KR100740139B1 - Process of producing radiopaque fibers and radiopaque fibers produced thereby - Google Patents

Abstract

A radio-opaque fiber and a manufacturing method thereof are provided to have the lighter weight than the existing radio-opaque fiber and to offer a harmless fiber. Chitosan, acetic acid and barium chloride are mixed so that the spinning solution is prepared and stabilized at the vacuum or in the air. Thereafter, the spinning solution is spun at the solidification solution comprising the mixing solution of sodium hydroxide solution and sodium sulfate solution. The spinning solution is solidified and simultaneously the barium chloride within the spinning solution is chemically changed into barium sulfate, so that the barium sulfate exists at the inside and outside of the chitosan fiber by the wet type spinning manner. The barium sulfate also exists at the inside and outside of poly vinyl alcohol fiber by the wet type spinning manner.

Description

Process of Producing Radiopaque Fibers and Radiopaque Fibers Produced Thereby

1 to 5 are SEM images of barium sulfate / chitosan fibers obtained in Examples 1 to 5 of the present invention, respectively.

6 is an X-ray diffractogram of barium sulfate / chitosan fibers obtained in Examples 1 to 5 of the present invention,

7 is a thermogravimetric analysis photograph of barium sulfate / chitosan fibers obtained in Examples 1 to 5 of the present invention;

8 to 12 are SEM images of barium sulfate / polyvinyl alcohol fibers obtained by Examples 6 to 10 of the present invention,

FIG. 13 is an X-ray diffraction analysis photograph of barium sulfate / polyvinyl alcohol fiber obtained in Examples 6 to 10 of the present invention;

14 is a thermogravimetric analysis photograph of barium sulfate / polyvinyl alcohol fiber obtained in Examples 6 to 10 of the present invention;

15 is an X-ray photograph of barium sulfate / chitosan fibers obtained in Examples 1 to 5 of the present invention;

16 is an X-ray photograph of barium sulfate / polyvinyl alcohol fibers obtained in Examples 6 to 10 of the present invention.

The present invention relates to a method for producing a radiopaque fiber and a radiopaque fiber produced by the same, and to a fiber that is lighter than a conventional radiopaque fiber and which is harmless to a human body.

It is well known that radiation, such as x-rays and gamma rays, causes many serious diseases and disorders, including carcinogenesis, genetic disorders, and cataracts. In particular, people who directly or indirectly deal with radiation, such as radiologists, doctors, and nuclear power personnel in hospitals, may be exposed to radiation because of their work characteristics. Therefore, optimal facilities and equipment are needed to reasonably reduce radiation exposure of occupational workers and surrounding environment related to radiation, and efforts should be made to optimize the protection of the body parts except the patient's medical part for diagnosis. .

As a method for shielding such radiation, it is common to wear a sheet-like gown formed by dispersing lead components in a rubber and then extruding them. However, gowns manufactured in this way are effective for radiation shielding, but are very heavy, such as 5 to 10 kg, and thus have a poor fit, and thus they are not universally worn except for those engaged in some areas of nuclear power plants. In particular, the radiation used in hospitals is not only low dose, but there is no risk of direct radiation exposure, and the risk of indirect exposure due to radiation diffraction is high, so that workers rarely feel the necessity of wearing heavy lead gowns. There was a problem not to take the inconvenience of poor workability.

In Korean Patent No. 10-0581554, it is in direct contact with a user's body to shield radiation. As a flexible material, the dermis composed of any one of cotton fabric and synthetic fiber, and directly contact or directly affect an object, a tool, or a radiation substance A vest or a vest to fasten a radioactive protective material composed of an outer skin coated with barium sulfate to any one of cotton fabric, nylon and polyester fiber, and an inner skin formed of a naphtha or lead layer between the dermis and the outer skin. It provides a radioactive protective clothing characterized in that it is formed by cutting into a cardigan-shaped clothing, but the patent uses a coating coated with barium sulfate on any one of cotton fabric, nylon, polyester fibers as the outer cover, and the fastness to washing Will reduce the durability of the dermis and the cortex Thus it forms the endothelial containing lead had a disadvantage in that heavy and do not decrease the activity good workability.

Accordingly, an object of the present invention is to provide a wet-spun radiopaque fiber having excellent durability, such as lightness and fastness to washing, by wet spinning by mixing barium sulfate and fiber to solve the problems of the prior art.

In addition, an object of the present invention is to provide a radiopaque fiber which is harmless to the human body in which barium sulfate is uniformly present in the fiber to be inserted into the human body so as to enable diagnosis of a specific site through X-ray imaging.

Therefore, according to the present invention, chitosan, acetic acid and barium chloride (BaCl ₂ ) is mixed to prepare a spinning stock solution, and stabilized in vacuum or air, and then mixed with a solution of sodium hydroxide (NaOH) and sodium sulfate (Na ₂ SO ₄ ) solution. Radiation of the spinning stock solution to the coagulation bath formed by the coagulation of the fiber and at the same time chemically change the barium chloride present in the spinning stock solution to the barium sulfate (BaSO ₄ ) radiation characterized in that the wet spinning so that the barium sulfate is present inside and outside the chitosan fiber A method of making an impervious fiber is provided.

In addition, according to the present invention, after preparing a spinning solution by mixing polyvinyl alcohol (PVA) and barium chloride, the spinning solution is spun into a coagulation bath made of sodium sulfate solution to coagulate fiber and present barium chloride in the spinning solution. There is provided a method for producing a radiopaque fiber characterized by chemically changing the barium sulfate to wet spinning so that barium sulfate is present inside and outside the solidified polyvinyl alcohol fiber.

According to the present invention, there is provided a radiopaque fiber, characterized in that the fiber was wet-spun so as to contain barium sulfate in and out of the chitosan or polyvinyl alcohol fibers by the production method.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing a radiopaque fiber and a radiopaque fiber produced thereby, wherein the radiopaque fiber of the present invention is obtained by wet spinning to contain barium sulfate in and out of the fiber.

In order to manufacture a fiber product that cannot transmit radiation such as X-rays, it is preferable to incorporate barium sulfate, which is harmless to the human body, which is used as an X-ray contrast agent as a radiopaque material, to be incorporated into the fiber as well as the outside of the fiber. In the present invention, the method of incorporating barium sulfate into the fiber is prepared by adding a water-soluble barium chloride to aqueous solution of chitosan and polyvinyl alcohol, which are water-soluble polymers, to prepare a fiber-forming polymer / barium chloride complex aqueous solution, and to which sodium sulfate is added. By wet spinning in a coagulation bath, coagulation of the fiber-forming polymer solution and formation of barium sulfate occur simultaneously to obtain radiopaque fibers containing barium sulfate in and out of the fiber.

The reaction of the fiber-forming polymer / barium chloride complex aqueous solution as a spinning stock solution in the coagulation bath is as follows.

BaCl ₂ + Na ₂ SO ₄ ⇒ BaSO ₄

The reason for not mixing the barium sulfate particles directly into the fiber-forming polymer in the present invention is that when the barium sulfate particles are directly mixed, it is difficult to evenly disperse the barium sulfate particles in the polymer solution, and the agglomeration of the particles occurs to cause the aggregated particles to radiate. This is because it is difficult to produce a fibrous form because the nozzle is blocked, and when the barium sulfate is added 5% or more, serious degradation of the fiber properties occurs.

When chitosan is used as the fibrous polymer, the spinning stock solution is prepared by mixing a chitosan solution, acetic acid, and barium chloride, preparing a spinning stock solution, stabilizing in vacuum or air, and then applying the spinning stock solution to a coagulation bath comprising a mixture of sodium hydroxide solution and sodium sulfate solution. At the same time as the fiber coagulates, the barium chloride present in the spinning stock solution is chemically transformed into barium sulfate to wet-spin the barium sulfate in and out of chitosan fibers.

In addition, in the case of using polyvinyl alcohol as the fiber-forming polymer, after preparing a spinning solution by mixing polyvinyl alcohol and barium chloride, the spinning solution is spun into a coagulation bath made of sodium sulfate solution to coagulate fibers and simultaneously to the spinning solution. The barium chloride present is chemically changed to barium sulfate and wet-spun so that barium sulfate is present inside and outside the solidified polyvinyl alcohol fiber.

In addition to the chitosan and polyvinyl alcohol, cellulose, alginic acid, polyacrylonitrile, etc. may be used as the fiber-forming polymer, and the composition of the coagulation bath may be changed according to the fiber-forming polymer.

The fiber produced by the wet spinning method of the present invention may be present in the fiber and the barium sulfate more than 50% of the weight of the fiber can be obtained impermeable to X-rays, there is an advantage that does not significantly decrease the fiber properties .

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

[Examples 1 to 5]

Preparation of Chitosan / Barium Sulfate Composite Fiber

Chitosan and barium chloride as shown in Table 1 Powder and acetic acid are mixed to prepare a spinning solution. Mixed Chitosan / Barium Chloride The solution is placed in a tank and stabilized in vacuo for 24 hours to remove bubbles from the solution. After preparing a coagulation bath composed of an 8% sodium hydroxide solution and an 8% sodium sulfate solution, spinning was performed using a nozzle of Φ 0.1 mm and 150 holes to prepare chitosan / barium sulfate composite fiber through washing, winding, and drying. .

Chitosan Acetic acid Barium chloride water Final Chitosan / Barium Sulfate Ratio Related SEM Pictures Example 1 40 g 20 g 35.6 g 904.4 g 50/50 1 Example 2 40 g 20 g 23.7 g 916.3 g 60/40 2 Example 3 40 g 20 g 15,25 g 924.75 g 70/30 3 Example 4 40 g 20 g 8.9 g 931.1 g 80/20 [Figure 4] Example 5 40 g 20 g 3.95 g 936.05 g 90/10 5

The characteristics of the obtained chitosan / barium sulfate composite fiber were analyzed by the following method, and SEM pictures are shown in FIGS. 1 to 5, XRD graphs are shown in FIG. 6, and TGA graphs are shown in FIG. 7.

※ Characteristic Analysis

X-ray diffractometer with angle from 5 degrees to 55 degrees.

SEM: HITACHI, S-3000N.

Thermogravimetric analysis of TGA: fibers was performed at a heating rate of 10 ° C./min in a nitrogen atmosphere.

According to the SEM photographs of FIGS. 1 to 5, it is possible to produce barium sulfate / chitosan composite fibers having various ratios, and even when the barium sulfate content is increased, the fiber shape is stable without deformation. According to the X-ray diffraction analysis of FIG. 6, barium sulfate is present in the fiber because it shows a typical peak of barium sulfate in the barium sulfate / chitosan composite fiber.

According to the thermogravimetric analysis of FIG. 7, since barium sulfate does not thermally decompose into an inorganic material, when barium sulfate / chitosan composite fiber is heated to 1000 ° C., chitosan is an organic material, and thus weight loss occurs due to pyrolysis, and a constant residual amount is determined according to barium sulfate content. It can be seen that barium sulfate is present in the fiber. According to the X-ray photograph of FIG. 15, it can be seen that the barium sulfate / chitosan composite fiber is clearly visible by X-ray imaging due to X-ray impermeability.

[Examples 6 to 10]

Preparation of Polyvinyl Alcohol / Barium Sulfate Composite Fiber

As shown in Table 2, polyvinyl alcohol and barium chloride having a degree of polymerization of 1700 and a degree of saponification of 99.8%. The powder is mixed with water to prepare a spinning stock solution. Each spinning stock solution was completely dissolved by stirring at 100 ° C. for 2 hours, cooled to room temperature, and subjected to a defoaming process using a vacuum pump. After preparing a coagulation bath composed of 40% sodium sulfate solution, the mixed polyvinyl alcohol / barium chloride The solution is placed in the spinning machine tank and discharged into the coagulation bath using a nozzle (1 hole) having a diameter of 0.25 mm at a pressure of 4 kgf / cm 2. The spinning stock solution discharged to the coagulation bath was stretched three times with a roller to form a fibrous form, and then a water / methanol (mixing ratio 50:50) solution was prepared to wash polyvinyl alcohol / barium sulfate composite fibers, respectively, and dried at 40 ° C. Polyvinyl alcohol / barium sulfate composite fiber was prepared.

Polyvinyl alcohol Barium chloride water Final Polyvinyl Alcohol / Barium Sulfate Ratio Related SEM Pictures Example 6 12 g 10.6 g 77.40 g 50/50 8 Example 7 12 g 7.12 g 80.88 g 60/40 9 Example 8 12 g 4.57g 83.43 g 70/30 10 Example 9 12 g 2.67 g 85.33 g 80/20 11 Example 10 12 g 1.18 g 86.82 g 90/10 12

The characteristics of the obtained polyvinyl alcohol / barium sulfate composite fiber were analyzed in the same manner as in Examples 1 to 5, and SEM pictures are shown in FIGS. 8 to 12, XRD graphs are shown in FIG. It was.

According to the SEM pictures of FIGS. 8 to 12, it is possible to prepare barium sulfate / polyvinyl alcohol composite fibers having various ratios and is stable without deformation of the fiber even when the barium sulfate content is increased. According to the X-ray diffraction analysis of FIG. 13, barium sulfate / polyvinyl alcohol composite fibers also show typical peaks of barium sulfate, and thus barium sulfate is present in the fiber. According to the thermogravimetric analysis of FIG. 14, since barium sulfate does not thermally decompose into an inorganic material, when the barium sulfate / polyvinyl alcohol composite fiber is heated to 1000 ° C., polyvinyl alcohol is an organic material, and thus weight loss occurs due to thermal decomposition, and the barium sulfate content is increased. Therefore, it can be seen that the barium sulfate is present in the fiber because it shows a constant residual amount. According to the X-ray photograph of FIG. 16, it can be seen that the barium sulfate / polyvinyl alcohol composite fiber is clearly visible by X-ray imaging due to X-ray impermeability.

According to the present invention, it is possible not only to effectively shield X-ray radiation, but also to provide a fiber that is lighter than the conventional radiopaque fiber and is harmless to the human body, and is harmless to the human body in which barium sulfate is uniformly present in the fiber. By providing permeable fibers and inserting them into the human body, X-ray imaging can be used to diagnose specific areas.

Claims (3)

Chitosan, acetic acid and barium chloride were mixed to prepare a spinning stock solution and stabilized in a vacuum or air, and then the spinning stock solution was spun into a coagulation bath consisting of a mixture of sodium hydroxide solution and sodium sulfate solution. And chemically changing barium chloride to barium sulfate to wet spin the barium sulfate so that the barium sulfate is present inside and outside the chitosan fiber. After preparing a spinning stock solution by mixing polyvinyl alcohol and barium chloride, the spinning stock solution is spun into a coagulation bath composed of sodium sulfate solution to coagulate fiber and chemically change barium chloride in the spinning stock solution to barium sulfate. A method of producing a radiopaque fiber, characterized in that the wet spinning so that the barium sulfate is present inside and outside the vinyl alcohol fiber. A radiopaque fiber, wherein the fiber is wet-spun so as to contain barium sulfate in and out of chitosan or polyvinyl alcohol fibers according to the method of claim 1.

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