JPH0214019A - Fibrous shaped material and production thereof - Google Patents

Abstract

PURPOSE:To obtain fibrous shaped material having compatibility with organism and excellent elasticity by bursting raw material solution containing mucopolysaccharide from nozzle to medium and making fiber flow, then affecting coagulant to said flow. CONSTITUTION:A raw material solution containing mucopolysaccharide preferably selected from hyaluronic acid, chondroitin(sulfate), dermathane sulfate, heparan sulfate, heparin and keratan sulfate is prepared. Said raw material solution is bursted from nozzle to make a fiber flow and a coagulant capable of coagulating said mucopolysaccharide is affected to said fiber flow. Next, resultant fiber flow is collected by transferring collecting device to obtain the aimed shaped material.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides Hll, which is useful as a bone filler in the medical field, particularly orthopedics, otolaryngology, and dentistry, and as a moisturizing agent in cosmetics and pharmaceuticals. Form into a II-shaped molded product.

[Prior Art] Bone filling materials for filling bones and other voids or defects have been developed, and metals and ceramics are known as the materials. Among these, particularly preferred from the viewpoint of biocompatibility are calcium phosphate compounds. Among calcium phosphate compounds, it is known that hydroxyapatite, which is a bone component, is particularly preferred. Hydroxyapatite fillers that have been developed so far include granular, powdered (JP-A-56-54841), porous and fibrous molded products (JP-A-62-221358). However, granular, powdery, and porous materials have difficulties in operability and workability during surgery. The disadvantages of granular, powdered, and porous products have been largely resolved in fibrous molded products, or conventional hydroxyapatite-based fibrous molded products have low strength fibers that make up the fibrous molded products. The fibers tend to come apart during the surgery, and therefore, the operability and workability are still unsatisfactory.

On the other hand, mucopolysaccharides have been conventionally used as moisturizing agents in cosmetics. However, all of these are in the form of final products such as freeze-dried powders or emulsions or creams containing a small amount of the same, and their moisturizing effects are still unsatisfactory.

[Problems to be solved by the invention] The object of the present invention is to provide excellent operability and workability when used as a bone filling material, and to have no problems in biocompatibility.
In addition, a novel molded product that can exhibit a high moisturizing effect even when used as a moisturizing agent in cosmetics, and the same! The objective is to provide a two-pronged method.

[Means for Solving the Problems] As a result of intensive research, the inventors of the present application succeeded in turning mucopolysaccharide into fibers, and used the fibrous molded product made of this mucopolysaccharide as a bone filling material. This invention was completed after discovering that it has good operability and workability, is excellent in biocompatibility, and also exhibits an excellent moisturizing effect when used as a moisturizing agent in cosmetics.

That is, the present invention has an average fiber diameter of 1μ to 2.
To provide a fibrous molded product made of 0,000 yen fiber.

Further, the present invention includes a step of preparing a raw material liquid containing mucopolysaccharide in a medium, a step of jetting the raw material liquid from a nozzle to form a fiber stream, and a step of coagulating the mucopolysaccharide in the fiber stream. Provided is a method for producing an m-male molded article, which includes the steps of applying a coagulating liquid capable of forming a coagulating liquid, and collecting the fiber stream on a moving collecting device.

Furthermore, this invention provides a step of preparing a raw material liquid containing mucopolysaccharide in a medium, and spouting the raw material liquid from an inner nozzle of a concentric double pipe nozzle, and discharging the mucopolysaccharide from an outer nozzle. a step of ejecting a coagulating liquid capable of coagulating the fibers to form a fiber stream; and a step of collecting the fiber stream on a moving collection device! (a) A method for producing a miscellaneous shaped article is provided.

[Effects of the Invention] According to the present invention, a novel fibrous molded product made of Mukota-tfj was provided. Since the mucopolysaccharide constituting the fibrous molded product of this invention is a substance that exists on the surface of cells, it has excellent biocompatibility. It can be used as a bone filling material in medical, dental, etc. In this case, the fibrous molded product of the present invention is male-shaped and has sufficient strength, so it does not come apart during surgery and has excellent operability and workability. Further, when the Mll-shaped molded product of the present invention is used as a moisturizing agent in cosmetics, etc., it exhibits an excellent moisturizing effect. Furthermore, according to the manufacturing method of the present invention, the fiber diameter of the fibers constituting the fibrous molded product can be adjusted to a desired range.

[Detailed Description of the Invention] The fibers constituting the fibrous molded product of the present invention are made of mucopolysaccharides coagulated with a coagulation liquid as described above. As the mucopolysaccharide, any mucopolysaccharide can be used, but preferred examples include hyaluronic acid, chondroitin, chondroitin sulfate, dermatan sulfate,
Mention may be made of heparan sulfate, hebarin or keratan sulfate. The molecular weight of these molecules is not particularly limited, but is usually about 500 to 1,000,000.

Liquid substances capable of coagulating mucopolysaccharides are known, and include alcohols such as acetone, methyl alcohol, and ethyl alcohol.

The average fiber diameter of the fibers forming the fibrous molded product of this invention is 1. ■Available in fiber sizes ranging from 0 to 2000 ru, depending on the application, the desired fiber diameter can be adopted.
That is, when a fibrous molded product is used as a bone filling base material, and flexibility is required for the H&female molded product, such as when filling a relatively small defect, for example,
It is preferable that the fiber diameter is relatively small, usually 1 = ■ to 100 μLs, preferably 2 μLs to 30 μLs,
More preferably, it is 5μ■ to 15JL−.On the other hand, when used as a bone filling base material for filling a relatively large bone defect, for example, it is preferable that the strength of the male shaped molding is larger, so the fiber The diameter is relatively thick, 10
0 u-■ to 2000 #Lm is preferable. When used as a bone filling base material, a fibrous molded product with a large fiber diameter and a thin fibrous molded product are used together to form a finely shaped part around the periphery of the defect. The molded material with thin fiber diameter is filled without any gaps, and the area near the center of the defect is made of strong thick fibers. It is also possible to fill it with an i-shaped molding. When used as a moisturizing agent for cosmetics, etc., it is preferably from 2 JL to 100, particularly preferably from 2 JL to 20 JL.

The fibrous molded product of this invention is non-woven fabric-like, cotton-like, absorbent cotton-like,
It may be in any form such as roving, and its basis weight ff1Ju is not particularly limited, but is usually 5 g/s.
to 500 g/2, preferably 20 g/2 to ZOOg/2.

The fibrous molded product of the present invention may be composed only of mucopolysaccharides, or calcium phosphate ceramics may be blended into the fibers in order to enhance bone formation ability, especially when used as a bone filling base material. Examples of calcium phosphate ceramics include tricalcium phosphate and apatite, but from the viewpoint of biocompatibility and osteogenic ability, hydroxyapatite, which is a component of bone, is the most preferable.The content of calcium phosphate ceramics in the fiber is is usually 1% to 90% by weight, preferably 1% to 80% by weight.

If desired, m111 of the present invention may be in a freeze-dried state.When it is in a freeze-dry state, the bulk specific gravity becomes small and it becomes spongy, so it has the advantage of being highly elastic and improving operability. be.

The fibrous molded product of this invention can be produced as follows.

First, a raw material liquid is prepared. The raw material liquid contains a medium, preferably an aqueous medium, and in some cases, the above-mentioned calcium phosphate ceramics. When an apatite compound is included, the apatite compound may be in the form of powder, slurry, or short fibers, and can be obtained by a method well known in this field. Further, it is preferable that the apatite-based compound be fired, and the firing temperature may be any degree within the range of 100°C to 1300°C.

The concentration of mucopolysaccharide in the raw material liquid is usually 0.1% to 5.0% by weight, preferably 0.5% to 2.0% by weight. O
i [(17%).If calcium phosphate ceramics are included, the concentration is usually 0.1% by weight.
It is from 1000% to 1000%, preferably from 0.31% to 5.0%. The weight ratio of the mucopolysaccharide and the calcium phosphate ceramics in the raw material liquid is selected so that the amount of the calcium phosphate ceramics in the fiber falls within the above range.

The ta fibrous molded product of the present invention can be produced using the raw material liquid E, for example, by the following method. The manufacturing method is suitable for manufacturing a fibrous molded article made of relatively thin fibers with a diameter of 1 to 100 gm, and a method suitable for manufacturing a fibrous molded article made of relatively thick fibers with a diameter of 20 gm to 2000 am. There are two methods suitable for the production of coagulation, and the former can be further classified into two methods depending on the method of applying the coagulation solution.

First, there is a method suitable for manufacturing fibers with a diameter of 1 to 100 g, which is a manufacturing method in which S solid liquid is ejected from a nozzle different from the spinning nozzle and sprayed onto the fiber flow (hereinafter referred to as manufacturing method 1). I will explain about it. This method can be carried out using, for example, an apparatus as shown in FIG.

First, the raw material liquid supplied to the raw material tank 2 via the raw material supply pipe 1 is passed through a die with a motor 3 and a die in which a plurality of melt spinning nozzles 5 having pores are arranged linearly in the width direction. At the same time, it is pumped out by the gear pump 4 driven by it.

From the air nozzle 7 arranged around the nozzle, the gas velocity is from 5 to about 200 m/sec, and the temperature is from 20°C to about 6.
A fiber stream 8 consisting of drawn fine fibers is formed by blowing out a gas, for example air, at 0°C. Air is supplied from floor 6. The diameter of the fiber in this case is adjusted depending on the velocity of the ejected gas, typically within the range of 1 to about 100 uLm. When the gas velocity is high, the fiber diameter becomes smaller, and when the gas velocity is small, the fiber diameter becomes large. When the gas velocity is 20 h/sec, the diameter is usually about 1 m, and when the gas velocity is 100 m/sec, the diameter is usually about 3 to 5 m.
At 30 m/sec, fibers with a diameter of about 20 JLr1 are usually formed. The fiber flow 8 is guided by the guide plate 12
guided by.

Next, the coagulating liquid stored in the coagulating liquid tank 10 is sprayed onto this fiber stream from the coagulating liquid spray nozzle 9. The amount of coagulation liquid supplied is the amount necessary to solidify the mucopolysaccharide, and is usually about 11/sec to 20111/sec.

The coagulated fiber stream 13, which has been stretched and solidified as a mucopolysaccharide, is collected by a moving collecting device such as a net-type rotating drum, a moving belt, etc. (the one shown in FIG. 1 is a net-type The fibrous material 15 is formed by intertwining and falling on the rotating tram 14). In this case, when the fiber stream 13 is dropped onto the contact point of the two rotating net-type collection drums 14, the spray is applied to the entangled fibers or the fibrous material in the thickness direction (that is, three-dimensionally). An arrayed, bulky, cotton-like or cotton-wool-like fibrous material is obtained. In addition, when the fiber stream is sprayed onto a point other than the contact point of the collection tram or onto a flat collection belt, etc., the fibers are scattered in t rows (that is, two-dimensionally) arranged on the y-plane. 41 pieces of fabric are obtained. Further, roving-shaped fibers can be formed using an apparatus in which melt spinning nozzles are arranged in circumference B. Furthermore, the weight of the fibrous material 1] can be arbitrarily adjusted by changing the moving speed of the collection device, for example, within the range of 5 g/s2 to 500 g/m2.

Been formed! a The fibrous molded product 15 is wound up by the winding device 16.

Next, a manufacturing method (hereinafter referred to as manufacturing method 2) in which a raw material liquid and a coagulating liquid are simultaneously ejected using a double nozzle will be explained based on FIGS. 2 and 3.

The device shown in FIG. 2 is structurally the same as the device shown in t51 U4, and like parts have been given the same reference numerals as in FIG. In production method 2, a coagulating liquid is stored in a coagulating liquid tank 17, and is injected by a gear pump 4 driven by a motor 3 from a nozzle 5b outside the two-ffi spinning nozzle 5 shown in FIG. That is, as shown in FIG. 3, the spinning nostle used in production method 2 consists of concentric double tubes, and the raw material liquid is ejected from the inner nozzle 5a and the coagulating liquid is ejected from the outer nozzle 5b. Ru. The ratio of the diameters of the inner nozzle 5a and the outer nozzle 5b is not particularly limited and is usually about 1:2 to 1:10. Other conditions are the same as in the manufacturing method 1 described above.

Next, the diameter of the fiber is 20 μ bacteria or 20004
A manufacturing method suitable for manufacturing a fibrous molded product (hereinafter referred to as
Manufacturing method 3) will be explained based on FIGS. 4 to 6 [2I]. FIG. 4 is a schematic diagram of the raw material supply section of the apparatus, which is essentially the same as the raw material supply section of the apparatus shown in FIG. 1, and the same members are given the same reference numerals.

The raw material liquid is supplied from the raw material liquid tank 2 to the spinning nozzle 5 as in Production Methods 1 and 2, and is jetted out from the spinning nozzle 5 by the gear pump 4 driven by the motor 3. However, in production method 3, air is not ejected from around the spinning nozzle, and therefore the air nozzle 7 and blower 6 shown in FIG. 1 are not provided. The ejection rIt of the raw material liquid from the spinning nozzle 5 is usually 0.217.
It is about 201/min to 201/min.

The fiber 21 spun by the spinning nozzle 5 is introduced into a coagulation tank 22 containing a coagulation liquid. FIG. 6 is a top view of the coagulation section, or as shown in FIG.
The coagulating liquid inside flows through a doughnut-shaped coagulating tank 22,
The flow rate is preferably 0.5 m/min to 30 m/min.

The fibers coagulated in the coagulation tank 22 are conveyed to the net type conveyor 241 via the fiber transport pipe 23, where an am-shaped molded product is formed, and the coagulated liquid and the fibrous molded product are separated here. The coagulating liquid that has fallen under the net is transferred to the coagulating tank 22 again by the pump 27 via the coagulating liquid circulation pipe 26.
transported to. The Fa fibrous molded product 25 formed as a net type conveyor 24 is conveyed to the right end of the figure by the conveyor 24 and collected there.

The fibrous molded article of the present invention produced by the above-mentioned manufacturing method 3 has sufficient strength because the strength of the mucopolysaccharide coagulated by the coagulating liquid is high, and the fibers do not come apart. It has excellent operability and workability when used as a material.

In addition, in J: Manufacturing method No. 3, a water-resistant molded product can be obtained because the TA fibers are not heated.

[Examples] Hereinafter, the present invention will be described in more detail based on Examples. It should be noted that the present invention is not limited to the embodiments described above.

Shown below! Using a raw material liquid having a lI structure.

A fibrous molded product was manufactured by the above-mentioned manufacturing methods 1 and 2. A fibrous molded article consisting of fibers having the average l@fiber diameter shown in the table was obtained. Note that acetone was used as the coagulating liquid.

In all of the molded male-shaped molded products, the Ia male did not come apart due to the high strength of the fibers, and was soft and pliable.

[Brief explanation of the drawing]

Figures 1 and 2 are schematic diagrams showing an apparatus for producing a fibrous molded product of the present invention, Figure 3 is a diagram showing a spinning nozzle used in the apparatus shown in Figure 2, and Figure 4 is a diagram showing a spinning nozzle used in the apparatus shown in Figure 2. Figure 5 is a schematic diagram showing the raw material supply section of the apparatus used in another method for producing the fibrous molded product of the invention. FIG. l... Raw material supply pipe, 2... Raw material tank, 3... Motor, 4... Gear pump, 5... Spinning nozzle,
6... Blower, 7... Air nozzle, 8... Fiber flow, 9... Coagulation liquid spray nozzle, 10... Coagulation liquid tank, 11... Compressor, 13...
Solidified fiber flow, 14...net type collection drum,
15... Fibrous molded product, 16... Winding device, 1
7... Coagulation liquid tank, 21... Fiber, 22.
... Dyeing tank, 23... Fiber transport pipe, 24...
Nent type conveyor, 25...ta male molded product, 2
6...Coagulation liquid circulation pipe, 27...Pump

Claims (10)

[Claims] (1) A fibrous molded article composed of fibers with an average fiber diameter of 1 μm to 2000 μm, which is made of mucopolysaccharide coagulated by a coagulating liquid. (2) The fibrous molded article according to claim 1, wherein the mucopolysaccharide is hyaluronic acid, chondroitin, chondroitin sulfate, dermatan sulfate, hebaran sulfate, hebarin, or keratan sulfate. (3) The fiber molded product according to claim 1 or 2, wherein the fiber further contains a calcium phosphate ceramic. (4) The fibrous molded article according to claim 3, wherein the calcium phosphate ceramic is hydroxyapatite. (5) The fibrous molded article according to any one of claims 1 to 4, which is in a freeze-dried state. (6) A step of preparing a raw material liquid containing mucopolysaccharide in a medium, a step of ejecting the raw material liquid from a nozzle to form a fiber stream, and a coagulation capable of coagulating the mucopolysaccharide into the fiber stream. A method for producing a fibrous molded article, comprising the steps of applying a liquid and collecting the fiber stream on a moving collection device. (7) The method according to claim 6, wherein the step of applying the coagulating liquid is performed by jetting the coagulating liquid from a nozzle and spraying it onto the fiber stream. (8) The method according to claim 6, wherein the step of applying the coagulating liquid is performed by introducing the fiber flow into the coagulating liquid. (9) A step of preparing a raw material liquid containing mucopolysaccharide in a medium, and ejecting the raw material liquid from the inner nozzle of a concentric double pipe nozzle, and coagulating the mucopolysaccharide from the outer nozzle. A method for manufacturing a fibrous molded article, comprising the steps of: spouting a coagulating liquid to form a fiber stream; and collecting the fiber stream on a moving collection device. (10) The method according to any one of claims 6 to 9, wherein the raw material liquid further contains a calcium phosphate ceramic.