The fibriilar size of the present invention is expressed as 0.05 to 8 μ m with equivalent diameter.According to the present invention, following definite fibriilar size: amplify fibriilar cross section with scanning or transmission electron microscope, measure this cross-sectional area, be defined as this size with this cross section diameter of a circle of the same area.N=20 or the bigger size that adds and on average be defined as the fibrillation bundle.Too thin so that fibrillation tangles mutually and forms this fibrillation of fibrillation conglomeration and can not evenly disperse thereby size is less than the fibrillation of 0.05 μ m.Thereby this fibrillation can not play fibriilar effect.On the other hand, size is too big so that specific area is too little greater than the fibrillation of 8 μ m.Thereby this fibrillation can not play fibriilar effect as capturing inorganic particle.From fibriilarly strengthen the property, absorptivity, granule capturing and the dispersibility aspect of alkaline solution, fibriilar 0.2 to the 5 μ m that is preferably dimensioned to be, more preferably 0.6 to 2.5 μ m.Island size in fibriilar size and the fiber of the present invention has some correlation, but fibrillation does not always split into the island component fully.When fiber when in the island, also having the three-phase structure as the island of island component, very possible described island component further divides.Thereby, fibriilar size needn't with island consistent size in the fiber before the making beating.
Fibriilar whole surface area can be covered by sea component PVA, but preferably can be exposed to part fibrillation surface sometimes as the plain polymer of island component fibers.Estimate the absorptivity of alkaline solution by the beating time that changes PVA and cellulosic sea-island fiber, almost the absorptivity with independent PVA is identical to show the absorptivity of this fiber, although this fiber included the cellulose of alkaline solution absorptivity before making beating.Yet pulling an oar has increased the absorptivity of alkaline solution, and when making beating proceeded to a certain degree, fibriilar size was tending towards descending, but the alkaline solution absorptivity is tending towards reaching balance, and this is unexpected discovery.Reason still imperfectly understands, but is presumed as follows.The whole surface of fiber is all covered by the lower PVA of swelling in alkali before the making beating, so even there is the cellulose of theobromine swelling in the fiber, lip-deep PVA also plays the effect of what is called " hoop ".Therefore, this fiber is only by the alkaline solution absorptivity of the fiber of only being made up of PVA, but after pulling an oar, fiber divides between PVA layer and cellulose layer, thereby exposes cellulose layer from the teeth outwards.Like this, PVA " hoop " unclamps, thus fiber brought into play cellulose intrinsic alkaline solution absorptivity.Further pull an oar and reduced the size of fiber, thereby lose PVA " hoop ".Then the absorptivity of alkaline solution may reach equalization point no longer increases.Therefore, based on above-mentioned supposition, fibrillation not only reduces fibre diameter.For alkaline solution absorptivity very important use, as the barrier film in the alkaline manganese battery, wherein there is the component of holding the liquid absorptivity than high alkalinity to be exposed to its surperficial fibrillation and preferably has 10% or more, more preferably have 20% or more, also more preferably have 30% or more.
According to the present invention, wherein there is the incremental raio that sucks the alkaline solution weight of fiber before alkaline solution weight that fibriilar ratio that the component of higher alkaline solution absorptivity is exposed to its surface sucks fiber by the making beating back simply and the making beating to represent.
Fibriilar draw ratio (length/diameter) is 50 or bigger.If draw ratio less than 50, is then strengthened the property and the granule capturing deficiency.If draw ratio is greater than 2000, then fibrillation more seriously tangles mutually, is difficult to even dispersion, thereby needs some dispersion steps.From strengthening the property and the catching aspect, draw ratio is preferably 100 or bigger, and more preferably 200 or bigger.Term " diameter " means the long-pending diameter of a circle of fibrillation average cross-section herein.
The fibriilar preparation method of the present invention is described below.Apply chemical solution expansive force or mechanical stress or its combination (preferably) separately by fiber and produce fibrillation to the sea-island structure of the present invention that comprises PVA (A) and water-insoluble cellulosic polymer (B).By the present invention, term " chemical solution expansive force " means the effectiveness of described sea component PVA of swelling (A) or the plain polymer of described island component fibre (B).For PVA (A) is expanded, PVA (A) is contacted with water.The swellbility of island component water-insoluble cellulosic polymer (B) in water is very little, thereby between PVA layer and cellulosic polymer layer stress deformation takes place owing to the difference of swelling power.If distortion is big, then only divide by this swelling power.Because the adhesion strength between PVA (A) and the cellulosic polymer (B) may not be very big, so fiber of the present invention can divide under higher mechanical shear stress at last, if but to fibre application machine tool shearing force, preferably under the swelling set state, then this fiber divides and fibrillation more completely.But the chemical solution expansive force is bigger to the influence of fibril voltinism.The principal character of fiber of the present invention is and can does not need any cheap material that depollutes or recycle to obtain the chemical solution expansive force by water.The swelling that has shown the island phase is important and swellings marine facies are inoperative to easily fibrillable for fibrillation.Yet the result of study of fiber of the present invention shows that the swelling of independent marine facies is enough effective, plays the effect of easily fibrillable because of the internal strain increase that difference produced of the alternate swelling power with the island of marine facies.
Thereby fibrillation methods comprises by making fiber fibrillation and making the gained fibrillation form the method that sheet shape is formed; With by before fibrillation, making fiber form the method that sheet shape is formed.
Wherein, last method comprises and fiber of the present invention is cut into 1 to 30mm short section, these short sections are immersed and are scattered in the water, utilize beater, purifier and blender etc. to make these short section fibrillation, be scattered in as the base stock papermaking of paper or with fibrillation by the gained fibrillation and make material in the cement solution by mechanical stress.But the paper of the Bao Erqiang of production high bulk density is because this paper bag is drawn together the fiber that becomes thinner because of fibrillation.Porous paper is preferred for the barrier film of alkaline manganese battery, because can increase the weight of absorbent solution between fiber.Preferably, make fibrillation of the present invention and other material for example 0.3 to 1d vinylon mix, make paper then, thereby this paper can obtain porous.When so the barrier film of producing is used for solution between fiber space and fiber internal pore higher alkaline solution absorptivity is all arranged.When this fibrillation under agitation mixed with fine inorganic particles or thermosetting plastics fine grained, fine grained was captured to fibrillation, thereby particle is made moulding material.Therefore, can produce the friction material that is applicable to brake block and clutch disc.
Back one method comprises a kind of typical method, comprises making fiber crimp of the present invention and cutting short-forming fiber, makes this staple fibre form fabric by carding machine then, applies 30kg/cm on this fabric
2Or higher High-Pressure Water, preferred 60kg/cm
2Or higher, thereby make fiber fibrillation of the present invention by the impact or the shearing force of High-Pressure Water; Or this method can comprise with fiber of the present invention be cut into 1 to 30mm the section, these sections are scattered in the base stock for preparing paper in the water by wet method as paper material, on this paper, apply 30kg/cm
2Or higher, preferred 60kg/cm
2Or higher High-Pressure Water, thereby make fiber fibrillation of the present invention by the impact or the shearing of High-Pressure Water.Owing to use High-Pressure Water fibrillation after forming fabric, the advantage of this method is to avoid because of having due to the fibrillation bad dispersiveness or because of there being high bulk density due to the fibrillation, producing the two-dimentional sheet of porous, although this sheet comprises superfine fibre.This sheet is suitable for makes battery diaphragm, also is suitable for and makes cleaning piece and filter.
In addition, often by water under high pressure stream division, but because their negative correlation, but be used for the machinability of high-pressure water jet method and inconsistent by the composite fibre that contains two kinds of incompatible fibrous material polymer except that PVA in the fissility of high-pressure water jet method.More specifically, in the high-pressure water jet method fiber of easily fibrillable spinning, stretching, curl and carding process in too easily division, and in these technologies, give rise to trouble.On the contrary, have than Hyposegmentation to be difficult to fibrillation at the composite fibre without any problem aspect the machinability with the high-pressure water jet method, thereby can not produce the supatex fabric that comprises ultra-fine devillicate until fabric formation technology.
On the other hand, as mentioned above, but PVA-of the present invention base fiber had lower fibril voltinism in its dry state before high-pressure water jet technology.Therefore, in drying process, can reduce because of fibrillation and produce trouble; At its hygrometric state with high-pressure water jet, internal strain is amplified immediately, so that utilizes high-pressure water jet to be easy to cause fibrillation in fiber.
Because fiber of the present invention also can only divide by the independent effect of strong mechanical shear stress, so needle point method also is suitable for as one of fibrillation methods.Yet, as mentioned above, but fiber of the present invention under its green deformation state with mechanical shear stress fibrillation more.Therefore, should strict restriction needle point method.Particularly, should be preferably 250 holes/cm at needling density
2Or higher, more preferably 400 holes/cm
2Or carry out fibrillation under the higher condition.
About the preparation method of the dried laid fabric that will be used for spraying or needle point method, carding method comprises the general known method that utilizes roller carding machine, half random carding machine and random carding machine; The method that forms fabric comprises the general known method of series connection fabric, intersection fabric and groove intersection fabric.
The preparation method who is used for the basic paper material of wet no latitude of spraying comprises those methods of paper making equipments such as using circular net, short net and fourdrinier wire; In preparation, all satisfy, as long as this material can be added to the matrix that is used for spraying in its dry state or any basic paper material before drying.
Raw material as sneaking into fiber of the present invention in fabric or the basic paper material uses general material known, comprises artificial silk, Lyocell fibre, Pori's nosik, polyester, acrylic compounds, nylon, polypropylene and vinylon.
As for fabric laminate products, not only can use the identical fabric laminated product that contains fiber of the present invention to small part, and can use the fabric laminated product of the present invention of different blended composition and division in a proportion or contain the fabric of fiber of the present invention and do not contain the laminated product of the fabric of fiber of the present invention to small part.In other words, fiber of the present invention can partly be included in this fabric with its fibrillation state, thereby this fiber is inhomogeneous and exist brokenly.
Can in the supatex fabric of gained, add general known resin binder such as vinyl acetate, acrylic acid, polyethylene, vinyl chloride, carbamate, polyester, epoxy, rubber adhesive, by emulsion binder Method for bonding and powder adhesive binding method, comprise saturated infusion process, spray bonding, printed adhesive method and foaming method.
Describe the present invention more specifically below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
Be 1 with the degree of polymerization under in 80 ℃ of following nitrogen current, stirring; 750, saponification degree is that the PVA of 99.9mol% and the degree of polymerization are 180, degree of acetylation is 55% cellulose acetate (below be abbreviated as " CA ") adds and is dissolved in methyl-sulfoxide (below be abbreviated as " DMSO "); stirred 10 hours, preparation PVA/CA weight ratio be 70/30 and the polymer total concentration be the mixed solution (slightly brown) of 18wt%.Not exclusively transparent and opaque a little this solution is the solution that sea-island is separated, wherein PVA is a sea component, and CA is the island component.Even under not stirring, after 80 ℃ leave standstill 24 hours, in this solution, do not observe the trend that further is separated yet.Therefore this solution is homodisperse stabilizing solution.Make this solution as spinning solution by having 1, the spinning plate in the hole of 000 diameter 0.06mm, in temperature is that 10 ℃ and DMSO/ methyl alcohol weight ratio are this solution of wet spinning in 25/75 the coagulating bath, the wet stretching 3.5 times, contained DMSO in this yarn of extraction in methyl alcohol, dry gained yarn in 80 ℃ hot-air, the xeothermic total drawing ratio that is stretched to is 13 under 220 ℃ then, produces PVA/CA sea-island fiber.In 50 ℃, 1N caustic soda, handle this fiber 30 minutes then so that CA is saponified into cellulose, again the gained fiber was immersed in the bath of 70 ℃ of 30g/L formaldehyde, 200g/L sulfuric acid and 150g/L saltcake 30 minutes, make the PVA acetylation.The cross section that amplifies fiber with transmission electron microscope is to determine the island size, and the result is 1.2 μ m.Almost do not observe the island of any circle, but these islands are erose if any four jiaos or more polygonal rectangle, star and amoebiform etc.2,000d/1, the intensity of the multifilament textile of 000f is 10.2g/d, and the intensity of this fiber is 11.2g/d.Although the content as the CA of island component is 30wt%, this fiber has higher relatively intensity and hot water melt temperature up to 120 ℃, and this perhaps shows sea component PVA orientation and crystallization fully.The making beating of this fiber is 18 minutes.
Then this PVA/ cellulose sea-island fiber is cut into the long section of 2mm, the short section of 5g is scattered in the water (500mL), pull an oar and stirred 10 minutes with family expenses fruit juice mixer (National MX-X40).Suction filtration gained making beating solution reclaims moisture fibrillation.Use this fibrillation of light microscope and electron microscope observation then.This fibriilar average-size is 1.0 μ m, and draw ratio is 800, and non-circular erose cross section is arranged.The diameter of this fiber is about 15 μ m before the making beating.
With described moisture fibrillation (4g; Net weight) the PVA binder fiber (0.2g) with 1 dawn and 3mm adds in the entry (1.5L), utilizes the disaggregation machine to make the abundant disaggregation of this mixture, adds adhesive and fully stirring then, reclaims the solution that is used for papermaking.It is 1L that water is added described solution (300mL) to the final volume that is used for papermaking, utilizes the papermaking of Tappi paper making equipment.Gained paper fully dewaters with the No.3 filter, then 110 ℃ with drum dryer dry 85 seconds, produce 40g/m
2Synthetic paper.
The alkaline solution absorptivity is 2.2g/g in the fiber of gained paper, apparently higher than alkaline solution absorptivity 0.5g/g, suitable with the alkaline solution absorptivity 2.2g/g of the paper of producing by the mixture of making beating polynoise fiber and vinylon fiber by 1 dawn paper that vinylon fiber is produced of routine.This paper has so higher alkaline solution absorptivity.The following measurement of alkaline solution absorptivity in the fiber of described paper.The paper (WD (g) weighs after drying) of 5-cm * 5-cm size was immersed in 20 ℃, the 35wt%KOH aqueous solution 30 minutes,, 000rpm under this solution centrifugal is separated 10 minutes to remove liquid, the weight (WC (g)) of measurement gained paper then 3.By formula (WC-WD)/WD (g/g) rate that is absorbed.
Comparative Examples 1
PVA/ cellulose sea-island fiber of producing among the embodiment 1 is cut into the long section of 2mm, and former state is made paper under situation about handling without making beating then.Though the alkaline solution absorptivity is 1.0g/g in the fiber of this paper, shows the obvious improvement that absorptivity is compared with conventional vinylon fiber, does not observe enough effects of improving.This may be because the upper space of fiber is covered by the PVA of alkali swellable difference, forms in fiber by " hoop ", even fiber contains the theobromine bloated cellulose that falls.
Embodiment 2
As being 4 under agitation among the embodiment 1 with the degree of polymerization; 000, saponification degree is that the PVA of 99.1mol% and the degree of polymerization are 110, degree of acetylation is that 45% cellulose acetate is dissolved among the DMSO, preparation PVA/CA weight ratio be 63/37 and the polymer total concentration be the opaque a little finely divided homogeneous phase solution of 13wt%.Even after this solution left standstill one day, also not observing phase-separated state has obvious change.Therefore this solution is stable.Make spinning plate as this solution of spinning solution hole by 500 diameter 0.08mm are arranged, in temperature is that 5 ℃ and DMSO/ methyl alcohol weight ratio are this solution of wet spinning in 30/70 the coagulating bath, the wet stretching 3.5 times, extraction then, dry and 235 ℃ down the xeothermic total drawing ratios that are stretched to be 12, produce PVA/CA sea-island fiber, wherein CA is the island component.The island is of a size of 1.8 μ m in this blend fibre.This island is non-circular erose.1, the intensity of the multifilament textile of 000d/500f is 8.5g/d, and the intensity of this fiber is up to 9.2g/d.The hot water melt temperature of this fiber is up to 118 ℃, and this perhaps shows sea component PVA orientation and crystallization fully.The making beating of this fiber is 20 minutes.
With this PVA/ cellulose sea-island fiber crimp and be cut into the long section of 38mm, make the gained staple fibre produce 40g/m then by parallel carding machine
2Fabric.Wetting this fabric of water spray is exposed to 80kg/m with fabric then on fabric
2High-pressure water jet in, make fiber division and mat.
The microscopic examination of gained supatex fabric shows, this fiber splits into and is of a size of 2 μ m and draw ratio is 2,000 or higher fibrillation.The diameter of the fiber of not pulling an oar before the inject high pressure water is 15 μ m.
Comparative Examples 1
Remove and be exposed to 20kg/cm
2High-Pressure Water in outside identical with embodiment 2, produce supatex fabric by water spray.The microscopic examination of this supatex fabric shows the fibrillation that has any division hardly.
Embodiment 3
Curl and cutting embodiment 1 in the PVA/ cellulose fibre produced, make the gained staple fibre form fabric by carding machine, wetting this fabric in water makes this fabric be exposed to 60kg/cm
2And 80kg/cm
2High-Pressure Water in each 2 seconds, dry then, produce 40g/m
2Supatex fabric.The microscopic examination of gained supatex fabric shows, this fiber splits into and is of a size of 1.2 μ m and draw ratio is 2,000 or higher fibrillation.Fiber before the division is made sheet fabric, make this fiber fibrillation and fiber keeps sheet, produce homodisperse supatex fabric, even be 2,000 or when higher in draw ratio.
Measure between the fiber of this supatex fabric and alkaline solution absorptivity in the fiber, be respectively 6.2g/g and 2.9g/g.By the paper of wet method by the fibrillation preparation of embodiment 1, the interior alkaline solution absorptivity of its fiber is up to 2.2g/g, and the alkaline solution absorptivity is low to moderate 2.5g/g between its fiber.This may be because this sheet is to be made by the ultra-fine fibrillation that forms, thereby this sheet is very close, and the space in the fiber is few.By the paper of wet method by the fiber production of not pulling an oar of producing in the Comparative Examples, the alkaline solution absorptivity is low to moderate 1.0g/g in its fiber, and between fiber the alkaline solution absorptivity up to 6.0g/g.The supatex fabric of being produced by the wet no latitude carded webs in the present embodiment by water spray has in the higher fiber and alkaline solution absorptivity between fiber.Solution absorption rate between the fiber of following measurement sheet shape paper and dried no latitude supatex fabric.The sample (WD (g) weighs after drying) of 5-cm * 5-cm was immersed in 20 ℃, the 35wt%KOH aqueous solution 30 minutes, dropping liquid 30 seconds, weighing then is defined as WT (g).Determine total solution absorption rate, i.e. (WT-WD)/WD.Determine intrastitial solution absorption rate then as mentioned above.From total solution absorption rate, deduct the fiber internal absorption factor, obtain the solution absorption rate of sheet official form for filing a lawsuit and supatex fabric.
Comparative Examples 2
Except that the PVA/CA weight ratio is 97/3 with identical with embodiment 1 the polymer total concentration is 16wt%, dissolve, spinning and xeothermic drawing process, produce the PVA/CA blend fibre.As among the embodiment 2 with this fiber dispersion in water, utilize the fruit juice mixer to stir then and making beating was handled 40 minutes.Use microscopic examination gained fiber then, prove almost without any division or fibrillation tendency.The making beating of this fiber is 40 minutes or bigger.
Comparative Examples 3
Except that the PVA/CA weight ratio is 40/60 with identical with embodiment 1 the polymer total concentration is 25wt%, in DMSO, dissolve.Attempt to spin gained solution, but this solution is difficult to normally discharge from nozzle in the mode identical with embodiment 1.In addition, gained gel yarn is very weak, so that this yarn can not be by the subsequent technique of preparation fiber.This may be because sea component is CA, and it is used as matrix in dissolution phase.
Embodiment 4
With PVA/ curly cellulose fiber of producing among the embodiment 2 and the section that is cut into 40-mm, make the gained staple fibre by half random carding machine, form 15g/m
2Half random fabric (A).Short artificial silk with 1.3 dawn and 40mm is produced 30g/m
2Half random fabric (B).
With overcoat with these fabric laminated together, so that fabric (A) can be at the highest and lowest layer, and fabric (B) can be placed on this laminated product on the wire netting braid over braid then in the intermediate layer, applies 80kg/cm
2High-Pressure Water make fiber division and tangle, dry products obtained therefrom under 110 ℃ dryer temperature is produced 60g/m by water spray
2Dried no latitude supatex fabric.
With microscopic examination gained supatex fabric, show that this fiber has split into that to be of a size of 2 μ m and draw ratio be 2,000 or higher fibrillation, wherein each fabric mat satisfactorily.
Comparative Examples 4
The short artificial silk that makes 1.3 dawn and 40mm with the method identical with embodiment 4 is produced 15g/m by half random carding machine
2And 30g/m
2Half random fabric.
With overcoat together, so that 15g/m with these fabric laminated
2Fabric can be at highest and lowest layer, 30g/m
2Fabric can then this laminated product be placed on the wire netting braid over braid in the intermediate layer, apply 80kg/cm
2High-Pressure Water make fiber division and tangle, dry products obtained therefrom under 110 ℃ dryer temperature is produced 60g/m by water spray
2Dried no latitude supatex fabric.
The density of gained supatex fabric is lower than the supatex fabric of producing among the embodiment 4, and the wiping properties of glass lens is poor.
Embodiment 5
The PVA/ cellulose sea-island fiber that curls and to produce among the embodiment 1 is cut into fiber the section of 51mm then, with parallel carding machine combing gained staple fibre, then by intersecting on the intersection fabric that packing prepares with 450 holes/cm
2The perverse density acupuncture of pin, make fiber division and mat, thereby produce 400g/m
2Dried no latitude supatex fabric.
With microscopic examination gained supatex fabric, show that this fiber has split into that to be of a size of 4 μ m and draw ratio be 500 or higher fibrillation, wherein each fibrillation mat satisfactorily.The diameter of this fiber of not pulling an oar is 15 μ m before the perverse technology of pin.
Embodiment 6
PVA/ cellulose sea-island fiber of producing among the embodiment 1 is cut into the section of 15mm, and amount and the wood pulp with 40wt% and 60wt% mixes respectively, prepares slurry.Utilizing then has the paper making equipment of short net that this slurry is made paper, and gained paper is 110 ℃ of dryings down in dryer temperature, preparation 25g/m
2Basic paper material.
Four these basic paper material are laminated together, then this laminated product is placed on the wire netting braid over braid, be exposed to 100kg/cm
2High-Pressure Water in, make fiber division and tangle, products obtained therefrom dryer temperature be 110 ℃ dry down, produce 91g/m
2Wet no latitude supatex fabric.
With microscopic examination gained supatex fabric, show that this fiber has split into that to be of a size of 1 μ m and draw ratio be 2,000 or higher fibrillation, wherein each fibrillation mat satisfactorily.The diameter of this fiber of not pulling an oar is 15 μ m before the spray water under high pressure technology.
Embodiment 7
Be 1 with the degree of polymerization under in 100 ℃ of following nitrogen current, stirring with 200rpm; 750, saponification degree is that the PVA of 99.8mol% and the degree of polymerization are 180, degree of acetylation is that 55% CA is dissolved among the DMSO; stirred 10 hours, preparation PYA/CA weight ratio be 60/40 and the polymer total concentration be the PVA/CA mixed solution of 20wt%.This solution is opaque.Observe phase structure as stated above, show that this phase structure has the particle diameter of 3 to 10 μ m, PVA is a sea component in the solution that wherein should sea-island be separated, and CA is the island component.After the deaeration in 8 hours of this solution left standstill, do not observe the trend that significantly is separated into two-phase.Prove that this solution has the phase structure of quite stable.
Make under 100 ℃ as this solution of spinning solution by having 1, the spinning plate in the hole of 000 diameter 0.08mm, in temperature is that 7 ℃ and DMSO/ methyl alcohol weight ratio are this solution of wet spinning in 25/75 the coagulating bath, the wet stretching 3.5 times, contained DMSO in this yarn of extraction in methyl alcohol.As last extraction bath, use by weight and consist of the bath that methyl alcohol/methyl iso-butyl ketone (MIBK)/water of 54/36/10 is formed.Add oil agent in the fiber after extraction, dry this fiber in 80 ℃ hot-air then, then 230 ℃ down this fiber of xeothermic stretching to last total drawing ratio (promptly wet draw ratio * xeothermic draw ratio) be 16, produce PVA/CA sea-island fiber.The intensity of this fiber is 10.3g/d; Making beating property is about 200 seconds; With the drainage time of making beating after 5 minutes be 120 seconds.The cross section that amplifies fiber with transmission electron microscope is to determine the island size, and the result is 1.2 μ m.
This sea-island fiber is cut into the long section of 2mm, the short section of 5g is scattered in the water (500mL), pull an oar and stirred 5 minutes with family expenses fruit juice mixer (National MX-X40), the suction filtration gained solution of pulling an oar reclaims moisture fibrillation.Use this fibrillation of light microscope and electron microscope observation then, show that this fibriilar diameter is 1.0 μ m, draw ratio is about 1,000, and non-circular irregular section shape is arranged.The diameter of this fiber is 15 μ m before the making beating.
Embodiment 8
Be that 97% coniferous tree slurry immerses in the methyl alcohol in advance with alpha-cellulose content, make this slurry through in advance the technology of removing liquid, grinding and drying under reduced pressure, the preparation degree of polymerization is 450 cellulose slurry.Make the liquefaction of N-MMO monohydrate, add the N-MMO aqueous solution that entry prepares 70wt%.Make this aqueous solution remain on 100 ℃, with this cellulose slurry and the degree of polymerization is 1,750 and saponification degree be that the PVA of 99.9mol% adds in the aqueous solution of this N-MMO monohydrate with cellulose/PVA weight ratio of 40/60, the final total concentration of cellulose and PVA is 11wt% to this aqueous solution, add then and dissolve aqueous hydrogen peroxide and oxalic acid as antioxidant, its gross weight with respect to cellulose and PVA is 0.8wt%.Under blanket of nitrogen,, reclaim viscosity half turbid solution with gained solution continuous stirring 5 hours.The main mutually cellulose in the island of this solution is of a size of about 5 μ m.This solution directly enters methanol bath as spinning solution from the spinning plate in hole that 400 diameter 0.09mm are arranged.Carry out 3.5 times wet stretching then, extract N-MMO in methyl alcohol, drying down further xeothermicly is stretched to 12 times at 230 ℃ then.The gained fiber is 800d/400f, and fibre strength is 6.8g/d, and making beating property is 25 minutes, and wherein the island component is a cellulose, and sea component is PVA.This fiber is cut into the section of 2mm, makes gained section making beating with family expenses fruit juice mixer in water, generation about 1 μ m of diameter and draw ratio are 700 fibrillation.
Industrial applicability of an invention
The density of the sheet material made from fibrillation of the present invention, shielding, alkali resistance, light-proofness, wiping, Water imbibition, oil absorption, poisture-penetrability, thermal insulation, against weather, high strength, high tear edge, wear-resisting Property, Electrostatic Control ability, drapability, dyeing affinity and security etc. are fabulous. Therefore, this sheet Material can be used for various application, comprise the filter cloth of various filters such as air cleaner, bag filter, The filter of liquid filter, vacuum filter, effluent filter and shielding bacterium; Be used for various The sheet material of electrical equipment such as capacitor barrier paper and floppy disk packaging material; Various industrial sheet materials such as FRP surface The base cloth of coating, adhesive tape, oil absorption material and insulating paper felt; Various cleaning wiping cloth such as family, clothes Affair industry and medical cleaning wiping cloth, print roller cleaning wiping cloth, cleaning used in copy machines cleaning wiping cloth and optical system Use cleaning wiping cloth; Various medical and health use cloth are such as operation robe, robe, drop cloth, cap, mouth mask, bed List, towel, gauze, poultice with in base cloth, diaper, the diaper, diaper face, adhesive plaster with base cloth, Wet towel and yarn; In various clothes cloths such as shield, pad, the dustcoat and disposable underclothes; Various lifes Live material such as artificial leather and use for synthetic leather base cloth, desktop, wallpaper, shoji-gami (paper screen paper using), Window shade, calendar, lapping, portable heater (kairo) bag and drier packaging bag, Shopping bag, packing sheet (furoshiki), garment cover and pillow cover; Various plastic sheeting for farm uses are such as the shielding cold-peace The cloth of sunlight, lining curtain, total coverlay, photomask and anti-careless film, pesticide packaging material, be used for The lining paper of the tank of seed growth; Various protection are long with sheet materials such as smoke-preventing mask and anti-dust respirator, laboratory Robe and dustcloth; Various civil engineering constructions usefulness sheet materials such as house wrappage, adrainage material, filtration Medium, isolated material, covering, roof, mattress and ground blanket base cloth, anti-reveal plate, within the walls material, Sound insulation or shock-proof plate, imitative plank and hanger plate (curing sheet); With sheet material such as ground in the various cars Seat and boot pavement, molding top material, headrest and lining cloth, and the barrier film in the alkaline battery.
When under agitation fiber of the present invention disperseed with inorganic particle, this fiber is produced by fibrillation to be had Good granule capturing and strengthening the property and excellent heat resistance and the fibrillation of anti-flammability. Therefore, This fibrillation is suitable for makes friction material. This fibrillation mixes and when being dispersed in the cement, this fibrillation is non-Often capture securely cement granules, also bring into play the effect of refinforced cement performance. Therefore, can easily give birth to Product has the slabstone of higher-strength.
Claims (16)
1. the easily fibrillable fiber of a sea-island structure, comprise vinyl alcohol based polyalcohol (A) and water-insoluble cellulosic polymer (B), wherein A is that sea component and B are the island component in fiber cross section, be characterised in that size average out to 0.03 to the 10 μ m on described island, with the TENSILE STRENGTH of described fiber be 3g/d or bigger, polymer A/polymer B weight ratio is 95/5-50/50; Polymer A contains 70mol% or more vinyl alcohol units; And the saponification degree of polymer A is 80mol% or bigger.
2. according to the easily fibrillable fiber of the sea-island structure of claim 1, wherein said fiber has 30 minutes or lower making beating.
3. according to the easily fibrillable fiber of the sea-island structure of claim 1, the drainage time after wherein pulling an oar 5 minutes is 75 seconds or longer.
4. a fibriilar preparation method comprises and will pull an oar in water according to the described fiber of claim 1, thereby makes described fiber fibrillation.
5. a fibriilar preparation method comprises and will comprise that the fabric according to the described fiber of claim 1 is exposed to 30kg/cm
2Or in the higher High-Pressure Water, thereby make described fiber fibrillation.
6. a method of producing dried no latitude supatex fabric by water spray comprises that the fibrous raw material that combing to small part contains according to the described fiber of claim 1 prepares fabric, is exposed to 30kg/cm with described fabric
2Or in the higher High-Pressure Water, thereby make described fiber fibrillation.
7. produce the method for doing no latitude supatex fabric for one kind, comprise that the fibrous raw material that combing to small part contains according to the described fiber of claim 1 prepares fabric, with 250 holes/cm
2Or the higher described fabric of needling density acupuncture, thereby make described fiber fibrillation.
8. a method of producing wet no latitude supatex fabric by water spray comprises by containing to small part according to the described fiber of claim 1 and makes paper material with its basic fiber, and the gained paper material is exposed to 30kg/cm
2Or in the higher High-Pressure Water, thereby make described fiber fibrillation.
9. a fibrillation comprises vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B), wherein fibriilarly is of a size of 0.2 to 5 μ m and fibriilar draw ratio is 50 or bigger.
10. a fibrillation comprises vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B), wherein fibriilarly is of a size of 0.05 to 8 μ m and fibriilar draw ratio is 50 or bigger.
11. the easily fibrillable fiber preparation method of a sea-island structure, comprise with vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B) be dissolved in prepare in the OOS A wherein be sea component and B be the sea-island of island component be separated solution and with gained solution as spinning solution wet spinning or dry-jet wet-spinning to coagulating bath.
12. easily fibrillable fiber preparation method according to the sea-island structure of claim 11, comprise the yarn introducing extraction bath that will in described coagulating bath, form, remove the described solvent of contained spinning solution in the described yarn, dry described yarn, with the described yarn of further stretching, wherein said extraction bath finally comprises alcohols, ketone and three kinds of components of water, and the weight ratio of described alcohol and described ketone is 9/1 to 1/9, is 1 to 30wt% by described three component gross weight water contents.
13. battery diaphragm, described barrier film comprises the easily fibrillable fiber of sea-island structure, comprise vinyl alcohol based polyalcohol (A) and water-insoluble cellulosic polymer (B), wherein A is that sea component and B are the island component in fiber cross section, be characterised in that size average out to 0.03 to the 10 μ m on described island and the TENSILE STRENGTH of described fiber are 3g/d or bigger.
14. a battery diaphragm, described barrier film comprise that being formed and diameter is arranged by vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B) is that 0.05 to 8 μ m and draw ratio are 50 or higher fibrillation.
15. use the battery of battery diaphragm, described barrier film comprises the easily fibrillable fiber of sea-island structure, comprise vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B), wherein A is that sea component and B are the island component in fiber cross section, be characterised in that size average out to 0.03 to the 10 μ m on described island and the TENSILE STRENGTH of described fiber are 3g/d or bigger.
16. use the battery of battery diaphragm, described barrier film comprises that being formed and diameter is arranged by vinyl alcohol based polyalcohol (A) and water-insoluble cellulose-based polymer (B) is that 0.05 to 8 μ m and draw ratio are 50 or higher fibrillation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN96195692A CN1080780C (en) | 1996-05-20 | 1996-05-20 | Easily fibrillable fibre |
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| CN96195692A CN1080780C (en) | 1996-05-20 | 1996-05-20 | Easily fibrillable fibre |
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| CN1080780C true CN1080780C (en) | 2002-03-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5861213A (en) * | 1995-10-18 | 1999-01-19 | Kuraray Co., Ltd. | Fibrillatable fiber of a sea-islands structure |
| GB2324064A (en) * | 1997-04-11 | 1998-10-14 | Courtaulds Fibres | Modified lyocell fibre and method of its formation |
| US6929884B2 (en) * | 2001-04-19 | 2005-08-16 | Zinc Matrix Power, Inc. | Method for manufacture of films containing insoluble solids embedded in cellulose-based films |
| EP1464737B1 (en) * | 2001-06-15 | 2009-08-05 | Kuraray Co., Ltd. | Composite fiber |
| US9056792B2 (en) * | 2011-06-30 | 2015-06-16 | Weyerhaeuser Nr Company | Internally curing cement based materials |
| JP2016513860A (en) | 2013-03-05 | 2016-05-16 | シオン・パワー・コーポレーション | Electrochemical cells containing fibril materials such as fibril cellulose materials |
| CN103451778A (en) * | 2013-08-15 | 2013-12-18 | 苏州龙杰特种纤维股份有限公司 | Polyvinyl alcohol fiber with flat cross section and non-woven cloth with same |
| CN108660524B (en) * | 2018-04-24 | 2021-07-06 | 青岛大学 | Sea-island fiber composite melt spinning method using water-soluble modified PVA as sea |
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| CN1137225A (en) * | 1993-12-14 | 1996-12-04 | 美国菲尔特罗纳有限公司 | Bicomponent fiber and tobacco filters formed therefrom |
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| Publication number | Publication date |
|---|---|
| CN1191581A (en) | 1998-08-26 |
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