CN1973087A - Cellulosic and para-aramid pulp and processes of making same - Google Patents
Cellulosic and para-aramid pulp and processes of making same Download PDFInfo
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- CN1973087A CN1973087A CNA2005800208653A CN200580020865A CN1973087A CN 1973087 A CN1973087 A CN 1973087A CN A2005800208653 A CNA2005800208653 A CN A2005800208653A CN 200580020865 A CN200580020865 A CN 200580020865A CN 1973087 A CN1973087 A CN 1973087A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
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Abstract
The present invention relates to cellulosic and para-aramid pulp for use as reinforcement material in products such as seals and friction materials. The pulp comprises (a) irregularly shaped, cellulosic fibrous structures, (b) irregularly shaped, para-aramid fibrous structures, and (c) water, whereby cellulosic fibrils and/or stalks are substantially entangled with para-aramid fibrils and/or stalks. The invention further relates to processes for making such cellulosic and aramid pulp.
Description
Background of invention
1. invention field
The present invention relates to be used to seal cellulose and para-aramid pulp with the series products of friction material as reinforcing material.The invention still further relates to the method for making this pulp.
2. description of Related Art
Fiber and non-fibre reinforced materials have been used to rub product, sealed product and other plastics or rubber product for many years.This type of reinforcing material generally must have high abrasion and heat resistance.
Asbestos fibre always has been used as reinforcing material, but because its insalubrity, so replaced or suggestion is alternative.But, have in this respect many in these substitutes or that aspect performance not as asbestos.
Open (Research Discloure) 74-75 of the research of publishing in February, 1980 discloses the method for being made pulp by the fibrillation KEVLAR board para-aramid fiber of various different lengths, and this class pulp is as the purposes of reinforcing material in various application.The open road of this publication, the pulp of being made by KEVLAR board para-aramid fiber can be used for articles of sheet material separately, also can with other material, be used for articles of sheet material as the fiber combinations of NOMEX board meta-aramid, wood pulp, cotton and other native cellulose, artificial silk, polyester, polyolefin, nylon, polytetrafluoroethylene (PTFE), asbestos and other mineral, glass fibre and other pottery, steel and other metal and carbon etc. together.This publication also discloses independent with KEVLAR board para-aramid fiber, or the application of pulp in friction material made from KEVLAR para-aramid fiber staple fibre, to substitute a part of asbestos volume, the remainder of asbestos volume is then substituted by filler or other fiber simultaneously.
United States Patent (USP) 5,811,042 (authorizing Hoiness) discloses a kind of compound friction or gasket material, made by thermosetting or thermoplastic matrix resin, fibre reinforced materials and the aramid particles that do not contain fibril substantially.Poly-(poly P phenylene diamine terephthalamide) and poly-(paraphenylene terephthalamide's m-phenylene diamine (MPD)) is preferred fibre reinforced materials, and this fiber can be Soft flocks (floc) or pulp form.
Application No. 2003/0022961 (authorizing people such as Kusaka) discloses the friction material of being made by following material: friction modifiers, binding agent and the fiber enhancer of being made by (a) the dried aramid pulp and the mixture of (b) wet aramid pulp, wood pulp or acrylic acid pulp.Dried aramid pulp is defined as the aramid pulp that usefulness " dried fibrillation methods " obtains.Dried fibrillation methods is that aramid fibre is placed the technology of dry grinding into pulp between rotating blade and the screen cloth.Wet aramid pulp is defined as the aramid pulp that usefulness " moor fibrillation method " obtains.Moor fibrillation method is the short aramid fibre in water to be placed between 2 rotating disks grind to form fibrillating fibre, makes fibrillating fibre then, that is, and and pulp, the technology of dehydration.The method that people such as Kusaka also disclose a kind of mixing-fibrillating fibre is as follows: but at first with the organic fiber mixed in accordance with regulations of multiclass fibrillation, this mixture of fibrillation is to form pulp then.
At present, just needing to provide can be in sealing and friction and so on be used the function admirable low again alternative reinforcing material of cost simultaneously.Although existing a large amount of open source literatures have proposed the alternative reinforcing material of lower cost, in the product of being advised, there are many performances in use bad, cost perhaps has other shortcoming again apparently higher than present commercially available prod.Therefore, still need at present not only to have high abrasion and heat resistance and cost but also the reinforcing material equally matched or more cheap with other commercially available reinforcing material.
Summary of the invention
The present invention relates to make first embodiment of the method for the cellulose that uses as reinforcing material and para-aramid pulp, comprising:
(a) all pulp components of combination comprise:
(1) cellulose fibre, its speed with 20 ℃/min in air is heated at least 10% of 700 ℃ of its weight of reservation, and this fiber accounts for 10～90wt% of total solid in all components, and has the average length that is no more than 10cm;
(2) para-aramid fiber accounts for 10～90wt% of total solid in all components and has the average length that is no more than 10cm; And
(3) water accounts for 95～99wt% of whole components;
(b) all components are mixed into basic slurry uniformly;
(c) finish grind this mixed slurry altogether, by carrying out simultaneously:
(1) fibrillation, the cellulose fiber peacekeeping para-aramid fiber that cuts off and plasticate make them become the erose fibrillating fibre structure with stalk and fibril; And
(2) disperse all solids, make the correct grinding slurry even substantially; And
(d) from the slurry of correct grinding, be dewatered to total moisture content and be no more than 60wt%,
Form cellulose and para-aramid pulp thus, wherein cellulose fento and/or stalk and para-aramid fibril and/or stalk obviously tangle.
The invention still further relates to second embodiment of the method for cellulose that manufacturing uses as reinforcing material and para-aramid pulp, comprising:
(a) make up all components, comprise water and first fiber of forming by following component:
(1) cellulose fibre, it keeps at least 10% of its weight when being heated to 700 ℃ with 20 ℃/min speed in air, and this fiber accounts for 10～90wt% of total solid in the pulp; With
(2) para-aramid fiber accounts for 10～90wt% of total solid in the pulp;
(b) component with combination is mixed into basic symmetric suspension;
(c) in disk refiner the correct grinding this suspended substance, thus fiber is cut into the average length that is no more than 10cm, and make to small part fiber fibrillation with plasticate into erose fibrillating fibre structure;
(d) make up all components, comprise second fiber of correct grinding suspended substance, (a) (1 and 2) group, and as needs, water is to be increased to water content the 95～99wt% that accounts for whole components;
(e), mix all components, to form basic suspended substance uniformly as needs;
(f) finish grind the suspended substance of this mixing altogether, by carrying out simultaneously:
(1) fibrillation, cut off and the suspended substance of plasticating in solid, make all or all cellulose and para-aramid fiber change the erose fibrillating fibre structure with stalk and fibril into basically; And
(2) disperse all solids, make the correct grinding slurry even substantially; And
(h) from the slurry of correct grinding, be dewatered to total moisture content and be no more than 60wt%,
Form cellulose and para-aramid pulp thus, wherein cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.
The invention still further relates to cellulose and para-aramid pulp, comprise as reinforcing material:
(a) erose cellulosic fibrous structure keep at least 10% of its weight when being heated to 700 ℃ with 20 ℃/min speed in air, and cellulosic structure accounts for 10～90wt% of total solid;
(b) erose para-aramid fibre structure accounts for 10～90wt% of total solid; And
(c) water accounts for 4～60wt% of whole pulp,
Wherein this cellulose and para-aramid fibre structure have the average largest dimension that is no more than 5mm, be no more than length weighted average and stalk and/or the fibril of 1.3mm, wherein cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.
The invention still further relates to friction material, it comprises friction modifiers; Randomly at least a filler; Binding agent; With the fibre reinforced materials that comprises pulp of the present invention.
In addition, the present invention relates to encapsulant, it comprises binding agent; Randomly at least a filler; With the fibre reinforced materials that comprises pulp of the present invention.
The accompanying drawing summary
About the present invention, can obtain to understand more fully from hereinafter detailed description and in conjunction with following accompanying drawing.
Fig. 1 implement to make " wet " the used equipment block scheme of wet method of pulp of the present invention.
Fig. 2 implements to make the used equipment block scheme of dry method that the present invention " does " pulp.
Fig. 3 is the microphoto image as the para-aramid particle of optional components in the inventive method.
Fig. 4 is the microphoto image according to the pulp of the inventive method manufacturing.
Glossary
Before describing the present invention, will be useful in some term definition vocabulary below, they all have identical meanings in the disclosure in the whole text, unless point out separately.
" fiber " is meant soft, its length and the high urstoff of ratio perpendicular to the width in the cross section of its length.Here, term " fiber " is used interchangeably with term " long filament " or " root ".Long filament cross section described here can be an arbitrary shape, but typical shape is circle or beans shape.The fiber of spinning on the package bobbin is known as continuous fibers.Fiber can cut into short length, is known as staple fibre.Fiber also can be cut to shorter length, is known as Soft flocks.Yarn or multifilament textile or tow comprise plurality of fibers.Yarn can be by twisted and/or twisting.
" fibril " is meant that diameter is little of extremely several microns of part microns, and the fubril of about 10～100 μ m of length.Fibril is that the trunk of the big fiber of 4～50 μ m extends out from diameter generally.Fibril plays hook or fastener, to snarl or to catch adjacent materials.Some fibers can fibrillation, other then can not or fibrillation effectively, thereby be the purpose of this definition, this kind fiber can not fibrillation.Poly-(poly P phenylene diamine terephthalamide) fiber easy fibrillation when being ground produces fibril.Cellulose fibre of the present invention also can fibrillation.
" fibre structure of fibrillation " is meant to have stalk and the material granule of extended fibril above it, wherein stalk generally is cylindric, about 10～50 μ m of diameter, fibril then is the hair-like part, diameter has only part micron or several microns, attached on the stalk and have the length of about 10～100 μ m.
" Soft flocks (floc) " is meant the fiber that length is shorter than staple fibre.The length of Soft flocks is between about 0.5～about 15mm, and diameter is preferably grown 1～12mm and diameter at 8～40 μ m between 4～50 μ m.Less than the not significantly contribution of intensity of the Soft flocks of about 1mm to the material that uses it.Soft flocks or the fiber of length more than about 15mm can not work usually well, because fiber may become mutually and tangles one by one, thereby can't fully and be evenly distributed in whole material or the slurry.The aramid fibre bits are made by aramid fibre being cut into short length, and do not have and significantly or at all do not have fibrillation, for example, as adopting United States Patent (USP) 3,063,966,3,133,138,3,767,756 and 3,869, those of the preparation of method described in 430.
" length weighted average " is meant the length of calculating according to following formula:
Length weighted average=∑ [(each single pulp length)
2]/∑ [each single pulp length]
The full-size of object " is meant 2 solstics air line distances each other on the object.
" staple fibre " can be no more than 15cm by long filament is cut to, preferred 3～15cm, most preferably 3～8cm length and making.Staple fibre can be straight (that is a non-crimping) or be curled into along its length indentation with any (or alternating bending) frequency of curling and curl.Fiber can exist with uncoated or coating or with the form of other preliminary treatment (for example, predraft or heat treatment).
Detailed Description Of The Invention
The present invention relates to make method as the cellulose and the para-aramid pulp of reinforcing material.The invention still further relates to cellulose and the para-aramid pulp that to make with method of the present invention as reinforcing material.The invention still further relates to product of the encapsulant of having mixed into pulp of the present invention and friction material and so on and their manufacture method.
I. first embodiment of the inventive method
In the first embodiment, the method for manufacturing cellulose and para-aramid pulp may further comprise the steps.The first, with the pulp combination of components, be added in or contact.The second, the pulp component of hybrid combining is to form basic slurry uniformly.The 3rd, slurry is finish grinded simultaneously or finish grindes altogether.The 4th, from the correct grinding slurry, dewater.
Combination step
In combination step, preferably all pulp components are added in the container together.The pulp component comprises (1) cellulose fibre, (2) para-aramid fiber, and (3) randomly do not contain the granular para-aramid particle of fibril substantially or fully, and (4) are other a small amount of additive randomly, and (5) water.
Cellulose fibre
The concentration that the addition of cellulose fibre will reach in all component total solids is 10～90 weight %, and preferably the concentration in all component total solids is 25～60 weight %, and most preferably the concentration in all component total solids is 25～55 weight %.
Be applicable to that cellulose fibre of the present invention is into the gray fibers cellulose fiber.So-called " becoming ash " is meant and keeps at least 10% of its weight when cellulose fibre is heated to 700 ℃ with the speed of 20 ℃/min in air.Preferred this cellulose fibre has added 10% inorganic compound in fiber.This fibrid and manufacture method thereof usually are disclosed in U.S. patent 3,565,749 and BP GB1, in 064,271.
Be applicable to that the gray fibers cellulose fiber that is preferably of the present invention is the fiber of silica of form that contains the salt of poly-silicic acid or acid in the cellulose supporting structure, wherein poly-silicic acid contains the alumina silicate position.The manufacture method of this fiber is as follows: the viscose that contains even abundance silica aqueous slkali in the fiber is carried out spinning, then, handle this fiber with aluminum solutions.Preferred silica aqueous slkali is the aqueous solution of silica and NaOH, and preferred for preparation is as follows: dissolve the soluble substantially silica of 0.5～25 weight % in concentration is the sodium hydrate aqueous solution of 10～25 weight %.In sour spinning bath the viscose that contains the silica aqueous slkali is carried out spinning, here, viscose is regenerated as cellulose fibre, gets off and with poly-silicic acid, promptly the moisture form of silica is evenly distributed in the cellulose and the silica aqueous slkali is precipitated.The coprecipitation mode of poly-silicic acid makes the primary granule of its regular distribution in cellulose form bigger aggregation, and it can be surveyed diameter and reach the nm magnitude.Fiber is the aluminum water solution of 0.1～10 weight % with concentration in case drawing-off and washing are preferably carried out in formation then, as sodium aluminate, at 0～100 ℃, handles for preferred 20～60 ℃.With the aluminum solutions modification time, the surface of poly-silicic acid aggregation is converted into alumina silicate in the cellulose supporting structure.The silanol on aluminate anion in the sodium aluminate and poly-silicic acid surface reacts, and form the alumina silicate position, and fiber surface is accepted electric charge, and this electric charge is neutralized by sodium cation.Can carry out modification with other salt of aluminium, in this case, use the aqueous solution of being made by them, aluminium is in suitable reactive form, the aluminum solutions after its occupation mode and the fibre spinning identical.These preferred fiber and manufacture methods thereof usually are disclosed in U.S. patent 5,417,752 and the International Patent Application WO 9217629.Further, representative fibers preferably contains about 31 ± 3% inorganic material, as Sateri Oy Company of Finland with trade name VISIL
The fiber of selling.One-tenth gray fibers of the present invention when adding pulp of the present invention, has better heat resistance than the cellulose fibre that does not add inorganic component.
The average length of optimum fiber cellulose fiber is no more than 10cm, more preferably 0.5～5cm, most preferably 0.6～2cm.With pulp all combination of components together before, the cellulose fibre of any continuous filament yarn form can both cut into short fiber, as staple fibre or Soft flocks.
The para-aramid fiber
The concentration that the addition of para-aramid fiber will reach in all component total solids is 10～90wt%, and preferably the concentration in all component total solids is 40～75wt%, and most preferably the concentration in all component total solids is 40～55wt%.The line density of para-aramid fiber preferably is not more than 10 dtexs, more preferably 0.5～10 dtex, most preferably 0.8～2.5 dtex.Also preferred para-aramid fiber is not more than 10cm along the average length of its longitudinal axis, and more preferably average length is 0.65～2.5cm, and most preferably average length is 0.65～1.25cm.
The para-aramid particle
Randomly, in one embodiment, the pulp component also comprises substantially or does not contain fully the granular para-aramid particle of fibril.If add these particles, then their concentration that should be added in all component total solids is no more than 50wt%, and preferably the concentration in all component total solids is 20～50wt%, and most preferably the concentration in all component total solids is 25～35wt%.In view of being made by the para-aramid fiber, they contribute to the excellent wear-resisting and dispersiveness of generation pulp.Because particle do not contain fibril substantially, so these particles also play mixing dose effect, impel other composition to be dispersed in mixture and the slurry.The particle that plays this kind effect is referred to as processing aid or auxiliary agent usually.Substantially or fully the average largest dimension that does not conform to the granular para-aramid particle of fibril be 50～2000 μ m (0.05～2mm), preferred 50～1500 μ m, most preferably 75～1000 μ m.But, less than the particle of about 50 μ m will lose the friction and sealing applications in validity.The above particle of about 2000 μ m can not keep fully being dispersed in the water when mixing with other composition.Fig. 3 is the microphoto image that can be used as the para-aramid particle of component in the inventive method.
Aramid polymer
The polymer that is suitable for making aramid fibre of the present invention and aramid particles is the synthesis of aromatic polyamide.This polymer must have into fine molecular weight just can be configured as fiber.This polymer can comprise polyamide homopolymer, copolymer and their mixture based on aromatics, and wherein (CONH-) key directly is connected on 2 aromatic rings at least 85% acid amides.These rings can be not replace or replace.When 2 rings along strand each other during para-orientation, this polymer is a para-aramid.Preferred copolymer contains and is no more than other diamines of 10% and substitutes main diamines used when being shaped this polymer, or is no more than other diacid chloride of 10% and substitutes main diacid chloride used when being shaped this polymer.Additive can use with aromatic polyamides; And found, can carry out blend with aromatic polyamides or combine up to other polymeric material of 13wt%.Preferred para-aramid be poly-(poly P phenylene diamine terephthalamide) (PPD-T) and copolymer.
Other optional additive
Other additive can randomly add, as long as they keep being suspended in the solution in blend step and the effect of step to top listed necessary solid constituent finish grinded in not obvious change.Suitable additive comprises pigment, dyestuff, antioxidant, flame-retardant compound, and other processing and dispersing aid.Preferred pulp component does not comprise asbestos.In other words, the pulp of making does not contain asbestos.
Water
It is 95～99wt% that the addition of water will reach its concentration in whole components, preferably accounts for 97～99wt% of whole components.In addition, water can add earlier.Disperse best when the adding speed of other component should remain on all component of hybrid combining simultaneously then.
Blend step
In blend step, all components are mixed into basic slurry uniformly.Its respective concentration in whole components is identical in the concentration expressed in percentage by weight that so-called " even substantially " is meant each starting ingredient in the chance sample of this slurry and the combination step, and error range is ± 10wt%, preferably ± and 5wt%, most preferably ± 2wt%.For example, if the concentration of solid is 50wt% cellulose fiber peacekeeping 50wt% para-aramid fiber in whole mixture, then basic mixture uniformly means in blend step, each chance sample of this slurry all contains the cellulose fibre concentration of (1) 50wt% ± 10wt%, preferably ± 5wt%, most preferably ± the aramid fibre concentration of 2wt% and (2) 50wt% ± 10wt%, preferably ± 5wt%, most preferably ± 2wt%.Mixing can be finished in any container that comprises revolving vane or certain other agitator.Mixing can be after all components add, and all components add or Assemble Duration carries out.
The correct grinding step
In the correct grinding step, it is as follows that all pulp components are carried out common correct grinding, conversion or modification simultaneously.Cellulose fiber peacekeeping para-aramid fiber by fibrillation, cut off with plasticating and become to have the erose fibre structure of stalk and fibril.If the para-aramid particle adds with other component, then less by plasticating into, as to justify, do not contain substantially fibril particle to small part para-aramid particle.All solids are all disperseed, and make the slurry of correct grinding even substantially." even substantially " is as preceding definition.This correct grinding step preferably comprises allows mixed slurry pass through one or more disk refiners, or makes slurry pass through single refiner circulation.Term " disk refiner " thereby be meant contains 1 pair or manyly finish grind the refiner of all components to rotating relative to one another by the shear action between the disk.In a kind of disk refiner of application type, the slurry pump that finish grind is advanced to each other apart between very little and counterrotating round rotor of energy and the stator disk.Each disk all has the surface that faces another disk, has the surface grooves of radially extending at least in part on it.Spendable preferred disk refiner is disclosed in United States Patent (USP) 4,472, in 241.If must reach even dispersion and enough correct grindings, then can allow the slurry that mixes pass through once above or the series of disk refiner by forming by at least 2 disk refiners.When mixed slurry was only finish grinded in 1 refiner, the slurry of making was tending towards finish grinding insufficiently and disperses inhomogeneously.Can form fully or basically by a kind of solid constituent, or another kind of, or 2 kinds simultaneously, or if any 3 kinds, one-tenth a small bundle of straw, etc. for silkworms to spin cocoons on of then whole 3 kinds of compositions or agglomerating aggregation, rather than be dispersed into basic dispersion uniformly.This kind becomes a small bundle of straw, etc. for silkworms to spin cocoons on or agglomerating aggregation, and be once above or during by the refiner more than 1 by refiner in mixed slurry, fragmentation takes place and the tendency that is dispersed in the slurry bigger.
In this step of this method, stand common correct grinding owing to contain the basic evenly slurry of various ingredients, so the non-pulp component of arbitrary class (for example, the para-aramid fiber) (for example be in the non-pulp component of all other classes, aromatic polyamides material fragment and para-aramid particle randomly) existence advanced pulp by correct grinding down, those other components are also finish grinded simultaneously.The made pulp of common correct grinding of planting non-pulp component thus is better than only 2 kinds of pulps being mixed the pulp blend that is produced.Add 2 kinds of pulps, only they are mixed then, can not make according to the present invention and finish grind even like that substantially, the close-connected fibre fractionation of pulp that into pulp produced altogether by non-pulp component.
Dehydration
Then, will finish grind slurry dewatering and be no more than 60wt% to total moisture content, preferred total moisture content is 4～60wt%, and most preferably total moisture content is 5～58wt%.Dehydration can be carried out as follows: pulp is collected in dewater unit such as the horizontal filter, if desired, also can further dewaters by pressurization or squeezing pulp filter cake.The dehydration pulp can randomly be dried to desired water capacity then, and/or can pack or coiling.
Fig. 1 and 2
Referring now to Fig. 1 and 2 the present invention is described.This detailed description from start to finish, the similar similar unit of letter representative in institute's drawings attached.
With reference to figure 1, this figure provides according to " wet " block diagram of wet method embodiment of pulp of manufacturing of the present invention.Pulp composition 1 is added container 2.Container 2 is equipped with internal mixer, is similar to the blender in the washing machine.This blender is distributed to all components in the water, forms basic slurry uniformly.The slurry that mixes is transferred in first refiner 3 of this slurry of correct grinding.Then, randomly, this correct grinding slurry can be transferred in second refiner 4, and randomly then in the 3rd refiner 5.Though what draw is 3 refiners, can use the refiner of arbitrary number, depends on desired uniformity and correct grinding degree.After last refiner of this refiner series, the correct grinding slurry randomly is transferred in filter or the sorting screen 6, dispersing solid less than selected mesh or mesh size is passed through, and the dispersing solid greater than selected mesh or mesh size is looped back in one or more refiners, for example, by pipeline 7, or, will finish grind slurry then thus and deliver in filter or the sorting screen 6 to the special refiner 8 that finish grindes this kind circulation slurry.Allow and lead to the horizontal vacuum water-strainer 9 from filter or sorting screen 6,, make water concentration contained in the pulp be no more than the 75wt% of whole components in this dehydration through the appropriate slurry that finish grindes.Slurry is available any conventional method and equipment from any to the transfer of another point, for example, by 1 or many pumps 10 implement.Then, pulp is transported to baking oven 11, to remove more moisture, is no more than the 60wt% of whole components until the moisture of pulp.Then, the correct grinding slurry is packed in baling press 12.
With reference to figure 2, this figure provides the block diagram of " doing " the dry method embodiment of pulp according to manufacturing of the present invention.This dry method is except the later part of horizontal vacuum Water Extraction Machinery 9, identical with wet method.After that filter 9, pulp is sloughed more water through squeezer 13, and the water concentration in pulp is no more than the 20wt% of whole components.Then, pulp makes fluffyization of pulp, then through rotor 15, to slough more juicy through loosening apparatus 14.Then, as wet method, allow pulp pass through baking oven 11 and packing in baling press 12.
II. second embodiment of the inventive method
In second embodiment, the method for making cellulose fiber peacekeeping para-aramid pulp is all identical except following difference with first embodiment of said method.
Before all components combination, no matter cellulose fibre or para-aramid fiber, or cellulose fiber peacekeeping para-aramid fiber the two, all may need to prescind.Its method can be as follows: combination water and cellulose fibre or para-aramid fiber.Then, water is become first suspended substance with mixed with fibers, process with first disk refiner then, fiber is shortened.Disk refiner prescinds average length to fiber and is no more than 10cm.This refiner is the partly fibrillation and the fiber of plasticating also.Another kind of fiber, the sort of fiber that does not add before this just, also mode is prescinded like this, makes the second processing suspended substance.Then, this another kind fiber (or second suspended substance, if process in water) that average length is no more than 10cm makes up with first suspended substance.
Before other component adds or later on or during, as needs, can add more water, water concentration is increased to 95～99wt% of whole components.All after the combination of components,, they can be mixed, to obtain basic slurry uniformly as needs.
Then, all components in the slurry together, promptly simultaneously, carry out common correct grinding.This correct grinding step solid in the slurry that comprises fibrillation, cuts off and plasticate makes all or basic all celluloses and para-aramid fiber are converted into erose fibrillating fibre structure.This correct grinding step also comprises disperses all solids, makes the correct grinding slurry even substantially.Then, as dewatering in this method first embodiment.These two kinds of methods all produce identical or essentially identical cellulose and para-aramid pulp.
Pulp of the present invention
The product of producing with method of the present invention is to be applicable to cellulose and the para-aramid pulp of making reinforcing material in the product.This pulp comprises (a) erose cellulosic fibrous structure, (b) erose para-aramid fibre structure, (c) randomly, substantially the granular para-aramid particle that does not contain fibril, (d) randomly, other a small amount of additive, and (e) water.
The concentration of each independent component in pulp is certainly corresponding to the aforementioned concentration of making the used respective components of this pulp.
Erose cellulose and para-aramid fibrillating fibre structure contain stalk and fibril.This cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.This fibril is very important, plays the effect of hook or fastener or hair pawl, makes adjacent particle bonding and maintains in pulp and final products, thereby the globality of final products is provided.
The average largest dimension of cellulose and para-aramid fibrillating fibre structure preferably is no more than 5mm, more preferably 0.1～5mm, most preferably 0.1～3mm.The length weighted average of this cellulose and para-aramid fibrillating fibre structure is no more than 1.3mm, more preferably 0.7～1.3mm, most preferably 0.75～1.2mm.
If in pulp, comprise the para-aramid particle, then the fibre structure of cellulose and para-aramid fiber also contact in addition and partly looping these are justified, are not contained substantially around the para-aramid particle of fibril at least a portion.The size of these para-aramid particles is preferably at least 50 μ m, more preferably 50～100 μ m, the most preferably size of 50～75 μ m also.With fibril along cellulose and para-aramid fibre structure surface can contact this circle, do not contain para-aramid particle of fibril and around particle, form cocoon shape thing substantially.
What this cellulose and para-aramid pulp did not contain same material substantially becomes a small bundle of straw, etc. for silkworms to spin cocoons on or agglomerating aggregation.Moreover the Canadian Standard Freeness of this pulp (CSF) as measuring of its drainage characteristic, is measured according to TAPPI test T 227om-92, between 100～700ml, and preferred 250～450ml.
The surface area of pulp is measuring of original fiber degree and influences the porosity of being made product by this pulp.The surface area of preferred pulp of the present invention is 7～11m
2/ g.
Fig. 4 is the image according to the microphoto of the cellulose of the inventive method manufacturing and para-aramid pulp.
It is believed that, substantially be evenly distributed on these aramid particles and fibre structure in whole reinforcing material and friction and the encapsulant, be inclined to by the hot properties of para-aramid polymer and the fibrillation of cellulose and para-aramid fiber, a large amount of enhancings position be provided and improve ABRASION RESISTANCE.When finish grinding altogether, the blend of cellulose and para-aramid materials is very abundant, so that in friction or encapsulant the adjacent cellulosic structure of some para-aramid fibre structures is always arranged, thereby can share stress and abrasion in the use.
Encapsulant
The invention still further relates to the method for encapsulant and manufacturing sealing material.Encapsulant is used to or prevents the leakage of fluid and/or gas and under the situation that 2 article link together, be used for preventing entering of pollutant as the barrier layer.It is pad that the typical case of encapsulant uses.Encapsulant comprises binding agent; Randomly at least a filler; And the fibre reinforced materials that comprises cellulose of the present invention and para-aramid pulp.Suitable binding agent comprises nitrile rubber, butadiene rubber, neoprene, butadiene-styrene rubber, acrylonitrile-butadiene rubber and their mixture.Binding agent can add with all other parent materials.Binding agent generally is to add in the first step that in the pad production process all dried components is mixed.Other component randomly comprises half finished rubber particle and rubber solvent, or the solution of rubber in solvent, so that the surface of adhesive-coated filler and pulp.Appropriate filler comprises barium sulfate, clay, talcum powder and their mixture.
The appropriate method of making encapsulant is, for example, makes the beater-addition method or the wet method of pad by the slurry of material, perhaps uses so-called rolling process or dry method, at this moment, with all combination of components in elastomer or rubber solutions.
Friction material
Pulp of the present invention can be used as reinforcing material and is used for friction material.So-called " friction material " be meant utilize its frictional behavior as stop or the coefficient of friction of transfer movement energy, high-temperature stability, ABRASION RESISTANCE, to the material of the damping capacity of noise and vibrations etc.The typical case of friction material uses and comprises brake pad, brake shoes, dried clutch surface layer, clutch surface interval, brake pad backing/insulating barrier, automatic transmission paper and friction papers.
In view of these new application, the invention still further relates to friction material and the method for the material that creates friction.Specifically, friction material comprises friction modifiers; Randomly at least a filler; Binding agent; With the fibre reinforced materials that comprises cellulose of the present invention and para-aramid pulp.Suitable friction modifiers is a metal dust, as iron, copper and zinc; Abrasive material is as magnesia and aluminium oxide; Lubricant, as synthetic and native graphite, and the sulfide of molybdenum and zirconium; And organic friction modifiers, as synthetic rubber and cashew nut resin particle.Suitable binding agent is a thermosetting resin, as phenolic resins (that is pure (100%) phenolic resins and various of rubber or epoxide modified phenolic resins), melamine resin, epoxy resin and polyimide resin and their mixture.Appropriate filler comprises barite, calcium carbonate, wollastonite, talcum powder, various clay and their mixture.
The actual step of material of creating friction can be different with the type of requirement friction material.For example, the method for making the molding friction parts relates generally to required combination of components solidify this part in mould, and as needs this part of shaping, heat treatment and grinding.Automatic transmission paper and friction papers generally can by will required combination of components in slurry also with the papermaking on paper machine of traditional papermaking process.
Test method
Following test method will be used for following examples.
Canadian Standard Freeness(CSF) be that knowing of easy degree of dehydration measured from the dispersion of slurry or particle.Freedom is determined according to TAPPI test T227.The data that obtain from this test are represented as Canadian freedom value, the milliliter number of the water that its representative is discharged from aqueous slurries under rated condition.Numerical value shows that greatly freedom is high and the draining tendency is big.Numerical value is low to show that dispersion has the slow tendency of draining.The original fiber degree of freedom and pulp is inversely proportional to, because will reduce speed by the draining of shaping paper washer than the macrofibril number.
The length weighted averageMeasure with " FiberExpert " desk-top analyzer (also be referred to as " PulpExpertFS " now, by Metso Automation of Helsinki, Finland supplies).This analyzer is with the photograph image of digital CCD camera picked-up pulp when the pulp slurry flow is crossed analyzer, and then, hybrid computer is analyzed the fiber in these images and calculated their length weighted average.
Temperature: all temperature are all with a degree centigrade ℃ measurement.
The dawn numberMeasuring according to ASTM D 1577, is the fiber linear density that the gram numerical table with 9000 meters fibre weight shows.The dawn number is at Textechno of Munich, and the Vibroscope that Germany makes goes up and measures.Dawn number * (10/9) equals dezitex.
Thermogravimetric analysis: used cellulose fibre among the present invention keeps the part of its fibre weight when being heated to high temperature with the specific rate of heat addition.Fibre weight is measured with TA Instrument (office of WatersCorporation) of Newark, the ThermogravimetricAnalyzer of Delaware (TGA) 2950 types.TGA provides sample weightlessness with the variation that heats up.Can record percent weight loss under any record temperature with the TA general parsing program.Program curve is composed as follows: at 50 ℃ of balance samples; Sample put into 500 μ l ceramic cup (PN 952018.910) sample cells and with the speed of 20 ℃/min air themperature from 50 ℃ of linear temperature increases to 1000 ℃, temperature is with the thermocouple measurement that is placed directly in specimen cup lid top; , infeed as gas with air with 10ml/min speed.
Test procedure is as follows.With the TGA screen editor TGA program on TA Systems 2900 controllers.The linear temperature program of input sample title and selected 20 ℃/min.Heavy with the heavy function of the peeling of instrument to empty specimen cup peeling.It is long also sample pine loose ground threading specimen cup that fiber sample is cut to about 1/16 inch (0.16cm).Example weight should be in 10～50mg scope.TGA has balance, therefore needn't pre-determine accurate weight.Sample should not fall outside cup.The specimen cup that installs is hung on day horizontal line, guarantee thermocouple near the cup upper limb but do not contact it.Stove lifted to covered specimen cup, starting TGA.In case EP (end of program), TGA will fall stove automatically, take out specimen cup and enter refrigerating mode.Then with TA Systems 2900 general parsing program analyses and produce percent weight loss scanning in the whole temperature range.
Embodiment
To the present invention be described by following specific embodiment now.All umbers and percentage refer to weight without exception, unless point out separately.Embodiment numeral according to method preparation of the present invention.
In this embodiment of the present invention, pulp of the present invention is made by para-aramid fiber and short fiber of cellulose raw material.Shearing length is that 2 inches, monofilament linear density are the VISIL of 3dpf (filament denier) (3.3 dtexs/rhizoid)
The board staple fibre is available from Sateri Oy of Finland.Shearing length is 1/4 inch commercially available KEVLAR
Board Soft flocks shape para-aramid fiber, Style 1F178, available from E.I.Du Pont Company, general headquarters are at Wilmington, Delaware, USA.
Feed the high-speed stirred groove short fiber of cellulose, para-aramid and water simultaneously, pump is crossed Sprout-Waldron12 simultaneously then " the table roller refiner, finish grind about 5min.With 3 mil plate cracks setting values, cellulose fluff peacekeeping water is directly fed Sprout-Waldron12 together " table roller refiner and be slurried into the processing length accepted in the 13mm scope in advance.
Then, press the solid concentration of 50wt% para-aramid fiber and 50wt% short fiber of cellulose, with the cellulose fibre of pre-pulp, the para-aramid fiber of cut-out and the mixing channel that water is combined into high-speed stirred, and be mixed into uniformly that but pump draws slurry, wherein all the solid concentration of components is about 2～3wt%.Then, allowing this slurry pass through Sprout-Waldron12 " the table roller refiner circulates and correct grinding altogether.
This refiner has following function simultaneously:
(1) the para-aramid fiber with short fiber of cellulose fibrillation, cut off and plasticate and become to have the erose fibre structure of stalk and fibril.
(2) disperse all solids, make the correct grinding slurry reach even substantially as preceding definition.
Then, filter the slurry of this correct grinding with filter bag, and, leave in then in the big ZIPLOC type storage bag by press dewatering.The average largest dimension of gained pulp is no more than 5mm, and the length weighted average is no more than 1.3mm, as uses FiberExpert
Survey.
The another kind of method that the present embodiment explanation is finish grinded pulp altogether by para-aramid fiber and the manufacturing of cellulose fibre raw material.2 inches of shearing lengths, monofilament linear density 3dpf (3.3 dtexs/rhizoid), cellulose fibre available from Sateri Oy, cut off 2～3 times with the right angle with cutting machine, with produce most of fibers be shorter than 3/4 inch (1.91cm) and average length about 1/2 inch (1.27cm) at random-length fiber.
The para-aramid fiber production is as follows: at the Lummus cutting machine (available from LummusIndustries, general headquarters are at Columbus, Georgia) on, be 1/2 inch (1.27cm) switching to nominal length available from the multiple yarn of the commercially available KEVLAR board bobbin of E.I.Du Pont Company.Originally not on bobbin and other KEVLAR board para-aramid fiber with multiple length, to cut off 2～3 times with the right angle with cutting machine, with produce most of fibers be shorter than 3/4 inch (1.91cm) and average length about 1/2 inch (1.27cm) at random-length fiber.
Then, press the solid concentration of 50wt% para-aramid fiber and 50wt% short fiber of cellulose, but 2 kinds of components of preparation as mentioned above and water is combined in the high-speed stirred mixing channel that is called hydrabrusher and is mixed into basic pump uniformly draw slurry, wherein all the total solid concentration in the components is about 2～3wt%.Then, as United States Patent (USP) 4,472,241 is described, and the slurry pump pressure is crossed the series that 3 refiners are formed.Refiner has following function simultaneously:
(1) cellulose fiber peacekeeping para-aramid fiber fibrillation, cut off and plasticate and become to have the erose fibre structure of stalk and fibril.
(2) disperse all solids, make the correct grinding slurry reach even substantially, " even substantially " is as preceding definition.
For the wet pulp dregs of rice, make the correct grinding slurry dewatering with horizontal hydroextractor then, and arrive the total water content of desired 50wt% at the baking oven inner drying.Then, with baling press the wet pulp dregs of rice are packaged into bag.When measuring with FiberExpert , the length weighted average of this pulp structure is no more than 1.3mm.
Other procedure of processings and the another embodiment of present embodiment explanation pulp of the present invention.Repeat the program of embodiment 2.But pulp will squeeze this pulp, with further dehydration in the mechanical expression machine after dehydration on the horizontal hydroextractor; (available from BepexCorporation, general headquarters are at Santa Rosa, and California) this pulp of fluffyization is to separate the wet pulp dregs of rice of compacting better to use loosening apparatus then.Then, in baking oven the wet pulp of loosening being dried to total moisture content is about 8wt%, press United States Patent (USP) 5 then, disclosed such in 085,136, in hypervelocity circulator (IIIA type, available from Altenburger Machinen Jackering GmbH, Voisterhauser, Germany) interior further processing is further to loosen and to disperse dry pulp.Then, dry pulp is packaged into bag.When measuring with FiberExpert , the length weighted average of this pulp structure is no more than 1.3mm.
The another embodiment of present embodiment explanation pulp of the present invention.Repeat the program of embodiment 2, but the para-aramid fiber of 1/3rd weight is changed into the para-aramid particle.The para-aramid resin particle is prepared as follows: make p-phenylenediamine (PPD) and paraphthaloyl chloride successive reaction in screw extruder, as United States Patent (USP) 3,884, general disclosed such in 881, but with N-Methyl pyrrolidone/calcium chloride as solvent, to generate granular polymer and from solvent, to be precipitated out.Extract solvent, wash and the oven dry polymer beads, form the nodular powder of various combination grains.Then, according to embodiment 2 in handle the essentially identical mode of para-aramid fiber and handle this para-aramid resin particle.But refiner is extra-milled fibre not only, also the para-aramid particle is cut off and/or plasticate justify, do not contain the particle of fibril substantially.After the dehydration, be a part of total moisture content that the gained pulp of 50wt% is packaged into bag.The remainder of gained pulp further squeeze to total moisture content be about 8wt%, then, as embodiment 3, loosen, disperse and pack.When measuring with FiberExpert , the length weighted average of pulp fibers structure is no more than 1.3mm.
The disc brake pad of pulp of the present invention that prepared blending as follows.About 20kg comprise containing of 7wt% cashew nut resin, 17wt% inorganic filler, 21wt% graphite, coke and lubricant, 18wt% inorganic abradant and 16wt% soft metal non--asbestos bases composite powder, be placed in the 50L Little ford mixer and be mixed together 10～20min.This mixer has 2 high speed choppers, and they have blade and the plough that rotation is slower of " star-rod " configuration.
Then, the fully mixing basic composite powder of 5kg and pulp of the present invention (the common correct grinding pulp that is made of 50wt% para-aramid and 50wt% cellulose fibre) are made up, and wherein the pulp consumption accounts for the 3.8wt% of composite powder and pulp gross weight.Then, by mixing 5～10min again pulp is dispersed in the basic composite powder.In case mixed, the brake pad composition of gained just has the normal vision outward appearance, the fiber fine dispersion coats in basic composite powder and by it fully, does not have the visible balling-up of pulp or the segregation phenomenon of any component substantially.
Pour into this brake pad composition in the single chamber steel mould that is applicable to the shroud brake pad then and cold pressing, in mould, take out then, form the preform brake pad of heavily about 200g to about 5/8 inch (16mm) standard thickness.This preform does not have undue resilience or swelling, and its fastness is enough to bear normal process and does not damage.Make 12 and duplicate preform.These preforms are put in 2 multi-cavity molds then, mould is put into commercially available press, at the about 15min of 300 (149 ℃) compacting-curing (binding agent phenolic aldehyde crosslinked-reaction), and periodically release pressure in case phenol-formaldehyde reaction gas overflow, in the baking oven of 340 (17l ℃) summary addition of constraints, solidify 4h then, to finish the crosslinked of phenol-formaldehyde binders.Then curing mold pad is ground to desired about half inch (13mm) thickness.When relatively the time, not seeing what difference this test is lined with the commercially available brake pad range estimation that contains full para-aramid pulp of equivalent or cellulose pulp, and it has mixing material and enters the broken phenomenon that falls of good fluidity in the backing plate hole and non-flanged.
Then to blending the brake pad sample of pulp of the present invention test to determine its frictional behaviour.
At Link Engineering, Detroig, on the Chase Machine that MI makes, with Society of automotive engineers (SAE) test procedure J661, the sample of test pad is taken from assessment, be generally 1 inch * 1 inch, thick about 3/16 inch (5mm) is to determine under constant voltage and control temperature the hot and cold coefficient of friction during the towing trial of heating steel drum.The periodically abrasion of working sample (thickness loss).Repeat this test with other 2 samples that downcut from other duplicate pad.Blending the brake pad sample of pulp of the present invention show and the essentially identical hot and cold frictional behavior of commercially available pad that contains the full para-aramid pulp of basic equivalent.This test shows that also uniformity and average friction grade between pad and the pad are also basic identical.
Then, (the single of MI lives for Link Testing Laboratories Inc., in Detroit with dynamometer
The plug dynamometer, rolling radius is 289.0mm), press test procedure J2681 (ISO-SWG4) and measure friction and the abrasion of examination pad under various different braking conditions.This test is made up of 17 operating modes that respectively are 5～200 brakings, also measures brake pressure, temperature, retro-speed and the rate of deceleration that The friction coefficient executes and situation about changing.This test also has 2 high temperature decline sections, and during this period, brake pad bears the high initial temperature that constantly increases between constant deceleration period, and reaches the temperature more than 600 ℃.Abrasion are determined in (608 brakings) thickness of pad and the minimizing of weight during according to off-test.The result of the pad of being made by the mixing material of present embodiment shows considerably less decline, even and if decline, also can recover (decline herein is defined in the loss that rubs when maximum temperature applies braking) well, has the coefficient of friction accepted between 0.25～0.4 in non-decline section, surface checking do not occur filling up, and pad and rotor all there is acceptable wear rate.
How the present embodiment explanation can be blended into pulp of the present invention the sealing of " beater-adding " with in the pad.Water, rubber, latex, filler, chemicals and pulp of the present invention as requested consumption be combined into slurry.On recycle metal bolting silk net (for example, paper-machine screen or woven wire), slurry is dried in adding heat tunnel, and be sulfided into the material of the about 2.0mm of maximum ga(u)ge on heated calender by basic elimination water content.This material of compacting increases its density and improves its sealing in hydraulic press or two roll calender.
The sealing of the gasket material of this kind beater-adding is used but be suitable for middle pressure high temperature most generally not as corresponding compression-fibrous material.The pad of this beater-adding can be used to make the auxiliary engine pad, perhaps after further processing, is used for cylinder cover gasket.For this reason, these semi-finished product are laminated to the two sides of spiketooth type sheet metal also by the spike-tooth physical positioning.
How present embodiment explanation can be blended into pulp of the present invention in the pad by the rolling process manufacturing is gone.Component, but do not comprise water, thoroughly do together and mix, carry out blend with the rubber solutions for preparing with appropriate solvent then as embodiment 6.
After the mixing, generally mixing material is transported to the roller calender with batch process.Calender is made up of the pony roll of cooling and the big roller of heating.Mixing material is fed and is drawn in the calender nip by rotatablely moving of 2 rollers.Mixing material will adhere to and around hot lower roll self writhing number layer, it is thick generally to reach about 0.02mm, decide on pressure, thereby form the gasket material that is made of all layer of accumulation of mixing material.At this run duration, the solvent evaporation, elastomer begins sulfuration simultaneously.
In case reach desired gasket material thickness, the roller that just stops, from hot-rolling downcut gasket material and its cutting and/or stamping-out to desired size.Need not further compacting or heating, this material just can be used as pad.In this way, can make the pad of the thickest about 7mm.But, want Bao Deduo by most of pads that this kind mode is made, usually at about 3mm or thinner thickness.
Claims (26)
1. a manufacturing comprises as the cellulose of reinforcing material and the method for para-aramid pulp:
(a) all pulp components of combination comprise:
(1) cellulose fibre, it keeps at least 10% of its weight when being heated to 700 ℃ with 20 ℃/min speed in air, and this fiber accounts for 10～90wt% of total solid in all components, and has the average length that is no more than 10cm;
(2) para-aramid fiber accounts for 10～90wt% of total solid in all components and has the average length that is no more than 10cm; And
(3) water accounts for 95～99wt% of whole components;
(b) all components are mixed into basic slurry uniformly;
(c) finish grind this slurry altogether, by carrying out simultaneously:
(1) fibrillation, the cellulose fiber peacekeeping para-aramid fiber that cuts off and plasticate make them become the erose fibrillating fibre structure with stalk and fibril; And
(2) disperse all solids, so that the slurry of correct grinding is even substantially; And
(d) from the correct grinding slurry, be dewatered to total moisture content and be no more than 60wt%,
Form cellulose and para-aramid pulp thus, wherein cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.
2. the process of claim 1 wherein
The line density of cellulose fibre is not more than 10 dtexs; With
The line density of para-aramid fiber is not more than 2.5 dtexs.
3. the process of claim 1 wherein that pulp does not contain the aggregation of same material substantially.
4. the process of claim 1 wherein that cellulose fibre contains the silica of the form of poly-silicic acid or salt that should acid.
5. the method for claim 4, wherein cellulose fibre also contains the alumina silicate position.
6. the process of claim 1 wherein that all components also comprise
Basically or fully do not contain the granular para-aramid particle of fibril, its amount is no more than the 50wt% of total solid in all components, and has the average largest dimension of 50～2000 μ m, and
In the correct grinding step, with at least a portion para-aramid particle plasticate become less, circle, do not contain the particle of fibril substantially,
Thus in cellulose that forms and para-aramid pulp, cellulose contact with the para-aramid fibre structure and partly looping justify at least a portion, do not contain around the para-aramid particle of fibril substantially.
7. the process of claim 1 wherein in combination step 25～60wt% of cellulose fibers comprise total solid.
8. the process of claim 1 wherein that in combination step, the para-aramid fiber accounts for 40～75wt% of total solid.
9. the process of claim 1 wherein that after dehydration, water accounts for 4～60wt% of whole pulp, and the Canadian Standard Freeness of pulp (CSF) is between 100～700ml.
10. the process of claim 1 wherein that the correct grinding step comprises and makes mixed slurry pass through a series of disk refiners.
11. a manufacturing comprises as the cellulose of reinforcing material and the method for para-aramid pulp:
(a) make up all components, comprise water and first fiber of forming by following component:
(1) cellulose fibre, it keeps at least 10% of its weight when being heated to 700 ℃ with the speed of 20 ℃/min in air, and this fiber accounts for 10～90wt% of total solid in the pulp; With
(2) para-aramid fiber accounts for 10～90wt% of total solid in the pulp;
(b) all components that will make up are mixed into basic suspended substance uniformly;
(c) in disk refiner the correct grinding this suspended substance, thus fiber is cut into the average length that is no more than 10cm, and make to small part fiber fibrillation with plasticate into erose fibrillating fibre structure;
(d) make up all components, comprise that suspended substance, the average length of this correct grinding are no more than second fiber of 10cm (a) (1 and 2) group, and as needs, water is to be increased to water concentration 95～99wt% of whole components;
(e), mix all components, to form basic slurry uniformly as needs;
(f) finish grind the slurry of this mixing altogether, by carrying out simultaneously:
(1) fibrillation, cut off and the mixed slurry of plasticating in solid, make all or all cellulose and para-aramid fiber are transformed into the erose fibrillating fibre cellulose fiber structure with stalk and fibril basically; And
(2) disperse all solids, make the slurry of correct grinding even substantially; And
(h) from the correct grinding slurry, be dewatered to total moisture content and be no more than 60wt%,
Form cellulose and para-aramid pulp thus, wherein cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.
12. the method for claim 11, wherein all components also comprise:
Basically or fully the granular para-aramid particle that does not contain fibril, its amount are no more than the 50wt% of total solid in all components and have the average maximum length of 50～2000 μ m; And
In the first or second correct grinding step, at least a portion para-aramid particle is plasticated into particle less, that justify, do not contain substantially fibril,
Thus in cellulose that forms and para-aramid pulp, cellulose contact with the para-aramid fibre structure and partly looping justify at least a portion, do not contain around the para-aramid particle of fibril substantially.
13. the method for claim 11, wherein after dehydration, erose cellulosic fibrous structure accounts for 25～60wt% of total solid.
14. the method for claim 11, wherein after dehydration, erose para-aramid fibre structure accounts for 40～75wt% of total solid.
15. the method for claim 11, wherein after dehydration, water accounts for 4～60wt% of whole pulp, and the Canadian Standard Freeness of pulp (CSF) is between 100～700ml.
16. cellulose and para-aramid pulp as reinforcing material comprise:
(a) erose cellulosic fibrous structure, it keeps at least 10% of its weight when being heated to 700 ℃ with the speed of 20 ℃/min in air, and this cellulosic fibrous structure accounts for 10～90wt% of total solid;
(b) erose para-aramid fibre structure accounts for 10～90wt% of total solid; And
(c) water accounts for 4～60wt% of whole pulp,
Wherein cellulose and para-aramid fibre structure have the average largest dimension that is no more than 5mm, be no more than length weighted average and stalk and/or the fibril of 1.3mm, wherein cellulose fibril and/or stalk and para-aramid fibril and/or stalk obviously tangle.
17. the aramid pulp of claim 16 also comprises
Basically or fully do not contain the granular para-aramid particle of fibril, its amount is no more than the 50wt% of total solid.
18. the pulp of claim 16, wherein erose cellulosic fibrous structure accounts for 25～60wt% of total solid.
19. the pulp of claim 16, wherein erose para-aramid fibre structure accounts for 40～75wt% of total solid.
20. the pulp of claim 16, wherein cellulosic fibrous structure contains the silica of the form of poly-silicic acid or salt that should acid.
21. the pulp of claim 20, wherein cellulosic fibrous structure also contains the alumina silicate position.
22. the pulp of claim 16, wherein water accounts for 4～60wt% of whole pulp, and the Canadian Standard Freeness of pulp (CSF) is between 100～700ml.
23. a friction material comprises
A kind of friction modifiers;
A kind of binding agent; With
A kind of fibre reinforced materials that comprises the pulp of claim 16.
24. the friction material of claim 23, wherein
Friction modifiers is selected from following one group: metal dust, abrasive material, lubricant, organic friction modifiers and their mixture; And
Binding agent is selected from following one group: thermosetting resin, melamine resin, epoxy resin and polyimide resin and their mixture.
25. an encapsulant comprises:
A kind of binding agent; With
A kind of fibre reinforced materials that comprises the pulp of claim 16.
26. the encapsulant of claim 25, wherein
Binding agent is selected from following one group: nitrile rubber, butadiene rubber, neoprene, butadiene-styrene rubber, acrylonitrile-butadiene rubber and their mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/877,845 US20050284595A1 (en) | 2004-06-25 | 2004-06-25 | Cellulosic and para-aramid pulp and processes of making same |
| US10/877,845 | 2004-06-25 | ||
| PCT/US2005/021343 WO2006012041A1 (en) | 2004-06-25 | 2005-06-16 | Cellulosic and para-aramid pulp and processes of making same |
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| Publication Number | Publication Date |
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| CN1973087A true CN1973087A (en) | 2007-05-30 |
| CN1973087B CN1973087B (en) | 2011-09-07 |
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| CN2005800208653A Expired - Fee Related CN1973087B (en) | 2004-06-25 | 2005-06-16 | Cellulosic and para-aramid pulp and processes of making same |
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| Country | Link |
|---|---|
| US (1) | US20050284595A1 (en) |
| EP (1) | EP1774096B1 (en) |
| JP (1) | JP4634447B2 (en) |
| KR (1) | KR100895185B1 (en) |
| CN (1) | CN1973087B (en) |
| BR (1) | BRPI0512487A (en) |
| CA (1) | CA2567363C (en) |
| MX (1) | MXPA06014286A (en) |
| WO (1) | WO2006012041A1 (en) |
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-
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- 2004-06-25 US US10/877,845 patent/US20050284595A1/en not_active Abandoned
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2005
- 2005-06-16 WO PCT/US2005/021343 patent/WO2006012041A1/en active Application Filing
- 2005-06-16 MX MXPA06014286A patent/MXPA06014286A/en active IP Right Grant
- 2005-06-16 KR KR1020067027088A patent/KR100895185B1/en not_active IP Right Cessation
- 2005-06-16 CA CA2567363A patent/CA2567363C/en not_active Expired - Fee Related
- 2005-06-16 BR BRPI0512487-5A patent/BRPI0512487A/en not_active Application Discontinuation
- 2005-06-16 CN CN2005800208653A patent/CN1973087B/en not_active Expired - Fee Related
- 2005-06-16 EP EP05766016A patent/EP1774096B1/en not_active Expired - Fee Related
- 2005-06-16 JP JP2007518132A patent/JP4634447B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106151331A (en) * | 2016-06-27 | 2016-11-23 | 杭州桑拉科技有限公司 | A kind of electric car automatic speed transmission Wet-type friction slice and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008503661A (en) | 2008-02-07 |
| BRPI0512487A (en) | 2008-03-04 |
| MXPA06014286A (en) | 2007-02-19 |
| CA2567363A1 (en) | 2006-02-02 |
| KR20070034004A (en) | 2007-03-27 |
| WO2006012041A1 (en) | 2006-02-02 |
| KR100895185B1 (en) | 2009-04-24 |
| CN1973087B (en) | 2011-09-07 |
| JP4634447B2 (en) | 2011-02-16 |
| CA2567363C (en) | 2013-10-01 |
| EP1774096A1 (en) | 2007-04-18 |
| US20050284595A1 (en) | 2005-12-29 |
| EP1774096B1 (en) | 2012-02-22 |
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