CN86101136A - Fibrous apatite and production method thereof - Google Patents
Fibrous apatite and production method thereof Download PDFInfo
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- CN86101136A CN86101136A CN86101136.8A CN86101136A CN86101136A CN 86101136 A CN86101136 A CN 86101136A CN 86101136 A CN86101136 A CN 86101136A CN 86101136 A CN86101136 A CN 86101136A
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Abstract
The invention provides a kind of non-woven fabric fibrous apatite product, this product comprise one or more to be selected from following general formula be one group of apatite: M of representative
10(ZO
4)
6X
6M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe etc., ZO in the formula
4Represent PO
4, ASO
4VO
4, CO
3Deng, X represents F, Cl, OH etc.This fibrous apatite product has many purposes, for example is used for medical treatment, and microbial culture medium and other purposes have the graft materials of excellent compatibility and superior practicality in particular for living tissue.
The invention also discloses the method for preparing fibrous apatite product.
Description
The method that the present invention relates to fibrous phosphoric acid ash stone material and produces this material.Especially the cotton shape that serves many purposes and non-woven fabric-shaped apatite material and production method thereof, as be used for medical treatment, culture medium of extensive microorganism or the like.In particular, the present invention relates to living tissue good compatibility is arranged and has the apatite of high workload efficient to move grow material and production method thereof.
Artificial moving grown material traditionally often by cutting patient oneself, and by similar bone or other non-similar bone and metal that the close relative provides, organic matter and material with carbon element are repaired fracture, bone split seam or tooth root.Yet if use patient's oneself bone, patient will stand pain tempestuously on the bone tissue of excision, because this bone tissue must cut down from intac other position.In addition, perhaps not necessarily there are enough bones can satisfy the quantity that is used to repair, therefore usually need to use substitute to replenish the shortage of bone.Do not use patient's oneself bone to make substitute in order to use similar bone that the close relative provides or non-similar bone, this just need implement operation on another living tissue, will cause major defect on one's body contributing the bone person like this.
On the other hand, the metal graft materials not only lacks the affinity with the group group of living, and another shortcoming is exactly that metal ion will dissociate out from graft materials and enters human body, thereby causes material rotten.These metal ions may be harmful.For these reasons, the metal of having demonstrate,proved moves to be grown material and is unsuitable for permanent use.This also is like this for organic material and material with carbon element.
For overcoming above-mentioned shortcoming, monocrystalline or polycrystal alumina, silica, aluminum phosphate or calcium phosphate glass and pottery (for example, are seen Japan patent applicant announce spare N as apatite
o52-64199) be proposed recently with always moving and grown material.Contain metal-cored composite and be published in Japan patent applicant announce spare N
o52-82893 on this is metal-cored, has hydroxyl-apatite powder with flame-spraying.What these ceramic materials were better than other material is that they and living tissue have very strong affinity, can also provide with bone tissue directly and closely to be connected.Especially people have known that hydroxyl-apatite is the main inorganic composition of bone or tooth.At this on the one hand, synthesis of hydroxy-apatite through roasting is grown material as so-called artificial moving, be used for artificial tooth, bone or the like has caused people's attention widely, because the foreign matter of phosphor lime stone demonstrates so good and affinity bone and dental tissue, with activation and bone tissue with the glue direct chemical is bonding (for example, sees chemistry and industry, 37 volumes, N
o4, the 247 pages, 1984).Apatite artificial dental root and porous apatite artifical bone through roasting have reached the practical stage.
Although the apatite of roasting has very high compression strength,, flimsy born of the same parents' property material when the apatite of roasting is still a kind of stretching.Therefore, if a crackle that hairline is thin is arranged, after being shaken, crackle will cause the tensile strength of apatite to reduce greatly in the expansion of apatite surface.This limitations restrict it be used for living tissue range of application.Thereby make these materials only be limited to class artificial dental root's purposes such as molar, these tooth root places can not apply excessive tension.In addition, when these materials were used as the filler of knochenbruch, when these materials of moulding, it was very difficult wanting to make the complicated profile phase in material and injury consistent.
For attempting to eliminate the shortcoming of above-mentioned apatite through roasting, Japan patent applicant announce spare N
o57-117621 and N
o58-54023 has delivered Phos lime stone fibrous material, and in this material, apatite is made into fibrous, to be applicable to bone damage and crack and bone split seam.Yet axially the apatite fibrous material delivered of patent is with so-called melt spinning method production, and its production stage is at high temperature apatite fusion and spinning.By its data of delivering, this melt spinning method needs 1500 ℃ high temperature to come the melt phosphorus lime stone, and consequently, apatite is sloughed hydroxyl, thereby has affinity.Compare with hydroxyl-apatite like this, the apatite fibrous material has a critical defect, and promptly it can not provide enough compatibilities to living tissue.For this reason, the apatite fibrous material of this melt spinning needs post processing, so that the compatibility material with affinity to be provided.
If apatite is made fibrous, and do not slough hydroxyl, just can not adopt melt spinning method, but another method such as the solvent spinning method, be should give consideration.Yet, owing to also do not develop the adhesive that is applicable to the solvent spinning method, and spinning process and method of roasting, so make fibrous apatite so far, it is impossible especially making cotton shape of maintenance or textile-like apatite.
In order to overcome the shortcoming of above-mentioned prior art, after further investigation and inquiring into, inventor of the present invention has found to make fibrous apatite, particularly cotton shape apatite and non-woven fabric-shaped apatite are possible, its method is to use special adhesive to come with solution spinning apatite, make it to become fibrous, especially become cotton shape and non-woven fabric-shaped, the apatite that roasting then made.
Therefore, an object of the present invention is to provide fibrous apatite, especially versatile cotton shape and non-woven fabric-shaped apatite for example are used for medical treatment, extensive biological culture medium or the like.
Another object of the present invention provides fibrous hydroxyl-apatite material, the cotton shape and the non-woven fabric-shaped apatite that especially can good compatibility be arranged with living tissue and have excellent rerum natura (as tensile strength etc.).
The present invention also has another purpose, just provides the method for producing above-mentioned fibrous type apatite material, the method for especially producing cotton shape and non-woven fabric-shaped apatite material.
The present invention also has another purpose, has very the apatite of number compatibility and high workability move with living tissue to grow material with regard to providing.
In a word, the invention provides a kind of product of fibrous apatite, this product comprises that one or more are selected from one group of apatite with following general formula,
M
10（ZO
4）
6X
2
M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe etc., ZO in the formula
4Represent PO
4, As, O
4, VO
4, CO
3Deng, and X represents F, Cl, OH etc.Specifically providing a kind of hydroxyl-apatite content is main fibrous apatite product.
The present invention also can provide a kind of fibrous apatite product that is mixed with calcium phosphate compound for enhancing.
If desired, can be processed into the apatite fiber product form of cotton shape or bondedfibre fabric according to the present invention.
On the other hand, the invention provides, comprise the dispersion for preparing the apatite fine powder with water-soluble high-molecular compound, with solution spinning this dispersion is carried out spinning then according to the method for producing above-mentioned fibrous apatite product.
Together with reference to the accompanying drawings, will fully understand these and those purposes and characteristics of the present invention of the present invention from following detailed description of the invention.In the accompanying drawings:
Fig. 1 is the diagrammatic side view that is used to produce a kind of equipment of cotton shape apatite of the present invention.
Fig. 2 is the diagrammatic side view that is used to produce a kind of equipment of non-woven fabric-shaped apatite of the present invention.
Fig. 3 is the X-ray diffraction figure line of cotton shape hydroxyl-apatite of the present invention.
Fig. 4 is the X-ray diffraction figure line of the hydroxyl-apatite cotton shape product of material before roasting of Fig. 3.
Fig. 5 is that cotton shape apatite product of the present invention is respectively at the forward and backward electron micrograph of roasting.
According to fibrous apatite product provided by the invention, particularly cotton shape or non-woven fabric-shaped apatite product, the raw material of these products comprise that one or more are selected from the one group of apatite material that is represented by a general formula. Its general formula is:
M
10（ZO
4）
6X
2
M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe etc., ZO in the formula4Represent PO4、As O
4、VO
4、CO
3Deng, X represents F, Cl, OH etc.
Here use " cotton shape product " word is to be that the explanation fiber twines mutually the product that forms, and just likes cotton. If need, cotton shape apatite product can be made into non-woven fabric-shaped apatite product.
According to the present invention, by the expressed any or multiple apatite of above-mentioned general formula can use separately or and usefulness, to make one or more fibrous apatite products. When producing medical moving when growing material, should select the apatite of calcium phosphate, this is because it and bone tissue are very similar. From with living tissue compatibility angle, use hydroxyl-apatite better (compound represents that with the said general formula in front M is that Ca, ZO are PO in the formula, and ethyl X is OH) yet, should think that the present invention does not get rid of to use in the above representative general formula at M, ZO4With other compound of some except Ca, PO and OH on the X position, as long as these compounds do not weaken and living tissue compatibility. In other words can use two kinds or more kinds of apatite materials.
According to most preferred embodiment of the present invention, can provide the fiber that accounts for Main Ingredients and Appearance with hydroxyl-apatite Shape apatite product.
Yet this fibrous apatite take hydroxyl-apatite as Main Ingredients and Appearance may can not be satisfactory aspect intensity. At this on the one hand, fibrous apatite product contains the inorganic compound such as calcium phosphate possibly, can improve physical property such as intensity etc. such as this class inorganic matter. Corresponding another embodiment of the present invention can provide except containing hydroxyl-apatite, also contains the fibrous apatite of calcium phosphate type compound. This compound is from calcium monohydrogen phosphate (Ca HPO at least4), tricalcium phosphate (Ca3（PO
4）
2) and tetracalcium phosphate (Ca4O（PO
4）
2) in select a kind of. May comprise these compounds in the apatite product, its percentage by weight is generally 5～95%, is preferably 80% or less than 80%, and preferably 50% or less than 50%. The calcium-phosphate type compound can be by beginning earlier a certain amount of required calcium phosphate compound, be blended into and carry out fusion in the Main Ingredients and Appearance, or use another kind of method, hydroxyl-apatite is carried out high-temperature process, produce the compound that contains a certain amount of calcium carbonate from part of hydroxyl-apatite, will narrate below.
According to fibrous apatite of the present invention, the average diameter of fiber is 1 μ m～30 μ m in general, and average length is 1mm～1,000mm. Certainly, be not limited thereto, and just to saying something. As previously mentioned, according to the present invention, fibrous apatite may be made cotton shape or non-woven fabric-shaped.
For this adhesive-bonded fabric, its basis weight is usually at 5g/m2～500g/m
2In the scope, but be not limited thereto.
Cotton-like fiber apatite of the present invention can be with the method production that comprises following operation:
(a) apatite is scattered in the water-soluble binder equably, to prepare a kind of apatite dispersion. Said apatite is that one or more are selected from one group of apatite that general formula represents, general formula is:
M
10（ZO
4）
6X
2
M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe etc., ZO in the formula
4Represent PO
4As O
4VO
4CO
3Deng, X represents F, Cl, OH etc.;
(b) extrude many spinneret orifices of dispersion that continuously will prepare from spray silk machine, meanwhile these dispersions are drawn into by high-speed air fibrous, to form the fine fibre bundle;
(c) heat above-mentioned fibre bundle, water is evaporated from fiber.
(d) the above-mentioned fibre bundle that anhydrates that removes is blown on the gatherer, to form a kind of cotton shape apatite product of binding agent bonding; With
(e) if desired, the above-mentioned cotton shape product of roasting.
According to a most preferred embodiment of the present invention, with hydroxyl-apatite that general formula is represented, M is Ca, ZO in the formula
4Be PO
4And X is OH.
The apatite that is used for purpose of the present invention both can be a kind of with the synthetic suitable material of known method, or a kind of natural materials.These apatite are fine graineds, and its average grain diameter is 50A °～1 μ m, are preferably 70～500A °.In this case, when the profile of apatite is not limited to a kind of special shape, preferably use rod-shpaed particle, become fibrous or cotton shape because this bar-shaped profile helps the apatite institutional framework.Although can't explain this reason fully, suppose that once in spray silk process, it is easy to make rod-shpaed particle to be orientated by predetermined direction.Bar-shaped apatite particle such as hydroxyl-apatite can be by preparing in the aqueous slkali (the pH value is 7～11) that phosphate aqueous solution is splashed into gradually calcium ions.
According to the present invention, the binding agent that is used for producd fibers shape apatite product can be common known water soluble binding agent.These binding agents can be water miscible, have-OH-COOH ,-CONH
2Base or in their molecules, have the cotton family macromolecule compound of other similar base, comprise pullulan, this is a kind of linear glucan, and wherein maltotriose bonds by the following material of slaking again, and these materials are α-1.6 glucoside keys, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethylacrylic acid, poly-clothing saccharic acid, polyethylene glycol oxide, PVP, polyvinyl methyl ether, hydroxypropyl cellulose, xanthic acid fat glue, guar gum, collagen, hydroxyethylcellulose, suchlike material such as carboxymethyl cellulose.When molecular weight was not had particular restriction, the molecular weight of this macromolecular compound was preferably 20,000～2, and 000,000, the best is 50,000～1,000,000.
According to the present invention, when fibrous apatite product was specifically designed to medical material, require binding agent should satisfy two conditions at least promptly: a pair of vital tissues was harmless, and two can be water-soluble.The suitable embodiment of this binding agent can comprise some macromolecular compounds, as polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, material like that such as collagen, and also comprise some macromolecule polysaccharidases, as pullulan, chitin, material like that such as glucan.Pullulan is particularly suitable.
According to the present invention, the dispersion that apatite particle is constituted sprays silk, and this apatite particle is dispersed in the aqueous solution of above-mentioned binding agent.The component of dispersal of feed body should be in predetermined scope.According to example, for hydroxyl-apatite, its component can comprise 10～90%, be preferably 50～70%, is more preferred from 60～65% water (weight) (following all by weight); 5～70%, be preferably 15～30%, be more preferred from hydroxyl-apatite of 15～20%; 5～40%, be preferably 15～30%, be more preferred from 20～25% binding agent.If hydroxyl-apatite percentage by weight less than 5%, just can not provide the fibrous apatite material with sufficient intensity.On the contrary, greater than 70% o'clock, will increase unnecessary viscosity extraly.
In order to improve hydroxyl in the raw material liq-apatite dispersion, organic carboxyl acid be can add or the plasticizer or the softening agent of polyhydroxy-alcohol contained, as glycerol, sorbierite, maltitol, ethylene glycol, material like that such as propylene glycol.
In addition, inorganic compound such as calcium phosphate except that apatite can be used as decentralized medium, for example add weight less than 5%, thereby improve the physical characteristic of gained fibrous apatite.
Prepare material solution by above-mentioned requirements when in the present invention, being preferably in temperature and being 20～70 ℃.The successive ground warp spinneret orifice extruding of Zhi Bei dispersion like this, gas is discharged at a high speed via the steam vent of next-door neighbour's spinneret orifice simultaneously, thereby makes dispersion make fibre bundle.The filament tow dehydration collects with the cotton-like fiber product form, if desired, and can be to the product roasting.
About hydroxyl-apatite, find that by the experiment that X-ray diffraction and infrared spectrophotometry degree are measured if not roasting, perhaps sintering temperature is lower than 1250 ℃, then this fibrous apatite material will be Ca
10(PO
4) OH
2Or Ca
5(PO
4)
3The structure of OH if sintering temperature is higher than 1250 ℃, will change into α-Ca
3(PO
4)
2Structure.The product of this conversion does not have hydroxyl, thereby causes reducing with living tissue compatibility performance.For just hydroxyl-apatite is Main Ingredients and Appearance, be preferably in when temperature is lower than 1250 ℃ and carry out roasting, be preferably lower than 1200 ℃.
An embodiment of fibrous apatite method produced according to the invention referring to Fig. 1, wherein uses hydroxyl-apatite fine grained as raw material, now is described below.
At first, hydroxyl-apatite, binding agent and water, and also can add dispersant if desired, and plasticizer or softening agent, these raw materials enter head tank 2 by feeding line 1, to make viscosity spray silk solution.Preparation when this solution is preferably in 20～70 ℃.Motor 3 driving gear pump 4 through conduit 15 chargings, are extruded solution then by spinneret, simultaneously, multistage blowers 6 are to discharge gas at a high speed through the steam vent 7 of spinneret orifice outer ring.Spinneret is by many horizontal compositions of mouth laterally arranged in a straight line.Fine fibre bundle 8 stretches under the gas effect, and prescinds, and the temperature of this gas (as air) is about 20～60 ℃, and the flow velocity around spinneret is 5～1000m/sec.The diameter of fiber and length can be adjusted by changing pressure at expulsion, so that make its diameter and length respectively in 1～30 μ m and 2～1, in the 000mm scope.
Then, as far infra-red heater 9 or other similar heater, this heater is placed on below the spinning nozzle fine fibre bundle 8 that has been shaped by the heater heating, so that water volatilizees up to moisture less than 10%(weight), preferably less than 7%, thereby fibre bundle is solidified.It should be noted that undue dehydration can cause can not produce the cotton-like fiber apatite that fine fibre is formed.For this reason, be heated to about 80～150 ℃ for making fibre bundle, the temperature that can make heater is generally in 200～500 ℃ of scopes.The adding temperature of fibre bundle selects to depend on the rate of extrusion of spray silk solution, the temperature of gas and flow.Needn't use too high temperature, can cause binding agent to decompose like this in the heating period.
With stretched, the fine fibre bundle 10 that prescinds and slough water blows on the suitable gatherer 11 at last, and this gatherer can be a net type collecting vessel, also can be net type collecting belt, thereby makes fibre bundle be collected and store at this.
If make the non-woven fabric-shaped fibrous apatite, the fine fibre bundle of above-mentioned drawn and dehydration will be fallen on the mobile gatherer, this gatherer can be net type turning barrel device 16(as shown in Figure 2), it also can be moving conveyor belt, fibre bundle twines mutually on gatherer, thereby forms bondedfibre fabric.If fibre bundle is blown in two folder cracks between the net type bucket 16, so just made along the bondedfibre fabric 17 of bondedfibre fabric thickness direction orientation (promptly in three dimensions).In another embodiment, if fibre bundle is blown into the turning barrel zone, rather than in the folder crack between two net type buckets or on the planar collecting conveyer belt, will produce the bondedfibre fabric of parallel, horizontal planar orientation (being in the two-dimensional space).The basis weight of bondedfibre fabric can be adjusted, and should make it be in 5g/m
2～500g/m
2In the scope, for example adjust by the translational speed that changes gatherer.
The fibrous apatite of Sheng Chaning like this, promptly so-called cotton shape or non-woven fabric-shaped apatite product with the binding agent bonding, soft touch is desirable.In addition, because cotton shape or non-woven fabric-shaped apatite product possess hydrophilic property, hygroscopicity, non-conductive property and cultivate facilitation, this product can be used as the culture medium of microorganism under green state.
Not the cotton shape product of roasting or non-woven fibre can about 500～1250 ℃, be preferably in about 600～1200 ℃, be more preferably under 650～1100 ℃ of roastings, with the burn off binding agent, obtain fibrous apatite material of the present invention thus.When sintering temperature is lower than 1200 ℃, the hydroxyl loss is few, although the hydroxyl loss amount is somewhat dependent upon sintering temperature, so the above-mentioned loss amount of hydroxyl can not considered.If required, the Ca in production hydroxyl-apatite
3(PO
4)
2Sintering temperature can be higher than 1200 ℃, to improve physical characteristic, for example, when hydroxyl-apatite as moving when growing material, can improve the intensity of cotton shape product or non-woven fibre.
Also can further process by cotton shape or non-woven fabric-shaped product that this method obtains by its application target.As embodiment, can or flood this product or fabric the ossein adding, so that further improve its required physical characteristic.Also can be in conjunction with culture, for example pullulan uses to be fit to making big rule culture medium.
According to another preferred embodiment of the present invention, be outside fibrous apatite material hydroxyl-removal-apatite, also contain calcium phosphate compound.This fibrous apatite material can be by following method production: add water-soluble binder in the fine grain aqueous solution of hydroxyl-apatite and calcium phosphate compound, form the viscosity dispersion; Make dispersion continuously by many spinneret orifice spray silks on the spray silk machine, simultaneously, by steam vent high speed exhaust, so that tensile fiber is become the fine fibre bundle from spinneret orifice near spinneret orifice; Heating fiber bundle to be removing moisture content wherein, and this fibre bundle is blown into collects board-like gatherer, makes cotton shape apatite product.
In this case, the raw dispersion composition preferably contains 5～90% water, 5～70% apatite, 5～70% calcium phosphate and 2～30% hydroxyls-apatite.Optimum component is 25% water, hydroxyl-apatite of 35%, 30% calcium phosphate, and 10% pullulan (all calculating by weight).Other working condition can be that the working condition of Main Ingredients and Appearance is basic identical with apatite with producing foregoing.
Various details embodiment is appreciated that these embodiment do not limit the present invention.
Embodiment 1
With 11%(weight) the pullulan particle, its mean molecule quantity is hydroxyl-apatite particle of 200,000,17%, its particle diameter is that 50～800A ° and 72% water are kneaded, so that hydroxyl-apatite is dispersed in the pullulan aqueous solution.At room temperature (25 ℃), in the solution deaeration that makes thus and the spinning appts as Fig. 1 of packing into, having many diameters on the transverse slat of this device is the spinneret horizontal arranged in a straight line of 0.3mm.Solution is extruded with 1.4kg/cm pressure by nozzle, simultaneously, passes through the pore exhaust with the speed of 250m/sec, forms fibre bundle thus.Far-infrared heater below nozzle of this fibre bundle (wavelength: 2～5 μ m) on its opposite in 400 ℃ of heating, water evaporates is fallen, and fibre bundle is blown on the net type band, produce fibrous product by the cotton shape hydroxyl-apatite of pullulan knot.The cotton shape product that makes by this method is with 50 ℃/hour rate of heat addition heating, 1100 ℃ of roastings 1 hour, and the cotton shape apatite product after so just obtaining the pullulan roasting and removing, its fiber diameter is 5 μ m, average fiber length 50mm.Show that through X-ray diffraction and infrared spectrophotometry the amount of hydroxyl groups of the hydroxy radical content of the cotton shape product of method acquisition and raw material is basic identical thus.Fig. 3 and Tu illustrate the X-ray diagram before and after the calcining process respectively.
With mean molecule quantity is that 200,000 pullulan dissolves in water, makes 21%(weight) aqueous solution, wherein be mixed with particle diameter and be hydroxyl-apatite of 6% of 50A °.Then, with this solution deaeration.At room temperature, the feed liquid that makes thus packed into is used for the device of embodiment 1, simultaneously, with the speed of 500m/sec air is discharged from steam vent, thereby forms fibre bundle.With the far-infrared heater (wavelength: 2～50 μ m) that is positioned under the spinneret, this fibre bundle on its opposite in 400 ℃ of heating, evaporating moisture content, and this fibre bundle is blown on the net type band, to produce fibrous product by the cotton shape hydroxyl-apatite of pullulan knot.The product that makes thus heats with 50 ℃/hour adding speed, 1400 ℃ of roastings 2 hours, and the cotton shape apatite product behind the burn off pullulan that obtains, its fiber diameter is 3 μ m, average fiber length is 30mm.Show that through X-ray diffraction and infrared spectrophotometry method mensuration cotton shape product has lost hydroxyl.
Except used pullulan particle, hydroxyl-apatite particle and water are respectively 19%, 31% and 50%(all by weight) in addition, pressing embodiment 1 same operation handles, with the cotton shape hydroxyl-apatite product after the acquisition roasting, its fiber diameter is 15 μ m, and average fiber length is 70mm.
Embodiment 4
Remove to use molecular weight be 190,000 polyvinyl alcohol as beyond the binding agent, press the same operation processing of embodiment 1, thereby obtain the cotton shape hydroxyl-apatite product after the roasting, its fiber diameter is 7 μ m, average fiber length is 65mm.
Except that using 50%(weight) hydroxyl-apatite particle and 15% pullulan particle and the speed exhaust with 7200m/sec, under the condition identical, prepare fibre bundle with embodiment 1, thereby obtain cotton shape hydroxyl-apatite product, its fiber diameter is 3 μ m, and average fiber length is 35mm.
With 11%(weight) the pullulan particle, its mean molecule quantity is 200000,17% hydroxyls-apatite particle, its particle diameter is that 50～800A ° and 72% water are kneaded together, and the apatite average mark is dispersed in the pullulan aqueous solution.With the solution deaeration that makes thus, and in the spray silk machine as Fig. 2 of under room temperature (25 ℃), packing into.Solution is subjected to the pressure extrusion of 1.4kg/cm by nozzle, and simultaneously, gas by the steam vent exhaust, forms fibre bundle with the speed of 250m/sec.Far-infrared heater below spinneret (wavelength: 2～50 μ m) with fibre bundle on its opposite in 400 ℃ of heating, evaporate moisture content and fiber is blown on the net type band, so that produce hydroxyapatite product by the non-woven fabric-shaped of pullulan knot.The bondedfibre fabric of producing by this method is with 50 ℃/hour rate of heat addition heating, 1100 ℃ of roastings 1 hour, obtains the hydroxyl-apatite bondedfibre fabric behind the burn off pullulan, and its fiber diameter is 5 μ m, and basis weight is 200g/m.Show that through X-ray diffraction and infrared spectrophotometry method mensuration the bondedfibre fabric that obtains thus contains the hydroxy radical content identical with raw material basically.Fig. 5 illustrates the electron micrograph of calcining process front and back non-woven fabric fiber.
With mean molecule quantity is that 200,000 pullulan particle dissolves in water to make 21%(weight) aqueous solution, be mixed with its particle diameter in the aqueous solution and be 6% hydroxyl-apatite particle of 50～300A °.Then, with the solution deaeration.At room temperature, the feed liquid of preparation is thus packed into and is used for the device of embodiment 6, and extrude with 1.4kg/cm pressure, simultaneously, gas by exhaust just with the speed exhaust of 500m/sec, the formation fibre bundle.Far-infrared heater below spinneret (wavelength: 2～50 μ m) on the fibre bundle opposite in 400 ℃ of heating, evaporating moisture content, and fibre bundle is blown on the net type band, produce non-woven fabric-shaped product by the hydroxyapatite of pullulan knot.The bondedfibre fabric of making thus heated with 50 ℃ of/hour rates of heat addition, 1400 ℃ of roastings 2 hours.Behind the pullulan burn off, obtaining fiber diameter 3 μ m and basis weight is the bondedfibre fabric of the apatite of 200g/m.Show that through X-ray diffraction and infrared spectrophotometry method mensuration the bondedfibre fabric that obtains by this method has lost hydroxyl.
Remove the pullulan particle, hydroxyl-the apatite particle and the used water yield are respectively 19%, 31% and 50%(all calculate by weight) in addition, undertaken by embodiment 6 same operations, obtain that fiber diameter is the hydroxyapatite bondedfibre fabric of 15 μ m after the roasting.
Remove using molecular weight is that 190,000 polyvinyl alcohol are done beyond the binding agent, is undertaken by embodiment 6 same operations, obtains that fiber diameter is hydroxyl-apatite bondedfibre fabric of 7 μ m after the roasting.
Except viscosity dispersion component in the head tank 2 comprises 25% water, 35% hydroxyl-apatite, 30% calcium phosphate and 10% pullulan (by weight) in addition, present embodiment carries out according to embodiment 6.The spinneret diameter is 0.3mm, and spray silk temperature is room temperature (25 ℃), and pressure at expulsion is 300～100mm HO.
In addition, far-infrared heater 9 length are 800～1000mm, and power output is 4～10kw, and the heating-up temperature that provides is 400 ℃.With 50 ℃/hour rate of heat addition heating apatite bondedfibre fabric, 1100 ℃ of roastings 2 hours.
To have fibre diameter and the high mechanical strength of 3～15 μ m be high-tensile and impact strength to Zhi Bei the apatite through roasting in the above-described embodiment.
Be understood that because apatite is fusion under solvent spinning rather than the high temperature at room temperature by above-mentioned, so the invention provides a kind of cotton shape and non-woven fabric-shaped apatite product, compare with prior art, this product is not removed hydroxyl (removing hydroxyl will damage and living tissue affinity).Therefore, unnecessaryly give fibrous apatite product with " affinity ", thereby simplified manufacturing technique and improved operating efficiency with post processing.Can believe that due to the fact that, promptly binding agent such as pullulan are found, it can satisfy living tissue nontoxic, water-soluble fluidity and not fusion at high temperature and three conditions such as decomposition make it at room temperature to carry out solvent spinning.And, thereby be used for the used common spinning equipment of so-called melt-blown method or melt spinning method through such improvement will spray the silk material solution make fibrous apatite product, this material solution forms fibre bundle by spinneret, rather than the raw material of use high-temperature fusion, heating fiber bundle is removed moisture content, fibre bundle blown on the gatherer as collecting board or net type drum gatherer on, and these gatherers are the devices that are used for conventional melt-blown method.
The present invention is that first successfully uses the solution spinning process to obtain high strength fibre shape apatite, And this method be it is believed that so far and can not be used for producing this apatite. According to the fibrous apatite that the present invention produces, particularly cotton shape product or apatite adhesive-bonded fabric are not removed hydroxyl, demonstrate the same with normal sintering apatite and living tissue affinity. Furtherly, the composition of hydroxyl-apatite can pass through to change the sintering temperature adjustment in the fibrous phosphorus ash, thereby controls its physical characteristic such as intensity. In addition, because product itself is fibrous, apatite material of the present invention can provide high impact resistance and good processing characteristics, so it also just is easy to consistent with the staggered profile of fracturing. Fibrous apatite so of the present invention can not only be used for artificial teeth and can also for artificial joint after the reparation of various bones, also can be used in addition the dimensional culture medium in Biological Technology.
Each embodiment of the present invention has been done as above to describe, and the present invention should be not limited to these embodiment, but the various changes and the remodeling that do not deviate from essence of the present invention and scope will be restricted.
Claims (22)
1, a kind of fibrous product of apatite comprises that one or more choosings have following general formula:
M
10(ZO
4)
6X
2
Be one group of apatite of representative, M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe and analog thereof, ZO in the formula
4Represent PO
4, AsO
4, VO
4, CO
3And analog, X represents F, Cl, OH and analog thereof.
2, the fibrous product of apatite according to claim 1, wherein M is a kind of and Sr that is selected from Ca, Ba at least, ZO
4At least be to be selected from PO
4, VO
4And CO
3A kind of, X is be selected from OH and F a kind of at least.
3, the fibrous product of apatite according to claim 1, the Main Ingredients and Appearance of said all phosphorus stones are hydroxyl-apatite, and wherein M is Ca, ZO
4Be PO
4, X is OH.
4, the fibrous product of apatite according to claim 3, described apatite also contain calcium phosphate compound except containing described hydroxyl-apatite.
5, the fibrous product of apatite according to claim 4 contains 5～95%(weight) hydroxyl-apatite and 95～5% calcium phosphate compounds.
6, the fibrous product of apatite according to claim 5, wherein said hydroxyl-apatite content is 20%(weight) or it is more, described calcium phosphate compound content is 80% or still less.
7, the fibrous product of apatite according to claim 5, wherein said hydroxyl-apatite content is 50%(weight) or it is more, described calcium phosphate compound content is 50% or still less.
8, according to the fibrous product of each described apatite of claim 4 to 7, wherein said calcium phosphate compound is to be selected from calcium monohydrogen phosphate at least, tricalcium phosphate and tetracalcium phosphate a kind of.
9, according to the fibrous product of each described apatite of claim 1 to 8, its fiber diameter is 1 μ m～30 μ m, and average fiber length is 1mm～1000mm.
10, according to the fibrous product of arbitrary auspicious described apatite of claim 1 to 9, it can be made into cotton shape product or nonwoven products.
11, apatite fibrous product according to claim 10, wherein said bondedfibre fabric basis weight is at 5～200g/m
2Scope in.
12, a kind of method of producing the fibrous apatite of cotton shape form comprises following operation:
(a) the apatite fine grained is dispersed in the adhesive solution, with the dispersion of preparation apatite, described apatite is more than one apatite, is selected from the phosphorus ash stone of following general formula representative:
M
10（ZO
4）
6X
2
M represents Ca, Ba, Mg, Sr, Pb, Cd, Fe and analog thereof, ZO in the formula
4Represent PO
4, As, O
4, VO
4, CO
3And analog, X represents F, Cl, OH and analog thereof;
(b) by the continuously extruded dispersion of many spinneret orifices, simultaneously, dispersion is drawn into fiber condition, to form the fine fibre bundle by means of high-speed air flow by this method preparation;
(c) the described fibre bundle of heating is to evaporate the moisture content in the fiber;
(d) fibre bundle that will remove water is blown in the gatherer, to form by the cotton shape product of the apatite of adhesive cementation; With
(e) if required, roasting should cotton shape product.
13, method according to claim 12 also comprises the operation of cotton shape apatite product being made bondedfibre fabric.
14, according to claim 12 or 13 described methods, the wherein said apatite that uses is that M is Ca, ZO
4Be PO
4, and X is the apatite of OH.
15, according to claim 12 or 13 described methods, wherein above-mentioned used apatite is that M is Ca, ZO
4Be PO
4, X is hydroxyl-apatite of OH.
16, according to claim 12 or 13 described methods, wherein said apatite particle is that average grain diameter is the club of 50A °～1 μ m.
17, according to claim 12 or 13 described methods, wherein said binding agent is a water-soluble high-molecular compound.
18, method according to claim 17, wherein said binding agent is a pullulan.
19, according to claim 12 or 13 described methods, wherein said apatite dispersion also contains the fine grained of calcium phosphate compound.
20, according to claim 12 or 13 described methods, wherein said fibre bundle need heat so that make the moisture content of fiber be reduced to 10% or lower.
21, according to claim 12 or 13 described methods, wherein said sintering temperature is in 500 ℃～1250 ℃ scope.
22, method according to claim 21, wherein said sintering temperature is in 650 ℃～1100 ℃ scope.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35362/85 | 1985-02-26 | ||
| JP3526385A JPS61201019A (en) | 1985-02-26 | 1985-02-26 | Production of apatite wool |
| JP35262/85 | 1985-02-26 | ||
| JP35263/85 | 1985-02-26 | ||
| JP60035262A JPS61201018A (en) | 1985-02-26 | 1985-02-26 | Apatite wool |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101136A true CN86101136A (en) | 1986-10-01 |
| CN1011320B CN1011320B (en) | 1991-01-23 |
Family
ID=26374214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86101136 Expired CN1011320B (en) | 1985-02-26 | 1986-02-25 | Fibrous apatite and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011320B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109072514A (en) * | 2016-04-28 | 2018-12-21 | 阿莫绿色技术有限公司 | Guided bone regeneration nano-fiber composite film and preparation method thereof |
-
1986
- 1986-02-25 CN CN 86101136 patent/CN1011320B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109072514A (en) * | 2016-04-28 | 2018-12-21 | 阿莫绿色技术有限公司 | Guided bone regeneration nano-fiber composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1011320B (en) | 1991-01-23 |
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