KR0157013B1 - Casting sheet for plastic surgery use - Google Patents

Abstract

DETAILED DESCRIPTION OF THE INVENTION The present invention disperses dyes, pigments, ceramic powders with far-infrared radiation, organic bioactive materials and / or antimicrobial agents in a resin film-forming binder used as a focusing agent in the manufacture of glass fibers, and then firmly adheres to glass fiber filaments. A method of manufacturing a casting sheet and a casting sheet produced by the method, wherein the fiber sheet is made and the glass fiber continuous yarn is woven to prepare a knitted fabric sheet, and then the glass fiber knitted sheet is coated with a moisture curable prepolymer. It is about.

Description

[Name of invention]

Orthopedic casting sheet and its manufacturing method

Detailed description of the invention

[Field of Invention]

The present invention relates to an X-ray surgical casting sheet and a method for manufacturing the same, and more specifically, a connection agent made by dispersing a dye, a pigment, and / or a ceramic powder having a far-infrared radiation function in a resin-based film-forming binder to a fibrous glass. It relates to an orthopedic casting sheet produced using a glass fiber continuous yarn made by a method of treating a filament surface and a method of manufacturing the same.

[Background of invention]

In orthopedics, gypsum bandages have been used to fix fractures. However, gypsum bandages are difficult to detect fractures due to poor permeability of X-rays, and they are heavy and impair the behavior of the patient. This may cause serious damage to the patient's skin. Moreover, plaster bandage casts are very sensitive to moisture, which causes problems such as a decrease in strength when they come in contact with moisture. Therefore, the plaster bandage cast cannot be in contact with water such as bath or face wash while the cast is worn. Was difficult and there were many hygienic problems.

Recently, in order to overcome the disadvantages of the gypsum bandages, a casting sheet coated with a water-curable polyurethane prepolymer on a knitted fabric sheet has been developed and is very useful. For example, U.S. Pat. No. 4,411,262 and the like disclose a method for producing the prepolymer and a method for producing a casting sheet in which the prepolymer is coated on a knitted fabric sheet. These casting sheets are used in the fractured areas of the patient after briefly soaking in water in the same way as gypsum bandages. The water begins to cure the polyurethane prepolymer coated on the knitted sheet and then hardens after a few minutes to fix the fracture site. For this reason, the knitted fabric sheet coated with the polyurethane prepolymer should be stored in a package which completely blocks moisture to avoid contact with moisture until immediately after use.

In addition, a method for producing a colored casting sheet is described in US Pat. No. 5,005,566, and a casting sheet obtained by dispersing an antimicrobial deodorant or a compound having far-infrared radiation in a polyurethane prepolymer and coating the knitted sheet is disclosed in Korean Utility Model. Publication No. 94-11930. However, the method described in U.S. Patent No. 5,005,566 and Korean Utility Model Publication No. 94-11930 is a method for producing a casting sheet by coating a polyurethane sheet with a polyurethane prepolymer in which a compound having far-infrared radiation function is dispersed. As dyes, darkeners and / or ceramic powders do not adhere firmly to the substrate, the color distribution of the casting sheet is not constant, discolors or flows out of the liquid polyurethane prepolymer during storage of the casting sheet. It is easy to discolor. The problem of color stability is exacerbated by the amine catalyst added to control the curing time of the polyurethane prepolymer, which causes the discoloration or discoloration by reacting with the chromophores of the dyes or pigments in which the highly reactive amine catalyst is used. Because. In addition, to evenly disperse the dyes, pigments and / or ceramic powders in the prepolymer, they must be dispersed in a strong stirrer for a long time, sometimes using a roll-mill. As such, it is difficult to evenly disperse dyes, pigments and / or ceramic powders in the polyurethane prepolymer, and even after dispersing, it causes a non-uniform state due to aggregation, so that addition of an anti-agglomerating agent such as polyvinyl alcohol, ether or surfactant is required to prevent this. There was a need to use or to remove the aggregates by filtration. Another problem is that dyes or pigments affect the stability of polyurethane prepolymers. In particular, since the dye mainly has a reactive chromophore such as azo group, the dye of the polyurethane prepolymer coated on the knitted fabric sheet is abnormally raised, making it difficult to use or hardening during storage. In addition, most of the chromophores greatly promote the curing reaction of the polyurethane prepolymer, so that it is not possible to guarantee proper treatment time such as hardening before the end of the procedure. Some dyes and pigments are toxic and can cause disturbances when they come in direct contact with the patient's skin. In addition, pigments and far-infrared radiation ceramic particles are mostly composed of inorganic particles, making it difficult to mix with the polyurethane prepolymer, which is an organic material, and metals or metal ions whose main components are -NCO and allophanet, which are terminal functional groups of the polyurethane prepolymer. Or because it is known to cause side reactions such as the burette reaction, to harden during storage, or to increase the viscosity abnormally, making it difficult to use and to greatly accelerate the curing reaction of the polyurethane prepolymers. Even dispersion may cause serious problems in the storage stability of the casting sheet and the work efficiency during the procedure.

As such, the dyes, pigments and / or far-infrared radiation ceramic particles are not only difficult to disperse in the polyurethane prepolymers, but even if successfully dispersed, they cannot react with the polyurethane prepolymers to ensure the storage stability and working efficiency of the casting sheet. .

[Purpose of invention]

Accordingly, an object of the present invention is to disperse dyes, pigments, and / or ceramic powders having far-infrared radiation in a resin-based film-generating binder used as a focusing agent in the manufacture of glass fibers, and then firmly adhere to the glass fiber filaments, thereby continuing the It is to provide a method for producing a casting sheet having a uniform color and distribution by coating a water-curable polyurethane prepolymer on a knitted sheet which is woven the glass fiber continuous yarn in a suitable manner.

Another object of the present invention is to provide a method for producing a casting sheet capable of preventing the dissolution of dyes, pigments and / or ceramic powder particles having a far-infrared radiation function.

It is yet another object of the present invention to provide a method for producing a stable casting sheet by preventing a reaction between a dye, pigment and / or ceramic powder particles having a far infrared radiation function and a moisture curable polyurethane prepolymer.

Another object of the present invention is to provide a casting sheet produced by the above method.

[Summary of invention]

The present invention is to disperse the dye, pigment and / or ceramic powder having a far-infrared radiation in a resin-based film-forming binder used as a focusing agent in the manufacture of glass fibers, and then strongly adhered to the glass fiber filament to form a glass fiber continuous yarn and the glass The present invention relates to a method for producing a casting sheet, wherein a fiber continuous yarn is woven to prepare a knitted fabric sheet, and then the glass fiber knitted sheet is coated with a moisture curable polyurethane prepolymer.

The invention also relates to a casting sheet produced by the method.

Detailed Description of the Invention

The casting sheet of the present invention is dispersed in a resin-based film-forming binder used as a focusing agent in the production of glass fibers by dyes, pigments and / or far-infrared radiation function to strongly adhere to the glass fiber filament to form a glass fiber continuous yarn The glass fiber continuous yarn is produced by a method of coating a moisture-curable polyethane ethane prepolymer on a knitted fabric sheet woven in a suitable manner.

When manufacturing the fiberglass, a focusing agent is used to prevent the breakage caused by friction of the filament in the process of focusing the filament filaments, to facilitate spinning, and to facilitate the post-treatment process such as weaving, such a binder Starch-based binding agents and resin-based film-forming binders. In the case of treatment with starch-based binding agent, it is inexpensive and easy to handle, while it is troublesome to completely remove the binding agent through heat treatment at 380-450 ° C. for 72 hours or more before coating the prepolymer. Since resin-based film-forming binders are expensive and not easily removed, they cannot often be used in combination with resins impregnated during the manufacture of glass fiber-reinforced full plastics, but they do not require heat treatment after being used for glass fibers. In this invention, it is preferable to use the glass fiber manufactured by processing with the resin film production binder.

The glass fiber used in the casting sheet is described in US Pat. No. 4,609,478, and mainly uses glass fiber such as ECE, ECC, ECG.

The resin-based film-forming binder is preferably one in which an epoxy resin is dispersed in a water-soluble polymer, but urea resin, polyurethane, polyacryl, polyester, ethylene-propylene copolymer, ethylene-vinylacetate copolymer or polyvinyl alcohol; natural rubber Or rubber such as synthetic rubber may be used. They are dissolved in water or other suitable solvent, or melted and melted to form a liquid state, and a small amount of surfactant and silane coupling agent are added thereto as a focusing agent.

As the dye used to express the color in the cast sheet, phthalocyanine-based, dioxazine-based, diazo-based, anthraquinone-based, queenacridone-based, perylene-based, or isoindolin-based dyes may be used. It is also possible to use inorganic pigments such as titanium dioxide, iron oxide, or carbon black and organic pigments made of various plastic particles exhibiting color or mixtures thereof. These pigments preferably have an average particle diameter of 0.1-15 micrometers, and can be used by being evenly dispersed in a resin film-forming binder used as a binding agent.

Ceramic powders with far-infrared radiation include silicon, aluminum, titanium, zirconium, magnesium, calcium, or iron oxides, nitrides, sulfides, carbonides, borides or mixtures thereof; Or porous inorganic particles such as zirconia. As with the pigment, the average particle diameter is preferably 0.1-15 micrometers, and can be uniformly dispersed in the resin film-forming binder used as the binding agent. During the manufacturing process of the glass fibers, the molten glass flows through the holes of the bushing made of an alloy of platinum and rhodium, and is fibrous. The fibrous glass is pulled into fine filaments with a diameter of 5-24 micrometers and used as a resin film-forming binder. After coating, focusing several strands creates a fiberglass continuous yarn. In this process, dyes, pigments, far-infrared radiation ceramic particles, organic bioactive materials and / or antimicrobial agents are added to the resin film-forming binder to coat the filaments with colored glass fibers, far-infrared radiation, bioactive or antimicrobial functions. The glass fiber with this can be obtained. When the glass fiber is woven in various widths in a knitting machine with a structure having moderate elasticity and porosity, the prepolymer is coated to obtain a casting sheet having color, far-infrared radiation, bioactive function, or antibacterial function.

Polyurethane prepolymers coated on glass-fiber knit sheets are prepared by the reaction between excess isocyanates and polyols, and a small amount of catalyst is added to control the rate of curing reaction during moisture contact and to suppress bubble formation during curing. Silicone antifoams, stabilizers and antioxidants for imparting storage stability, and small amounts of surfactants are added for operational efficiency. For example, 45-62% polyisocyanate, 25-45% polyol, 0.3-2.5% catalyst, 0.05% stabilizer, 0.5-1.0% antioxidant, and 0.5-1.5% defoamer and surfactant 1 Used at a rate of -5 weight percent. An amine catalyst and a tin catalyst are used as a catalyst, benzoyl chloride is preferable as a stabilizer, BHT is used as an antioxidant, a silicone oil is used as an antifoaming agent, and a nonionic surfactant is used as a surfactant. It is preferable. First, the reaction vessel is put in a vacuum state, and then polyisocyanate is first added thereto, and dried nitrogen gas is supplied thereto, and then a stabilizer, an antioxidant, and an antifoaming agent are added at intervals. Put the polyol vacuum-dried in another reaction vessel, stir well, add the surfactant and catalyst, and then slowly add the mixture to the first reaction vessel using a dropping funnel. When the temperature rises to 50-60 ° C. due to the exothermic reaction, the reaction is continued while maintaining this temperature to complete and cool the reaction.

The prepolymer prepared by the above method is coated on a glass fiber knitted fabric sheet to which dyes, pigments and / or far-infrared radiation ceramic powder particles are fixed by a known method, and then placed on a wheat shelf package which blocks moisture to avoid contact with moisture. Nitrogen packed packaging produces a casting sheet that retains storage stability for more than two years.

The casting sheet is opened immediately before use, soaked for several seconds in water, and then wrapped with 4-5 layers of fractures on the patient's fracture area, which is firmly fixed in 20-30 minutes to form a cast of adequate strength.

The casting sheet of the present invention prepared in this way is not a dye, pigment, and / or cerium powder particles having far-infrared radiation function are dissolved or dispersed in the prepolymerization system as in the known art, Because it is strongly adhered to the glass fiber, it does not react with the liquid prepolymer during storage and does not excessively accelerate the moisture curing reaction, and it also aggregates without flowing or eluting in the liquid prepolymer, causing discoloration and discoloration. And because it has a uniform distribution at all times, it can be expected to show the effect of stability of color and excellent far-infrared radiation function.

EXAMPLE

Example 1

The resin-based film-forming binder prepared by dispersing dyes or pigments having various color indices is coated on the surface of the glass fiber filament melted and spun, and then the glass fiber twisted through the focusing and drying process is known to have elasticity and porosity. To obtain a glass fiber knitted fabric sheet.

A 3-liter reaction vessel was placed in a vacuum state, and 1593 g of polyisocyanate (Isonate 143LK, manufactured by HDPU) was added thereto, and 2.5 g of a stabilizer (benzoyl chloride) was added while blowing dried nitrogen gas. 5.4 g of antifoaming agent (manufactured by KF-69 Shinetsu Silicon Co., Ltd.) and 14.4 g of antioxidant (BHT) are slowly added at 6-8 minute intervals. Put 1238 g of polyol (KONIX PPG-725 Korea Polyol Co., Ltd.) vacuum-dried in another reaction vessel and stir well, and 12 g of surfactant (KONION PE-88 Korea Polyol Co., Ltd.) and 9 g of catalyst (manufactured by Niax A-1 UCC) Slowly add the mixture to the first reaction vessel over 25-40 minutes using a dropping funnel so that the temperature of the reactor does not exceed 60 ° C. Pre-polymer was prepared by stirring for 1-2 hours while maintaining the temperature of 50-60 ℃ to complete the reaction and cooled.

The prepolymer prepared in the above method is coated on the glass fiber knitted fabric sheet by a known method, and then cut into a suitable size to fill a sealed packaging paper sealed with nitrogen to seal the packaging to prepare a casting sheet.

Example 2

Ceramic powders having an average particle diameter of less than 1 micrometer with a far-infrared function in place of the dyes or pigments of Example 1 (oxides, nitrides, sulfides, carbonides, borides or oxides of metals such as silicon, aluminum, titanium, zirconium, magnesium, calcium, or iron) Or a mixture of these; or a porous inorganic particle such as zirconia) is coated on a surface of a glass fiber filament melt-spun and coated on a surface of a fiberized glass fiber filament, followed by focusing and drying to stretch the glass fiber. It is prepared by a known method to have a porosity and to obtain a glass fiber knitted fabric sheet.

The prepolymer synthesized in the same manner as in Example 1 is coated on the glass fiber knitted fabric sheet by a known method, and then cut into a suitable size to fill a sealed packaging paper sealed with nitrogen to seal the packaging to prepare a casting sheet. .

Example 3

The resin-based film-forming binder prepared by dispersing an organic bioactive material (such as chitosan salt) or an antimicrobial agent (manufactured by DOWSIL Dow Chemicals, etc.) instead of the dye or pigment of Example 1 was coated on the surface of the fiberized glass fiber filament by melt spinning The glass fiber knitted through the condensation and drying process is manufactured by a known method to have elasticity and versatility to obtain a glass fiber knitted fabric sheet.

The prepolymer synthesized in the same manner as in Example 1 is coated on the glass fiber knitted fabric sheet by a known method, and then cut into a suitable size to fill a sealed packaging paper sealed with nitrogen to seal the packaging to prepare a casting sheet.

Example 4

The glass fiber treated with a commercial starch-based binding agent was heat-treated at 380-450 ° C. for 72 hours to completely remove the binding agent, and then coated the resin film-forming binder prepared by the method of Example 1, 2, or 3 After drying to make a glass fiber having the same function to prepare a casting sheet in the same manner as in Example 1.

Claims (18)

Disperse dyes, pigments, ceramic powders with far-infrared radiation, organic bioactive materials and / or antimicrobial agents in resin-based film-forming binders used as a focusing agent in the manufacture of glass fibers, and then firmly adhere to the glass fiber filaments to form glass fiber continuous yarns. And manufacturing the knitted fabric sheet by weaving the glass fiber continuous yarns, and then coating the glass fiber knitted fabric sheet with a moisture curable prepolymer. The method of claim 1, wherein the dye is a phthalocyanine, dioxazine, diazo, anthraquinone, quinacridone, perylene, or isoindolinone-based dye. The method of claim 1, wherein the pigment is an inorganic pigment such as titanium dioxide, iron oxide, or carbon black, or an organic pigment made of various plastic particles exhibiting color. The method of claim 3, wherein the average particle diameter of the pigment is 0.1-15 micrometers. The method of claim 1, wherein the far-infrared radioactive ceramic powder is silicon, aluminum, titanium, zirconium, magnesium, calcium or iron oxides, nitrides, sulfides, carbohydrates, borides or mixtures thereof; Or a porous inorganic particle such as zirconia. The method of claim 1, wherein the average particle diameter of the far-infrared radioactive ceramic powder is 0,1-15 micrometers. The method of claim 1, wherein the organic bioactive material is chitosan. The method of claim 1, wherein the resin film-forming binder is epoxy resin, urea resin, polyurethane, polyacryl, polyester, ethylene-propylene copolymer, ethylene-vinylacetate copolymer or polyvinyl alcohol; A rubber, such as natural rubber and synthetic rubber. The method of claim 1 wherein the prepolymer has an isocyanate functional group. Dyestuffs, pigments, ceramic powders with far-infrared radiation, organic bioactive materials and / or antimicrobial agents are dispersed in a resin film-forming binder used as a focusing agent in the manufacture of glass fibers, and then firmly adhered to the glass fiber filaments to form a glass fiber continuous yarn. And weaving the glass fiber continuous yarns to produce a knitted fabric sheet, and then casting the water-curable prepolymer onto the glass fiber knitted fabric sheet. The casting sheet according to claim 10, wherein the dye is a phthalocyanine, dioxazine, diazo, anthraquinone, quinacridone, perylene, or isoindolinone-based dye. The casting sheet according to claim 10, wherein the pigment is an inorganic pigment such as titanium dioxide, iron oxide, or carbon black, or an organic pigment made of various plastic particles exhibiting color. The casting sheet according to claim 12, wherein the average particle diameter of the pigment is 0.1-15 micrometers. The method of claim 10, wherein the far-infrared radioactive cerium powder is silicon, aluminum, titanium, zirconium, magnesium, calcium, or iron oxides, nitrides, sulfides, carbohydrates, borides or mixtures thereof; Or a porous inorganic particle such as zirconia. 15. The casting sheet according to claim 14, wherein the average particle diameter of the ceramic powder with far infrared radiation is 0.1-15 micrometers. The casting sheet according to claim 10, wherein the organic bioactive material is chitoate. The method of claim 10, wherein the resin film-forming binder is epoxy resin, urea resin, polyurethane, polyacryl, polyester, ethylene-propylene copolymer, ethylene-vinylacetate copolymer or polyvinyl alcohol; A casting sheet characterized by being rubber such as natural rubber or synthetic rubber. The casting sheet of claim 10 wherein said prepolymer has an isocyanate functional group.