CN1798534A - Composite of support substrate and collagen, and process for producing support substrate and composite - Google Patents
Composite of support substrate and collagen, and process for producing support substrate and composite Download PDFInfo
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- CN1798534A CN1798534A CNA2004800150465A CN200480015046A CN1798534A CN 1798534 A CN1798534 A CN 1798534A CN A2004800150465 A CNA2004800150465 A CN A2004800150465A CN 200480015046 A CN200480015046 A CN 200480015046A CN 1798534 A CN1798534 A CN 1798534A
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Abstract
A composite of cylindrical material and collagen is produced by fabricating a cylindrical material of 0.5 to 50 mm diameter constituted of a fiber structure of 1 to 50 g/m<2> basis weight, the cylindrical material having bellows of 2 mm or less pointed part/pointed part spacing and 0.01 to 1 mm valley part depth from pointed part, and applying collagen to the cylindrical material.
Description
Technical field
The present invention relates to the support substrate material of the fiber construct that the aliphatic poly ester fiber by average fiber footpath 0.05～50 μ m constitutes and the complex that collagen protein constitutes, cylindrical support matrix material with corrugated part, and the manufacture method of the manufacture method of this support substrate material and this complex.
Background technology
In recent years, be badly damaged or one of the bio-tissue lost and Therapeutic Method of internal organs, utilize the differentiation of cell, the regenerative medicine research that multiplication capacity makes up protozoa soma and internal organs again to be able to broad development as treatment.Neuranagenesis also belongs to one of them branch, and it has been carried out following research: the pipe that utilizes artificial material to constitute at the cut patient's of nervous tissue neurologic defect position carries out crosslinked between the plane of disruption, and then induces neurocyte.Employed pipe is made of silicon, polyurethane, polylactic acid, Polyethylene Glycol acid, polycaprolactone, their copolymer or complex, and face is coated with collagen protein, laminin within it.
In addition, employed artificial material pipe is to be made of politef, polyester, polylactic acid, Polyethylene Glycol acid, polycaprolactone, their copolymer or complex in revascularization, and face is coated with gelatin, albumin, collagen protein, laminin within it.
For example, open the content of having put down in writing relevant artificial blood vessel in the flat 6-285150 communique the spy, it is to be pressed into insoluble collagen protein on the tube wall of the tubular body that is made of cellulosic, and former state is carried out chemical treatment and formed under its undried state afterwards.
Open in the flat 7-148243 communique the spy and to disclose a kind of embedded material, its with the bulky structure body that possesses biocompatible as matrix material, wherein this structure is by making organic fiber three-dimensional woven tissue or knitting technology weave or the form of complex tissue of their combinations being formed the preferred 20～90vol% of its in-house voidage.
Open in the flat 8-294530 communique the spy, put down in writing the cardiovascular repair materials, it is characterized by absorbent material in the organism that on the porous matrix material, adheres to, utilize complexation, heat treatment and charged and at least a method in the physical action that property of water-bearing swelling that carry out constitutes is carried out insoluble processing.
Open in the flat 8-33661 communique the spy, put down in writing relevant artificial blood vessel's content, it is on the inner cavity surface of the artificial blood vessel's matrix material that is being made of synthetic resin, directly or coating gelatin or collagen protein and with cross-linking agent fixing after, thereon coagulation water solublity elastin laminin, utilize cross-linking agent and fixed.
Open the content of having put down in writing relevant artificial blood vessel in the flat 9-173361 communique the spy, it is on the inner cavity surface of the artificial blood vessel's matrix material that is made of synthetic resin, the coating albumin, further carrying out crosslinked after heating or the heating on the albumin layer that makes up with cross-linking agent, coagulation water solublity elastin laminin utilizes cross-linking agent and fixed.
Open in the 2003-126125 communique the spy and to have put down in writing the artificial blood vessel, it is in the artificial blood vessel with column porous artificial blood vessel matrix material, and dipping contains that the gel solution of organism working substance forms in the hole of above-mentioned porous artificial blood vessel's matrix material.
But, matrix material as such artificial blood vessel, record tube that plain weave that synthetic resin is made or warp plain stitch form, with synthetic resin make fibrous and rolling layer on the plug suppress the non-woven fabrics tube, in synthetic resin, add tube that the aqueous solution of particulate sodium chloride etc. obtains by extrusion modling etc., but as the pipe of artificial blood vessel's matrix material, above-mentioned any one all lacks retractility and Young's modulus (elastic modelling quantity) is also insufficient.
In addition, open to disclose in the flat 5-23362 communique the spy and try every possible means by giving the artificial blood vessel that special shape improves retractility, its warp and parallel use the multifilament threads that is made of polyester superfine fibre, knit the seamless pipe that tissue obtains being processed with corrugated part by carrying out bag.
In addition, open the spy that to disclose in the flat 8-71093 communique be the way etc. that forms gauffer on the conical fabric blood vessel restoration of raw material with the fibrous material.
Therefore the problem of long-term safety can take place owing to do not possess bioabsorbablely in above-mentioned silicon, polyurethane, politef, polyester, and then compressing occurs or hinder the problem of regenerated nerve or blood vessel.In addition,, on Young's modulus (elastic modelling quantity) and retractility, have problems, therefore can oppress or hinder the problem of regenerated nerve or blood vessel though that polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer possess is bioabsorbable.That is to say up to the present also there is not good pipe on bioabsorbable, Young's modulus (elastic modelling quantity), retractility.
In order to address these problems, consider elasticity raw materials such as collagen protein carry out compoundization with the support substrate material that is formed by polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer.But well-known, there is not retractility by polylactic acid, Polyethylene Glycol acid, polycaprolactone or their the support substrate material that copolymer constituted, therefore damage the elasticity of collagen protein, use in vivo is restricted.That is to say up to the present, also ungood in polylactic acid, Polyethylene Glycol acid, polycaprolactone or their the support substrate material that copolymer constituted on retractility, and the complex that forms of support substrate material and collagen protein thus.
Summary of the invention
The object of the present invention is to provide a kind of matrix material, its pipe as the matrix material that constitutes artificial blood vessel or neuranagenesis is rich in retractility and Young's modulus (elastic modelling quantity) is abundant.
The matrix material of the macromolecular compound of this pipe for possessing bioresorbable is provided in more detail.
The present invention is as follows:
1. a species complex, its support substrate material and collagen protein by the fiber construct that average fiber directly constitutes by the aliphatic poly ester fiber of 0.05～50 μ m is constituted.
2. invent the complex described in 1, wherein above-mentioned fiber construct is the biodegradability polymer.
3. invent the complex described in 2, wherein above-mentioned fiber construct is an aliphatic polyester.
4. invent the complex described in 3, wherein above-mentioned aliphatic polyester is polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer.
5. invent the complex described in 1, wherein above-mentioned support substrate material is the cylinder with corrugated part.
6. invent the complex described in 5, wherein this cylinder is by quantitatively being 1～50g/m
2Fiber construct constitute, thickness is that 0.05mm～0.2mm and diameter are the cylinder of 0.5mm～50mm, this cylinder has ripple, and to be spaced apart the 2mm degree of depth following and ripple be the corrugated part of 0.1mm～10mm.
7. cylinder, it is by quantitatively being 1～50g/m
2Fiber construct constitute, thickness is that 0.05mm～0.2mm and diameter are the cylinder of 0.5mm～50mm, it is characterized in that having ripple, to be spaced apart the 2mm degree of depth following and ripple be the corrugated part of 0.1mm～10mm.
8. invent 7 described cylinders, wherein above-mentioned cylinder is a Biodegradable polymer.
9. invent 8 described cylinders, wherein above-mentioned cylinder is an aliphatic polyester.
10. invent 9 described cylinders, wherein above-mentioned aliphatic polyester is polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer.
11. invent 7 described cylinders, wherein above-mentioned cylindrical average fiber directly is 0.05～50 μ m.
12. cylindrical manufacture method, it is by quantitatively being 1～50g/m
2Fiber construct constitute, having ripple, to be spaced apart the following and ripple degree of depth of 2mm be the cylindrical manufacture method of the corrugated part of 0.01mm～0.1mm, wherein contain make the step that is dissolved with the solution of aliphatic polyester in the volatile solvent, with above-mentioned solution by method of electrostatic spinning carry out spinning step, obtain the step of cumulative fiber construct on the catcher and above-mentioned fiber construct is configured as the cylindrical step that possesses corrugated part with the interval below the 2mm.
13. the manufacture method of the complex that is made of cylinder and collagen protein, it is undertaken compoundization by cylinder and collagen protein that method described in the invention 12 makes.
14. the manufacture method of the complex that constitutes by cylinder and collagen protein, it will be impregnated in solvent dissolving and/or be dispersed with in the solution of collagen protein by the cylinder that makes of method described in the invention 12, implement thereafter to carry out immobilized at least a method with collagen gelization or crosslinkedization or by drying.
Description of drawings
Figure 1 shows that in manufacture method of the present invention, spinning solution is ejected into an example of the method for electrostatic spinning equipment therefor in the electrostatic field.
Figure 2 shows that in the manufacture method of the present invention, the microdroplet of spinning solution is imported an example of the method for electrostatic spinning equipment therefor of electrostatic field.
Figure 3 shows that cylindrical profile of the present invention.
The specific embodiment
Below the present invention is described in detail.These embodiment wait and explanation is to be used for illustrating of the present invention, but also can carry out accommodation within category of the present invention.
The fiber that fiber construct used herein can be enumerated odd number or plural number carries out lamination, accumulation and the 3 dimension structures that form.The form of structure can be enumerated non-woven fabrics, woven cloth, looped fabric, mesh, silk etc.
Complex used in the present invention is made of above-mentioned fiber construct and collagen protein.
Fiber construct used in the present invention is made of aliphatic polyester.
Aliphatic polyester can be enumerated polylactic acid, Polyethylene Glycol acid, lactic acid-glycolic acid copolymer, polycaprolactone, polybutylene succinate, polyethylene succinate and their copolymer.Wherein, the preferred polylactic acid of aliphatic polyester, Polyethylene Glycol acid, lactic acid-glycolic acid copolymer, polycaprolactone, preferred especially polylactic acid, polycaprolactone.
Fiber construct used in the present invention, the preferred cylinder that uses with corrugated part.
Fiber construct of the present invention quantitatively be 1～50g/m
2If, 1g/m
2Following, can't form structure, therefore not preferred.In addition, 50g/m
2Above, it is therefore preferred to damage retractility when being configured as pipe yet.Quantitative more preferably 5～30g/m
2, preferred especially 5～20g/m
2
The thickness of fiber construct is 0.05～0.2mm, more preferably 0.1～0.18mm.
Fiber construct of the present invention is that diameter is the cylinder of 0.5mm～50mm, and containing ripple, to be spaced apart the following and ripple degree of depth of 2mm be the corrugated part of 0.1mm～10mm.Ripple more than 2mm, is being configured as Guan Shihui infringement retractility at interval, so not preferred.Ripple is at interval more preferably below 1mm.
Fiber construct of the present invention is formed at the fiber of 0.05～50 μ m by the average fiber footpath.When average fiber footpath when 0.05 μ m is following, can not keep the intensity of this fiber construct, therefore not preferred.In addition,, when being configured as pipe, might reduce retractility, infringement elasticity when average fiber footpath during greater than 50 μ m, therefore not preferred.The average fiber footpath is 0.2～25 μ m more preferably, and preferred especially 0.2～20 μ m most preferably is 0.3～10 μ m.What fiber was directly represented is the diameter of fibre profile.
The mechanical property of fiber construct of the present invention is preferably, elastic modelling quantity 1 * 10
2～1 * 10
7Pa, the elongation at yield rate is more than 20%.Elastic modelling quantity is 1 * 10
2Below, 2 * 10
7More than or the elongation at yield rate 20% when following, elasticity and retractility all can have problem, can have compressing or hinder the problem of regenerated nerve, blood vessel.
The manufacture method of fiber construct of the present invention can be enumerated method of electrostatic spinning, spun-bond process, molten stream method, flash method etc., wherein preferred method of electrostatic spinning.
In method of electrostatic spinning, the solution that will be dissolved with aliphatic polyester in volatile solvent is ejected in the electrostatic field that forms between electrode, and solution is pulled along electrode direction, can access by collecting the fibrous material that forms.So-called fibrous material not only refers to the distillation of the solvent of solution removed and becomes the state of fiber construct, also refers to contain the state of the solvent of solution.Used electrode can be metal, inorganic matter or organic any material among the present invention, as long as show electric conductivity.In addition, also can be the electrode that on insulant, has conductive metal, inorganic matter or organic thin film.Electrostatic field among the present invention forms between a pair of or a plurality of electrodes, can apply high voltage to any electrode.This is comprising for example using by 2 different high-voltage electrodes of magnitude of voltage (for example 15kV and 10kV) and the electrode that links to each other with ground electrode in the situation of 3 electrodes of interior total or use the situation that surpasses 3 electrodes.
Aliphatic poly ester concentration in the aliphatic poly ester solution of the present invention is preferably 1～30 weight %.During the concentration less than 1 weight % of aliphatic polyester, cause fiber construct to form difficulty because concentration is low excessively, therefore not preferred; When surpassing 30 weight %, the fiber of resulting fiber construct directly becomes greatly, and is therefore not preferred.The concentration of aliphatic polyester is 2～20 weight % more preferably.
The volatile solvent that forms solution among the present invention is that boiling point is being the material of liquid below 200 ℃, 27 ℃ the time under dissolved fat adoption ester, the normal pressure.
Specifically, volatile solvent can be dichloromethane, chloroform, acetone, methanol, ethanol, propanol, isopropyl alcohol, toluene, oxolane, 1,1,1,3,3,3-hexafluoroisopropanol, water, 1,4-diox, carbon tetrachloride, cyclohexane extraction, Ketohexamethylene, N, dinethylformamide, acetonitrile etc.Wherein, consider preferred especially dichloromethane, chloroform, acetone from aspects such as aliphatic polyester dissolubilities.
These solvents can use separately, also can be used in combination by multiple solvent.In addition, in the present invention as long as in the scope of not damaging the object of the invention, can and use with other solvent.
Below, employed symbol in simple declaration Fig. 1～3.
1, solution nozzle
2, solution
3, solution keeps groove
4, electrode
5, fibrous material passive electrode
6, high-voltage generator
7, solution nozzle
8, solution
9, solution keeps groove
10, electrode
11, fibrous material passive electrode
12, high-voltage generator
13, thickness
14, the interval of ripple
15, the degree of depth
16, diameter
Can use any method that this solution is ejected in the electrostatic field.For example, carry out following explanation with Fig. 1 as an example.By solution 2 is supplied to nozzle, solution is placed on definite position in the electrostatic field, because electric field, solution is pulled and fibrosis from this nozzle.For this reason, can use suitable device, for example the solution in the column of syringe keeps the leading section of groove 3 to utilize appropriate device, for example high-voltage generator 6, and the acicular solution nozzle 1 of injection that has applied voltage is set, and solution is directed at its front end.Dispose the front end of this nozzle 1 in the suitable distance of the fibrous material passive electrode 5 of distance ground connection, solution 2 has formed fibrous material when the front end of this nozzle 1 flows out between this front end and fibrous material passive electrode 5.
In addition, those skilled in the art can use known method that the microdroplet of this solution is directed in the electrostatic field.Carry out following explanation with Fig. 2 as an example.This moment, unique important document was to be placed on drop in the electrostatic field and to remain on apart from fibrous material passive electrode 11 can cause on the Fibrotic position.For example, can in the solution 8 in having the solution maintenance groove 9 of nozzle 7, directly insert the direct electrode 10 that resists mutually with the fibrous material passive electrode.
This solution is being supplied to from nozzle under the situation of electrostatic field, can using a plurality of nozzles to improve the speed of production of fibrous material.Interelectrode distance depends on carried charge, jet size, spinning solution flow, spinning solution concentration etc.The distance of 5～20cm is more suitable when being the 10kV left and right sides.The electrostatic potential that applies is generally 3～100kV, preferred 5～50kV, more preferably 5～30kV.Desirable current potential can obtain by any suitable method.
Above-mentioned explanation is the double situation of doing catcher of electrode, but also can catcher be set separately by the article that can become catcher are set outside electrode between electrode.By selecting the shape of catcher, can obtain sheet material, tubing.And then, for example, banded material forms catcher between electrode by being set, can carry out continuous production.
In the present invention, this solution during along the traction of the direction of catcher, is being formed fibrous material according to the condition solvent evaporation.As long as solvent just can evaporate fully before being collected the device collection under the common room temperature, if still the incomplete words of solvent evaporation also can be drawn under reduced pressure.The temperature of traction depends on the viscosity of the evaporating state and the spinning solution of solvent, is generally 0～50 ℃.And fibrous material accumulates the formation fiber construct on catcher.
Make the cylindrical method that constitutes by fiber construct of the present invention and be not particularly limited, but the catcher of above-mentioned method of electrostatic spinning preferably uses the plug that does not carry out the mirror finish processing, can make this cylinder easily like this.By above-mentioned method of electrostatic spinning on plug, form fiber construct until reach certain quantitatively, the friction that keeps appropriate is on one side taken out fiber construct from this plug, can obtain having the cylinder of corrugated part thus easily.
More than the preferred 0.2-S of mandrel surface roughness, more preferably 1.5～400-S.
When from this plug with suitable surface roughness, taking out fiber construct, preferred only in the end application of force of fiber construct.Earlier an end of fiber construct is fixed, plug is extracted along the direction of this stiff end, institute's applied pressure is only on this end like this.
When on plug, forming fiber construct, plug is along the circumferential direction rotated, because can form the cylinder of homogenizing like this by method of electrostatic spinning.
Resulting cylinder can use separately according to the present invention, also can require to unite use with other parts according to operability and other.For example, by with the combination of elastomers such as this cylinder and collagen protein, can make parts with best elasticity and intensity.
Employed collagen protein can use the collagen protein in any biological species such as mammals, birds, Fish according to its source and indefinite among the present invention.The collagen protein that can also use cell classes such as antibacterial, fungus, yeast to make in addition.If the collagen protein in organism source, preferred mammiferous collagen protein also can use the collagen protein by the resulting recombinant of genetic manipulation such as the cell class that derives from antibacterial, fungus, yeast.The chemical constitution of collagen protein also is not particularly limited, and can use acid-solubility collagen protein, neutral salt soluble collagen albumen, enzyme soluble collagen albumen, alkali-soluble collagen protein etc.Be the arbitrary amino acid sequence of representative or the saccharic class that collagen protein combines with end peptide etc. in the collagen protein, can remove preferred using-system reparation albumen according to application target.
During collagen, its separation method is not particularly limited from organism.Preferred each soluble component that from acidic aqueous solution or alkaline aqueous solution, extracts that uses.Collagen protein by extraction obtains can directly use in the mode of acidic aqueous solution or alkaline aqueous solution, but preferred use is dialysed, ion exchange is removed the back with the small molecular ion of surplus and used.
The method of composite fiber structure and collagen protein is preferably used following method among the present invention: with collagen protein dissolving and/or be dispersed in the resulting solution in back in the appropriate solvent, be impregnated into the inside of fiber construct, carry out gelation, crosslinkedization thereafter, by at least a method in the exsiccant immobilization, form the reticulated structure of collagen protein.
In such cases, collagen protein can use collagen solution when solvable in solvent, and collagen protein can use dispersion liquid when insoluble in solvent.In addition, in the present invention, although, comprise dissolving and disperse the situation of two aspects also can utilize in the present invention when collagen protein when only some dissolving or swelling can not be consoluet.
Solvent can be selected arbitrarily in the sulfone series solvent of the amide series solvent of water, dimethyl acetylamide etc., dimethyl sulfoxide etc. etc., but preferably makes water.In addition can mixed chlorinated as required calcium in solvent or the surfactant of polyhydric alcohol of inorganic salt, glycerol or the Polyethylene Glycol etc. of lithium chloride etc., glyceryl monostearate etc.
The method that collagen protein is immersed in fiber construct is not particularly limited, under the normal pressure, decompression down, add to depress and all can.Can use mold in order to obtain suitable cylindrical shape.
Gelation is meant the operation that makes collagen gelization under neutrallty condition by heating, is not particularly limited for adjusting the employed reagent of pH value.Crosslinkedization be meant with possess more than 2 can with chemical compound and the collagen protein phase reaction of the functional group of collagen protein reaction, preferred use has the material of carbon diimino or has the material of active ester.
Collagen concentration in collagen solution, dispersion liquid, half solution is preferred more than 0.1%, below 10%.More preferably in the scope more than 0.2%, below 8%.
Cylinder shown in the present can carry out lyophilization as required.Cryodesiccated condition is not particularly limited, and preferred cryogenic temperature be below-5 ℃, and preferably the vacuum during lyophilization is below the 100MPa.
As required, the collagen protein that is immersed in the fiber construct can be a porous mass.Be not particularly limited the preferred spongiform porous mass that obtains by lyophilization that uses on the manufacture method of porous mass.In addition, also can use the particle that contains soluble material in organic solvent in the collagen protein in advance, utilize organic solvent then its method that extracts.In addition, by can utilize the space of fiber construct to greatest extent at fiber surface coating collagen protein.
The resulting complex of the present invention can use separately, also can be used in combination according to operability and other needs and miscellaneous part.For example,, the additive of glycerol, Polyethylene Glycol etc. can be contained, also the protein-based of somatomedin or cytokines etc. can be contained in order to improve the flexibility of complex integral body.
Embodiment
By the following examples, the present invention is carried out more detailed, specific description.But the present invention is not limited to these embodiment.
Employed polylactic acid (Lacty9031) uses Shimadzu Seisakusho Ltd.'s (strain) system product in the present embodiment, and dichloromethane (superfine) uses and the pure pharmaceutical worker's industry of light (strain) system product.
Room temperature (25 ℃) is mixed polylactic acid 1g, dichloromethane 8g down, makes jelly.Use device shown in Figure 2, this solution is ejected into per minute 60 to be changeed in the fibrous material passive electrode 5 (diameter 2mm, long 200mm, surface roughness 70-S) of rotation, and this process is 5 minutes.At this moment, passive electrode 5 is rotated with 150rpm along circumferencial direction.The internal diameter of nozzle 1 is 0.8mm, and voltage is 12kV, and nozzle 1 is 10cm to the distance of fibrous material passive electrode 5.One end that will be collected in the fiber construct on the fibrous material passive electrode 5 with finger is pushed and is fixed, and extracts fibrous material passive electrode 5 along the pressure that press...withes one's finger, the direction of fixing a side, obtains the polylactic acid pipe.The polylactic acid pipe that obtains is diameter 2mm, length 20mm, quantitatively 20g/m
2, the interval 0.5mm of corrugated part, ripple degree of depth 0.1mm.With reference to DIN53507,53504, utilize テ Application シ ロ Application device (INSTRON) to measure elastic modelling quantity and elongation at yield rate to the molded body of gained.The result is as shown in table 1.
The physics value of the various materials of table 1.
| Material | Quantitative (g/m 2) | The interval of corrugated part (mm) | Elastic modelling quantity (MPa) | Elongation at yield rate (%) | |
| | Polylactic acid | 20 | 0.5 | 20 | 50 |
| | ″ | 40 | 0.5 | 35 | 30 |
| Than glue example 1 | Polylactic acid | 100 | 0.5 | 170 | 5 |
| Comparative example 2 | ″ | 20 | 3.0 | 100 | 10 |
Quantitatively become 40g/m except making
2In addition, carry out the processing identical with embodiment 1.
In the polylactic acid pipe that in embodiment 1, obtains, insert the rod of a diameter 2mm again, be fixed in the center of the pipe of internal diameter 3mm, make it become the center.The Gao Yan (strain) of 10 unit volumes system 0.3% collagen protein aqueous solution (II type) and 1.5 unit volumes, the buffer that contains 260mM sodium bicarbonate, 200Mm HEPES and 50mM sodium hydroxide are mixed under ice bath, put into the container that is fixed with the polylactic acid pipe.With outside atmosphere decompression, return to normal pressure then, after the repeatable operation 3 times, it 37 ℃ of insulations, is carried out gelation.After the gelation, take out the rod of diameter 2mm, wait until the collagen protein cylinder by lyophilization.
With reference to DIN53507,53504, utilize テ Application シ ロ Application device (INSTRON) to measure the elongation at yield rate to the molded body of gained, the result is 38%.
Comparative example 1
Remove and quantitatively to become 100g/m
2In addition, carry out 1 identical operations with embodiment.
Comparative example 2
Except using fibrous material passive electrode 5 (diameter 2mm, long 200mm, surperficial) in addition through mirror finish (below the surface roughness 0.1-S), other and embodiment 1 same operation.The polylactic acid pipe that obtains will be except will quantitatively becoming 20g/m
2, corrugated part the interval become beyond the 3.0mm other and embodiment 1 same treatment.
Comparative example 3
At room temperature mix 0.5g polylactic acid and 10g dichloromethane, obtain jelly.Fill it into nozzle directly in the spray gun HG-S type of 0.2mm (palace, field model system), the air pressure of using 0.08MPa with its spray to rotation, on the rod of diameter as 2mm ф.When the fiber structure that will form on the rod surface took off, having obtained quantitatively was 50g/m
2, mould is the fiber construct that 0.3mm does not have ripple.Similarly to Example 3, with this and compoundization of collagen protein, measure the elongation at yield rate, the result is 8%.
Industrial applicability
Can obtain the complex structure body of the good collagen of retractility and fiber according to the present invention. This collagen complex can replace material at artificial blood vessel's etc. blood vessel, uses in the regeneration of nerve or urinary catheter. In addition, the experiment material that also can be used as invisible spectro cell culture vector, cell evaluation usefulness is used.
Claims (14)
1, a species complex, its support substrate material and collagen protein by the fiber construct that average fiber directly constitutes by the aliphatic poly ester fiber of 0.05～50 μ m is constituted.
2, the complex described in the claim 1, wherein above-mentioned fiber construct is a Biodegradable polymer.
3, the complex described in the claim 2, wherein above-mentioned fiber construct is an aliphatic polyester.
4, the complex described in the claim 3, wherein above-mentioned aliphatic polyester are polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer.
5, the complex described in the claim 1, wherein above-mentioned support substrate material is the cylinder with corrugated part.
6, the complex described in the claim 5, wherein this cylinder is by quantitatively being 1～50g/m
2Fiber construct constitute, thickness is that 0.05mm～0.2mm and diameter are the cylinder of 0.5mm～50mm, this cylinder has ripple, and to be spaced apart the 2mm degree of depth following and ripple be the corrugated part of 0.1mm～10mm.
7, a kind of cylinder, it is by quantitatively being 1～50g/m
2Fiber construct constitute, thickness is that 0.05mm～0.2mm and diameter are the cylinder of 0.5mm～50mm, wherein this cylinder has ripple to be spaced apart the 2mm degree of depth following and ripple is the corrugated part of 0.1mm～10mm.
8, the described cylinder of claim 7, wherein above-mentioned cylinder is a Biodegradable polymer.
9, the described cylinder of claim 8, wherein above-mentioned cylinder is an aliphatic polyester.
10, the described cylinder of claim 9, wherein above-mentioned aliphatic polyester are polylactic acid, Polyethylene Glycol acid, polycaprolactone or their copolymer.
11, the described cylinder of claim 7, wherein above-mentioned cylindrical average fiber directly are 0.05～50 μ m.
12, cylindrical manufacture method, it is by quantitatively being 1～50g/m
2Fiber construct constitute, having ripple, to be spaced apart the 2mm degree of depth following and ripple be the cylindrical manufacture method of the corrugated part of 0.01mm～0.1mm, wherein contain make the step that is dissolved with the solution of aliphatic polyester in the volatile solvent, with above-mentioned solution by method of electrostatic spinning carry out spinning step, obtain the step of cumulative fiber construct on the catcher and above-mentioned fiber construct is configured as the cylindrical step that possesses corrugated part with the interval below the 2mm.
13, the manufacture method of the complex that is made of cylinder and collagen protein, it is that cylinder and the collagen protein that will be made by method described in the claim 12 carry out compoundization.
14, the manufacture method of the complex that constitutes by cylinder and collagen protein, it will be impregnated in solvent dissolving by the cylinder that method described in the claim 12 makes and/or be dispersed with in the solution of collagen protein, implement thereafter to carry out immobilized at least a method with collagen gelization or crosslinkedization or by drying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP094399/2003 | 2003-03-31 | ||
| JP2003094399 | 2003-03-31 | ||
| JP383432/2003 | 2003-11-13 |
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2004
- 2004-03-31 CN CNA2004800150465A patent/CN1798534A/en active Pending
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| CN105339485A (en) * | 2013-06-06 | 2016-02-17 | Sns纳米光纤技术公司 | Three-dimensional structures for cell or tissue culture |
| CN106659822A (en) * | 2014-06-11 | 2017-05-10 | 雅培心血管系统公司 | Solvent method for forming a polymer scaffolding |
| CN104984411A (en) * | 2015-07-17 | 2015-10-21 | 厦门浩益视生物科技有限公司 | Smart plug and preparation method thereof |
| CN111569161A (en) * | 2020-05-27 | 2020-08-25 | 天新福（北京）医疗器材股份有限公司 | Decompression material for microvascular decompression and preparation method and application thereof |
| CN111569161B (en) * | 2020-05-27 | 2022-04-19 | 天新福（北京）医疗器材股份有限公司 | Decompression material for microvascular decompression and preparation method and application thereof |
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