JPS584821A - Production of calcium phosphate fiber - Google Patents

Abstract

PURPOSE:The starting materials, which, after melted, will contain specific amounts of calcium oxide and phosphorus pentoxide at a specified molar ratio of Ca/P, are melted and made into fiber to produce the titled fiber of high strength that is suitably used to fill defect parts of living bones. CONSTITUTION:The starting materials, which will contain more than 8wt% of calcium oxide and phosphorus pentoxide at a Ca/P molar ratio of 0.6-1.7 after melted, preferably calcium phosphate and/or a mixture of phosphoric acid and calcium substance, are preferably pyrolyzed, melted and made into fiber under forced cooling of the nozzle to give the objective fiber. The above melting process preferably contains preliminary melting stage, cooling one and remelting one.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 7-Ipar, especially calcium phosphate 7-IPAR (fiber containing cJSPjiP and 0, hereinafter the same) which has a therapeutic effect as a filling material for bone defects in living bones and has high tensile strength. The present invention relates to a manufacturing method.

Conventionally, various metal alloys and organic substances have been used as hard tissue substitutes for living organisms, but these have the potential to cause problems such as SM and deterioration in the harsh environment of living organisms, and to be accompanied by toxicity and foreign body reactions. For these reasons, ceramic materials, which have excellent compatibility with living organisms and do not have the above-mentioned drawbacks, are now being used. Among these materials, alumina and carbon have excellent biocompatibility.

Biokarasu, Tricalcium Phosphate (Can(PO4)
z) or hydroxyapatite [:Ca1(PO4
) sOH) Artificial bone 9 Artificial tooth roots made of sintered bodies, glass, or single crystals have been developed and are attracting attention.

Attempts have been made to fill bone defects and voids with these sintered bodies or single crystals, but the shapes of bone defects that require cold treatment are irregular and complex. It is difficult to process these sintered bodies, glass, or single crystals to fit the shape of the sintered body, and furthermore, when filled with aluminum-based sintered bodies or single crystals, the surrounding bone may be damaged. Because it is significantly harder than tissue, the stimulation causes bone resorption around the filling material, causing problems such as loosening, and it has not been put to practical use in trenches.

7 used for FRP, FRTP, FRR, etc.
For example, glass 7 eyeper is used as the eyeper, but its tensile strength is only 1150-160 to 7-1 degrees, so it has been desired to produce a fiber with even higher tensile strength.

In order to solve the above-mentioned drawbacks, the present inventors chose a method of making a calcium phosphate material (a material containing C, Pl, and O; the same applies hereinafter) into a 7-Iper material through a melting process and a fiberization process. The present invention was completed as a result of various researches on this method, as well as research on the surface treatment of the 7-eyeper produced by this method as a way to further improve its therapeutic effect and tensile strength. Both of these methods have never been attempted before. The gist of this is that after melting 01
79 molar ratio (Cm/p ratio, hereinafter the same) is 0.6 to 1.7, and CaO + P2O5 is 80 weight - (
Hereinafter, it will simply be written as -. ) A method characterized in that the above-mentioned raw materials are made into fibers by a melting process and a fiberizing step, and the fibers produced by the above method are characterized in that they contain phosphoric acid groups and have a pH of 2 to 7. The method is characterized by immersion in a liquid solution.

First, to explain the first invention in detail, raw materials are melted and flowed out from a nozzle to produce fiberized calcium phosphate fibers. It must not only be able to solve the above problems, but also have a temperature that can be industrially processed (2) and a viscosity that allows the melt to be made into a 7-Iper.

9. The reason why the calcium phosphate material has a superior therapeutic effect as a filling material for bone defects in living bodies compared to other filling materials is that it contains Ca and P, which are the same as those that mainly make up the hard tissues of living bodies. These ingredients have the effect of promoting the generation of new bone. On the other hand, components other than Ca and P may become foreign substances to living organisms, and it is preferable to reduce the number of such foreign substances as much as possible. O
It is desirable that the S content be large.

Therefore, after melting various Ca/p molar ratios and CaO+P!
Possibility of fiberization by melting the raw material containing - and letting it flow out from a nozzle, and immediately blowing gas on the melted material, or cooling and solidifying it and winding it on a spinning wheel. At the same time, if the fibers could be made into fibers, tensile strength tests were conducted on the fibers, and the therapeutic effects were observed by filling defects in living bones.

As a result of these studies, even if fiberization is possible, if the cao + P2O1 after melting is less than 80qII, the therapeutic effect as a filler for living bone defects is insufficient compared to when it is sO - or more. It has been found. Furthermore, even when using a raw material with a cao + PxOs value of 8091 or higher after melting, if the NCa/p molar ratio is less than 0.8, PxOs will be too much) The viscosity of the melt will be too low, resulting in stable fiber formation. It becomes impossible to do so, and C
When the 1/P molar ratio exceeds 1.7, the melting point of the raw material rises rapidly, making it impossible to melt and form into fibers on an industrial scale.

``In the melting process and fiberizing process, it is possible to use materials that are not corroded during the melting of the raw materials of the present invention, such as crucibles or equipment made of platinum-rhodium, to prevent P contamination due to corrosion of melts, etc. It is preferable because it can remove impurities.

As the raw material used in the present invention, a calcium phosphate raw material, or a mixture of two or more selected from among a calcium phosphate raw material, a calcium raw material, and a phosphate raw material can be used.

C1140 (PO4) as a calcium phosphate raw material
2, Ca5(POn)sOHl(Jl(PO4)2, C
aHPO4, CaHPO4・21E (zO%Ca(addition a
) z, etc. contains one or more components that remain after melting, such as lime, slaked lime, calcium carbonate, etc. as calcium raw materials, but phosphoric acid, ammonium phosphate, etc. as ti phosphoric acid raw materials. , sodium phosphate, etc., containing one or more components that leave Pros after melting, such as sodium phosphate, are used.

When the Ca/p molar ratio is 0.6 to 1.7, one or two or more calcium phosphate raw materials are used, and when the Ca/p molar ratio is other than 0.6 to M1.7, two or more are used. It is used in combination with calcium and/or phosphate materials. Alternatively, a mixture of a calcium raw material and a cynic acid raw material may be used.

The selection and combination of raw materials can be determined as appropriate, taking into consideration their availability, price, and impurity content.

Next, the melting step is preferably a melting step including a 1: thermal decomposition step before melting the raw materials.

For example, when a raw material containing calcium carbonate is used as the calcium raw material, the calcium carbonate is decomposed by heating into CaO, which remains as a component of the fiber, and CO2, which is volatilized as a gas. Since this can be carried out industrially at a much lower temperature of about 900 DEG C., there is no need to use expensive refractory materials such as platinum-rhodium as the refractory material used in the apparatus for carrying out this decomposition. That is, by heating and scaling the raw materials and then melting, it is possible to downsize the melting equipment that uses the expensive platinum-rhodium refractory material, and it is also possible to avoid the difficulty of work due to volatilization of 002 gas during the melting process.

9. When a raw material containing ammonium phosphate, for example, is used as a phosphoric acid raw material, the ammonium phosphate is decomposed by heating into PxOs, which remains as a component of the sifter fiber, and PxOs, which volatilizes as a gas. Decomposition can also be carried out industrially at a temperature of about 200°C or less, which is much lower than the melting temperature of the raw material of the present invention, so melting the raw material after heating it will have the same effect as that of calcium carbonate. I: Corrosion of the melting equipment by volatilized IN and bagasse can be avoided. When the raw material is made into a sintered body or a semi-molten body through the thermal decomposition process, the operation becomes easier than when the raw material is fed into a powder trench/melting device.

Further, it is preferable that the melting step includes a temporary melting step, a cooling step, and a re-lighting step. In the method of producing fibers by melting raw materials once and then combining the fiberization process, in order to stabilize the fiberization process, it is necessary that the composition of the melt be uniform and that it does not contain gas particles.

Therefore, first of all, the melt #ica/p molar ratio according to the present invention is 0.
．． 6 to 1.7 and CaO+ P20s is limited to 80- or more, so the melting point is high, and the composition of the melt can only be made uniform by keeping it at a higher temperature than the melting point for a long time. Therefore, if each raw material is first melted (temporary melting) and cooled, then pulverized and mixed by galvanization if necessary, and then melted again (re-melted), the process is compared to the melting process that does not use these steps. Sufficient homogenization of the melt can be achieved with a short melting time.

In addition, when raw materials are melted, fine bubbles often exist in the melt, which often inhibits stable fiber formation. The small air bubbles in the product are reduced, the clarification of the melt is promoted, and fiberization can be made stably.

Next, it is preferable that the cooling step is one step of rapid cooling. If the cooling process is performed naturally, the galvanic current may crystallize and devitrify. When such a molten material is rapidly cooled by being poured into water, for example, the devitrification of the galvanic current is melted, and the remelting temperature can be lowered or the remelting time can be shortened, as well as melting. The product can be clarified better, so that the heat consumption can be reduced and the fiberization can be made more stable.

Preferably, the fiber chemical process is a process in which the nozzle is forcedly cooled. Conventional fiber 1 For example, in the case of alkali-free glass Fino (-), the viscosity that can be made into a fiber by melting raw materials is about 10 m to 10 m.Due to voids, the temperature of the melt is about 350° C., which is about 88 G to 1200° C.
Although it is possible to form a 7-eyeper over a wide range of temperatures, the melt of the raw material C2 of the present invention is CIO+P20! l is 8
Since the melt is a high-crystalline calcium phosphate substance whose composition is specified to be 0- or higher and the Ca/p4 ratio is in the range of 0.6 to M1.7, the viscosity is such that the melt can be made into fibers. The temperature range that can be achieved is a narrow range that is a fraction of the temperature range in the production of alkali-free glass, and even if the composition of the melt is sufficiently uniform, the temperature of the melt in the fiberization process is not appropriate. If this is not maintained, the viscosity of the melt will be too low or too high, making stable fiberization impossible.

Therefore, the temperature of the melt was set slightly higher than the appropriate temperature,
A forced cooling nozzle is used as the nozzle, and when the state of fiberization is observed and the degree of cooling of the nozzle is adjusted, the temperature and viscosity of the melt in the nozzle are adjusted to appropriate values. The amount of outflow can be maintained at an appropriate level, the fiberization process can be stabilized, and fibers with uniform diameter can be obtained.

The forced cooling nozzle may be any device as long as it is equipped with a mechanism that can lower the temperature of the molten material within the nozzle. For example, a nozzle equipped with a cooling fluid ejection pipe around the nozzle may be used.
The degree of cooling is adjusted by varying the location of the jet tube, the flow rate and/or temperature of the cooling fluid.

Next, the fiberization step is preferably a step of adjusting the spinning speed. Invention: Although the two-way fiber can be either long or short, it is sometimes desirable to keep the diameter constant in the production of long fibers, and by doing so, the fiberization can be carried out continuously. can be performed stably.

As the melt flows out from the nozzle, it loses its viscosity and solidifies as it cools.The diameter of the fiber is determined by increasing the spinning speed to make it thinner, and decreasing the spinning speed to thicker it. This desire was achieved by varying and adjusting the spinning speed, ie, the rotational speed of the spinning wheel. The rotational speed of the spinning wheel can be automatically controlled based on the measured value of the fiber diameter, and the diameter of the fiber can be made even more constant by automatically controlling the forced cooling mechanism of the nozzle.

The third invention relates to a method for further improving the properties of the calcium phosphate fiber obtained according to the first invention, and is manufactured by combining the above-mentioned processes as necessary. By immersing a calcium acid fiber in a solution containing phosphate groups and having a plate size of 2 to 7, calcium phosphate is formed on the surface of the fiber through a reaction between the components of the fiber and the phosphate groups in the solution. can be precipitated to further improve the therapeutic effect and/or tensile strength as a filling material for defects before living.

The above solution can be prepared, for example, by adding aqueous ammonia to an aqueous solution of cynic acid or aqueous solution of chloric acid. The degree of immersion of the chloric acid group and the immersion temperature and time can be selected in consideration of the composition of the fiber to be immersed and the amount of calcium phosphate to be deposited on the surface of the fiber.

It is necessary that the days of the solution are from 2 to 7.

If the solution number is less than 2, it tends to deteriorate the fiber, and if it exceeds 7, the precipitation of calcium henophosphate on the fiber surface becomes insufficient, both of which improve the therapeutic effect and tensile strength of the fiber. I can't do it.

This method can be used for both long and short single fibers, and if multiple long fibers are bundled and immersed, each 71 Iper will be strongly bonded to each other by the precipitated calcium sulfate, resulting in tensile strength. It is possible to improve the

In addition, single fibers or bundles may be dipped in the form of cotton, mat, thread, or cloth or mesh made of threads.

Moreover, it is particularly preferable that the number of circles in the solution is 4 to 7 because the therapeutic effect and tensile strength are large.

Example 1 Using reagents such as quicklime, triammonium 9ophosphate, alumina, etc., the Ca/p molar ratio was 0.5°0.6 after melting.
1.0, 1.7, 1.8, and each Cm/
In the case of P4 ratio, CaO+PzOs is 70% and 80% by weight.

eo*, 1s + 9-, and melted using a platinum crucible with a nozzle to form a fiber.
Regarding this, tensile strength measurements and animal experiments have shown the effectiveness of bone treatment. I guessed it. The results are as described in Table 1, Comparative Examples, and 4. The width symbols for the 7 eye barization methods in the same table represent the following.

As shown in Table 1, when the Ca/p molar ratio is 0.5, the viscosity becomes too low and it is impossible to form a fiber.

Therefore, it was estimated that the value less than 0.5 was similar to 4. A material with a Ca/p molar ratio of 1.8 was extremely difficult to melt and could not be made into a fiber. Therefore, 1 again,
It is presumed that the same is true for Ama over 8, and therefore C.
It has been found that fiberization is possible only when the a/p ratio is in the range of 0.6 to 1.7.

It was found that the tensile strength becomes particularly large when the content of 20g of CaO+P is 81OIII or more. Tensile strength of short fiber: It's straight! 1# Rounding is omitted because it is not constant and difficult to measure accurately.

In addition, among the long fibers that can be made into fibers, a bone defect artificially formed in the large bone of a domestic rabbit was filled in, and the development of new bone after that was observed.9. CaO in Honoku example
+For those containing 80% or more of P2o@, new bone formation was observed around the filled fibers in just 3 weeks, and there was no foreign body reaction at all, and a large healing effect was observed at an early stage.

But CaO+P! When the 011 content was 70%, it took about 4 weeks to reach a state similar to 7, which was not much different compared to the conventional method.

Similar animal experiments were conducted using short fibers, and the results showed that the generation of new bone was comparable to that of long fibers, and the early healing effect was similarly great.

Example 2 The raw materials in Table 1 containing components that generate smoke gas upon heating were compared between those that were directly melted and those that were previously thermally decomposed and then melted. The results of these raw material compositions and conditions are shown in Table 2, and the heat-resistant container was corroded by the gas that was rapidly generated by the direct melting, and the fiberization was also unstable. On the other hand, it was found that when the material was thermally decomposed in advance, the heat-resistant container was not eroded and fiberization could be carried out relatively stably. That is, in the case of direct melting to form fibers, the fibers often break every minute of the spinning width, but by melting after thermal decomposition, it has become possible to reliably and continuously form fibers for 5 minutes or more.

In Table 2, an aluminum crucible was used and a platinum-rhydium crucible was used for melting.

Example 3 Concerning the step of temporarily melting and then cooling 410 and 416 in Test A of Table 1 above to make long fibers,
The results are shown in Table 3, comparing the tensile strength and stability of 71 Iperization between the natural cooling method and the round shape that was quenched in cold water.

Table 3 The symbols representing cooling method (■) in Table 3 are as follows.

As shown in Table 3, when only natural cooling is performed, the continuous fiberization time is extended by about 5 minutes sIF compared to when no cooling step is performed, but when further quenched in cold water, natural cooling increases. The remelting temperature is slightly lower than in the case of
It became clear that the tensile strength became higher after drying, and the stability of the 7-eye condition was also relatively high. If we express this stability in terms of the time required for continuous fiberization, in the case of natural cooling, it is possible to make fibers continuously for 1 degree per 5 minutes, whereas in the case of quenching in cold water, it takes an additional 5 minutes or more. Continuous fiberization time becomes longer. This is because when natural cooling is used, the molten material tends to crystallize and devitrify, making it difficult to remelt, and also because air bubbles are present in the melt due to crystallization, making it easy to break during fiberization. In the case of medium rapid cooling, crystallization is prevented, so remelting is easy at a relatively low temperature, and since the state is fluorine-crystalline and uniform, the time required to continuously form fibers from h without containing air bubbles is relatively short. This is probably because it is longer. Therefore, during the above-mentioned method, temporary melting is required.

Example 4 Using the same formulation as Test 4410.414 in Table 1 above, a forced cooling nozzle by passing water after melting was placed in a Bimi-9 heat-resistant container, and the effect of forced cooling of the φ difference and the spring outside nozzle was compared. .

In this case, the cooling method is to install a water cooling pipe around the nozzle!
While passing water through the spinning process and monitoring the spinning status using a microscope with a magnification of 200 times, if the fiber becomes thin, increase the amount of cold water to increase the viscosity of the melt, and if the fiber becomes too thick, repeat the operation in reverse. As a result of the control, the time required to form continuous fibers was extended to several times longer, that is, approximately 1° or more, compared to the case without control. It also supports fiber tensile strength of 4410! 4 Tsuka17y4/j (A 10#″11
68Kr/sJ), the number of books corresponding to 414 is 18
911/J (A 14Fi188V'wJ) and 10\
An increasing trend was observed. This is also considered to be an effect of improved uniformity of fiber diameter.

Example 5 Using the same formulation as in Test AAIO, Mu14 in Table 1 above, melting was performed in the same manner as in Example 1, and during spinning, the diameter of the fiber was monitored using a microscope with a magnification of 200 times. When the diameter is smaller than the average value of about 15 μm and there is a risk of the spinning wheel being broken, the rotation speed of the spinning wheel is reduced, and when the diameter becomes large, the rotation speed is increased to control the spinning speed. Continuous fiberization time is approximately 1
It was extended to over 0 minutes. The average value of the spinning speed was about 550-hakama, the lowest was 460!71/min, the highest was 650-1/min, and the tensile strength was 171'/J, which corresponds to 410.
, the number of books corresponding to 1614 was 187"17'-, which showed the same increasing trend as in Example 4. Effects when using the present invention and carrying out the respective processing operations of the present invention (comparative experiments were conducted using two samples).

As mentioned in Example 2, if the processing operations after thermal decomposition are not performed, the continuous fiberization time will be approximately 1 minute longer.
By performing slow cooling and remelting operations, the possible melting time can be further extended to about 10 minutes. Next, when the slow cooling during the above operation was changed to rapid cooling in water, the testable time was significantly extended to around 6 minutes. Furthermore, in addition to these, the degree of cooling of the nozzle was adjusted according to the change in the diameter of the fiber, and the possible processing time #i became even longer to around 1 hour.

Finally, in addition to the above-mentioned operations, the spinning speed was controlled in accordance with changes in the diameter of the fiber, and it was found that the fiber could be formed with almost no breakage. In this way, what was newly discovered through this experiment is that the effect of extending the continuous fiberization time by performing each of the processing operations of the present invention is about 5 to 10 minutes, and In addition, the effect is an extension of less than one hour, but if all the operations are used together, it is possible to produce continuous fibers with almost no yarn breakage, so a near synergistic effect can be observed. It is.

Regarding the tensile strength of the single fiber, by using the above operations in combination, the one corresponding to A6 is ts811/j
, the corresponding one to 10 is 1741/j.

The number corresponding to 414 was 191 (-), and an increase of - in each case was observed.

Example 7 The length 7 eyeglass obtained in Test 446 in Table 1 above was prepared by adding ammonia water to an aqueous solution of cynic acid to give circles of 1.2.4, 7.
8 and immersed in a pressure liquid for about 10 minutes and dried.

Of these, the long 7 eyepers immersed in pH 1 solution (hereinafter referred to as pressure side ones) were corroded and deteriorated, but the ones with pH 2, 4, and 7 had sufficient calcium phosphate compounds on the surface. Precipitation was observed. When the pH was 8, precipitation of the calcium phosphate compound was insufficient.

Next, these treated long fiber bags, Deer 2.4, 7
．． When we filled artificially created bone defects in the large calvaria of domestic rabbits with 8 and treated them and observed the state of new bone formation, we found that with PH 8 and 4, new bone formation was observed in about 3 weeks. However, the same effect as in Example 1 was obtained, but P
New bone formation can be seen in H2 in about 2 weeks, and in about 1 week in PH4 and 7, and a much greater early treatment effect can be obtained compared to 4 which is not treated with cynic acid solution. I understand that.9.

A similar experiment was conducted on the short fiber obtained in the trench test 441B, and almost the same results were obtained.

Example 8 What is the procedure of Example 6 using the combination? Ten long fibers obtained by using the method II were bundled and treated in the same manner as the phosphoric acid treatment in Example 7, and the tensile strength was compared with that before surface treatment. The results are shown in Table 4. It was shown to.

Table 4 $11: According to Table 4, the tensile strength of all but those treated with pH 1 and 8 solutions increased compared to those before treatment.
In particular, the increasing tendency is remarkable at pH 4 to 7. This is because the calcium phosphate compound deposited on the surface of each single fiber was firmly and integrally bonded to each other.

Furthermore, among these treated long 7 eyepers, PH2,4
, 7, and 8 were used to conduct the same animal experiment as in Example F, and the state of new bone formation was observed. In the case of PH 8, new bone formation was observed approximately 3 weeks after the surgery. The effect is similar to that of PH2, but it takes about 2 weeks for PH2.
At a pH of 4°7, new bone formation can be seen in about 1 hour.
As in the case of Example 7, a very large early treatment effect was obtained compared to that untreated with the cynic acid solution.

Based on the above, the effects of the manufacturing method of the present invention are as follows.

(1) Through the invention of the production method of the present invention, a method for producing calcium phosphate fibers, which has not been produced using conventional techniques, has been established for the first time.

(萵) The invention of the production method of the present invention has clarified the compositional requirements and operational requirements for producing calcium phosphate 7-eyeper, making it possible to produce calcium phosphate fibers continuously and with little change in diameter. It became.

(萵) It has been difficult to continuously fiberize for a long time due to the raw material composition requirements of the present invention, but if each operation of the present invention is performed separately, the continuous fiberization time can be extended. When these operations are carried out in combination, there is a synergistic effect in that the processing time is longer than the addition of the above-mentioned extension times, and almost complete continuous fiberization is possible.

(4) With the establishment of a manufacturing method for calcium phosphate fibers, the drawbacks of various conventional materials have been eliminated, making it a special product! - It has become possible to supply a large amount of biocompatible material for filling bone defects in living organisms.

(5) The tensile strength of the newly created nine fibers (by the manufacturing method of the present invention) is much higher than the tensile strength of conventional ordinary glass fibers of 150 to 1601if/-.
80 to 200 (-) and has a toughness equal to or higher than that of steel fiber.
When used in , FRTP, FRB, etc., it is possible to make composite materials that are lighter and stronger than conventional ones. By treating calci phosphate and lamb fibers with a solution containing the following, it is possible to obtain a treatment material for living bone that has a particularly great therapeutic effect.

(7) Furthermore, when a plurality of calcium phosphate fibers are bundled and treated with the phosphoric acid solution, they are chemically bonded to each other and become a single piece, so the toughness is improved by so-called twisting. By synergistically increasing the number of strands or more, a very large effect can be expected in improving the performance of FRP etc. using this strand.

Patent Applicant: Mitsubishi Mining and Cement Co., Ltd. Procedural Amendment (Voluntary) November 26, 1980 Director General of the Patent Office Shima 1) Haruki Tono1, Indication of the Case 1982 Capital Patent Application No. 1022132, Name of the Invention: Sinic acid Production method of Calcium 7 Eyepar 3, Person making the correction Representative: Hisaaki Kobayashi 4, Agent Address: 166 On (999) 207B Address No. 3, Saginomiya S-chome ils, Nakasho-ku, Tokyo Name (83)
73) Patent Attorney 1) Sadao Naka 5. Date of amendment order (voluntary amendment) 6. Number of inventions increased due to amendment
None & Contents of Amendment (1) The scope of the patent claims after the amendment of the symbols used in the description of the claims is as follows.

2. Scope of Claims (1) A raw material having a Ca/P molar ratio of 0.6 to 1.7 after melting and a cao+p,o of 80 weight or more is processed through a melting process and a fiberization process. A method for producing calcium 9-phosphate fiber, which is characterized by the percentage of kernels used as fiber.

(2) The raw material is a mixture of two or more selected from among a calcium phosphate raw material, a calcium phosphate raw material, a calcium raw material, and a phosphoric acid raw material. A method for producing a calcium phosphate fiber according to item 1.

(31) The calcium phosphate fiber OS manufacturing method according to claim 1 or 2, wherein the melting step includes a thermal decomposition step before melting the raw material.

(4) The method for producing calcium phosphate fibers according to any one of claims 1 to 3, wherein the melting step includes a temporary melting step, a cooling step, and a remelting step.

(5) The method for producing calcium phosphate fibers according to claim 4, wherein the cooling step is a rapid cooling step.

(6) The method for producing calcium phosphate fiber according to any one of claims 1 to 5, wherein the fiber forming step includes forced cooling of a nozzle.

(f) The method for producing a calcium 9-phosphate fiber according to any one of claims 1 to 6, wherein the fiberizing step includes controlling the spinning speed.

(8) Ca/p molar ratio after melting is 0.6 to 1.7, and Cao+P, 0. Using raw materials with a weight of 80% or more, the fibers made into fibers by the melting process and the fiberizing process are made into fibers containing phosphate groups and having a pH of 2 to 7.
A method for producing calcium phosphate fibers, which comprises immersing them in a solution.

(9) Claim 8, wherein the pH of the solution is 4 to 7.
The method for producing the calcium phosphate fiber described in section.

(2) Correction of the description of the detailed description of the invention in the summer ■ Correct [Ca/p J in the 5th member, line 10 of the specification to l Ca/P J.

■ Line 16 of the same page of the specification [Correct PHJ to rpHJ.

■Page 6, line 16 of the specification Correct r　Ca/p　J to RCA/PJK.

■Page 7, line 3 of the specification Correct "do" to "1 - do".

■ RCA/P on page 7, line 10 and line 13 of the specification
Correct J to RCA/PJ.

■ Line 16 of the 8th line of the specification Correct r　Ca/p　J to [Ca/P　J.

■　In the 11th member, 1st line of the specification Correct rca/pJ to rCa/PJK.

■ Line 14 of the same page of the specification Correct "remelting" to "remelting".

■ [Ca/
Correct p j to [Ca/P J.

[Phase] Page 14, line 2 of the specification Correct "to do" to "to do as well."

■ Line 3 on the same page of the specification Correct "sometimes" to "especially."

■ Same/negative line 6 of the statement Correct "do" to "do".

■ [PHJ, , on page 15, line 1, line 15, and line 16 of the specification are corrected to rpHJ.

0 Line 9 of the 16th member of the specification “PI (Correct J to rpHJ.

@ rca/ on page 16, lines 13 and 14 of the specification
Correct pJ by [Ca/P j K.

0 “70%” on page 16, line 15 to line 16 of the specification
, 80%, 90%, 98%, 99%" should be corrected to [the percentages shown in Table 1].

@ r on page 17, line 5, line 8, and line 11 of the specification
Correct ca/pJ to [Ca/P J.

[Stocks] "Cureative effect" in lines 5 and 11 of line 18jj of the specification is corrected to "therapeutic effect."

■ It took about 4 weeks, as shown in lines 7 to 8 on page 18 of the specification, which was not much different than before. ]of[
It took about 4 weeks. ” is corrected.

No. 191 of the specification! r Ca in the top column of L No. 11p
/p J to [Ca/P J K Correct.

@ 20th member line 6 of the statement Correct ``Shitamono ga'' to ``Shitamoto no wa''.

[Stock] Specification No. 20J [Line 1θ Correct "Gyoi" to "Gyoi".

O statement 22nd member 1st line Correct ``I went'' to ``Yukihikota''.

[Phase] Page 23, line 4 of the specification [Test A6, top 10. A14J [M10, M1 in Test A
4] is corrected.

@l! [Book, page 23, line 12! ! l) @ line 13 O “
Correct “Go” to “Go”.

[Phase] "Test A6 A610 + Consideration 14" on page 24, line 2 of the specification.
, ^14".

[Stocks] Change "Test/% Muro, /%10.mu14" in the 24th member, line 16 of the specification to [AS in Test A
, 410. /%14 Correct to J.

0 Specification 011E24j [Correct "I went." in line 18 to "I did it."

[Phase] Page 24, line 19 of the specification Correct "do not do" to "do not do".

@Page 25, line 1 of the specification Correct ``Go'' to ``Go one line.''

■ Statement No. 25 Purchase line 5, line 9 to line 10, line 1
In the second line, ``Go to 9 places'' is corrected to ``Go to place''.

@ Correct “to do” in lines 13 and 16 of the specification No. 25 to “to do” K.

0 Line 8 of line 26 of the specification "Test/16/%6" [Test Yunaka Muro JK corrected.

0 Statement No. 26 Purchase Line 9, Line 12, Line 14.

Lines 15 and 18 Correct r PHJ to rpHJ.

@ Specification No. 27jj 1st line, fft, 3rd line and 4th line rPHJ is corrected by rpHJK.

[Phase] [Test, %, %15J in the 27th negative line 8 of the specification is corrected to 415J in [Test].

[Stocks] Details II No. 27 No. 9 ``I did one line of ``Goda.'''' K corrected.

■ [Examination Mafu 6. All, genus 15'' to ``exam nakagata 6..
%11. Corrected to ``Consideration 15''.

■Page 27, line 15 of the specification Correct [act 1] to ``do'' K.

0 Table 4 on page 28 of the specification “Correct PH1 to rpHJ.

Correct the rPHJ in the 1st, 3rd, 9th, and 11th lines of the specification by rpHJK.

O Specification, page 28, line 10 Correct "deed" to "deed".

O Specification, page 29, line 1 r　Pi(correct J by rpHJK.

0 Specification page 29 line 18 Correct "if done" to "if done".

that's all

Claims (1)

[Claims] (1) After melting, the 01/P4# ratio is Ol/No II 1.
7. A method for producing calcium phosphate fiber, in which the raw materials are molten ball 1, fiber chemical 1 and heat; In a patent claim, the raw material is a mixture of three or more selected from among calcium phosphate raw materials, calcium phosphate raw materials, lucium raw materials, and sino acid raw materials. Range I! A method for producing a calcium phosphate fiber according to paragraph 1, subsection 2. (Claim S, paragraph 1 or 2, where the melting process l1 includes heating and scaling before melting the raw materials) J
[The method for producing calcium phosphate fiber described in [. (6) The cynic acid according to any one of claims 1 to 3, wherein the molten ball @ is a device 1 that connects a temporary melting device 1, a cooling device 1, and a remelting device. Method for producing calcium fiber. (Claim S in which 1 m of cooling equipment is 1 meter of cooling equipment)
A method for producing calclum 71 ipar [according to item 4]. (@ 71 Ipar manufacturing method for producing calcium yanate substance 71 Ipar according to any one of claims 1 to 5, wherein the nozzle is forcedly cooled.) (n 71 Iper Kako S meets to control spinning speed l1
Therefore, a method for producing a calcium phosphate fiber according to any one of claims 1 to 1. (After melting, the raw material has a mu/p4 ratio of 0.6 to 1.7 and 0ρ+Pack is greater than or equal to the weight of the molten ball 1 and the fiber chemical 1.)
Calcium phosphate substance 7 characterized by immersing the Eyeper in a solution containing phosphoric acid groups and having a PR of 8 to M7.
How to make eyewear. (Gin) The method for producing calcium phosphate 7-iper according to claim 8, wherein the number of circles of the solution is 4 to 7.