KR100428747B1 - Fast-setting polyurethane resin composition for casting tape - Google Patents

Abstract

The present invention relates to a fast curing polyurethane resin composition for casting tape, and more particularly, a polyol component as a polyol component by containing a certain amount of polyether glycol, polyester glycol and amino polyol in the entire polyurethane resin composition to form a fast curing polyurethane resin composition By manufacturing, it is not only excellent in lubricity, molding and strength, but also can reduce the phenomenon that the resin is localized when used in orthopedic casting tape, fast curing type polyurethane resin composition for casting tape convenient during the procedure It is about.

Description

Fast-setting polyurethane resin composition for casting tape

The present invention relates to a fast curing polyurethane resin composition for casting tape, and more particularly, a polyol component as a polyol component by containing a certain amount of polyether glycol, polyester glycol and amino polyol in the entire polyurethane resin composition to form a fast curing polyurethane resin composition By manufacturing, it is not only excellent in lubricity, molding and strength, but also can reduce the phenomenon that the resin is localized when used in orthopedic casting tape, fast curing type polyurethane resin composition for casting tape convenient during the procedure It is about.

Conventionally, gypsum bandages have been used as a method for fixing fractures, but the procedure is inconvenient and heavy, and the air permeability is poor and the comfort is poor and the X-ray permeability is poor. There was a problem that it was difficult to pinpoint the progress. Therefore, in recent years, in order to supplement the disadvantages of the gypsum bandage has been replaced by orthopedic splint prepared by coating a polyurethane resin on a flexible support such as glass fiber substrate.

U.S. Patent Nos. 3,241,501, 3,881,473, 4,667,611 and 4,774,937 refer to UV curable polyurethane resins. However, this UV curing method requires an ultraviolet lamp and has a disadvantage of long curing time, and thus does not have a great effect on commercialization.

In order to solve this problem, U.S. Patent Nos. 4,131,114, 4,502,479, 4,376,438, and 4,411,262 disclose a casting tape coated with a glass fiber substrate with a hydrocurable polyurethane resin. In addition, US Patent No. 4,433,680 discloses a catalyst that effectively acts on the curing reaction of the hydrocurable polyurethane resin.

In the known art, glass fiber knitted fabric is mainly used as the fibrous support used in the synthetic casting tape. Glass fiber knitted fabrics have excellent fracture and impact strengths compared to general gypsum bandages and are recognized as suitable materials for casting tape supports. However, the glass fiber knitted fabric has a low elongation of the fiber itself and thus lacks consistency with the fractured part of the body, as well as tearing of clothing and skin in this part after hardening due to loosening of the loop at the part cut after casting or during manufacture of the product. Has problems such as.

On the other hand, U.S. Patent No. 4,667,661 discloses the improvement of the lubricity by introducing polyethylene polyols or polysiloxanes having a plurality of hydrophilic groups in the water-curable polyurethane resin. there is a problem. In addition, US Pat. No. 4,655,208 discloses a method of improving the curing rate by introducing a hydrophilic polyol in a hydrocurable polyurethane resin, but the casting tape is not completely incinerated after use by using a glass fiber substrate, thereby preventing environmental pollution. When cut, glass fiber dust can penetrate the patient's skin and cause itching or acute dermal toxicity.

In addition, US Pat. No. 4,937,146 uses mineral oils and natural oils to improve adhesiveness and lubricity, but there is a problem in that the oil escapes from the substrate and deteriorates in appearance during long-term storage.

Korean Patent Application No. 95-34111 mentions a method for improving lubricity by adding dimethylolpropionic acid to a hydrocurable polyurethane resin, but it does not loosen well during the procedure due to localization of the coated resin during long-term storage. This casting tape has a problem of bringing color unevenness.

In order to solve the above problems, the present inventors prepare a fast curing type polyurethane resin composition for a casting tape by containing a predetermined amount of polyether glycol, polyester glycol and aminopolyol as a polyol component in the entire polyurethane resin composition. Was completed.

Therefore, the present invention is excellent in lubricity, molding and strength, as well as can reduce the localization of the resin due to the flow of resin during long-term storage and fast curing type polyurethane resin composition for casting tape that is cured quickly upon water penetration The purpose is to provide.

The present invention provides a polyurethane resin composition comprising a polyol component and an aromatic diisocyanate as a main component, wherein the polyol component includes 10 to 25% by weight of polyether glycol, 6 to 13% by weight of polyester glycol, and an amino polyol represented by the following Chemical Formula 1. It is characterized by the fast-curing polyurethane resin composition for casting tape containing 0.2 to 7 weight%.

In Chemical Formula 1; a + b represents the integer of 5-42.

Referring to the present invention in more detail as follows.

The present invention comprises a polyol glycol, polyester glycol and amino polyol as a polyol component in a predetermined amount of the entire polyurethane resin composition to prepare a fast curing polyurethane resin composition, excellent lubricity, molding and strength as well as orthopedic casting The present invention relates to a fast curing type polyurethane resin composition for a casting tape which can reduce the phenomenon in which the resin is localized when used in a tape and has a fast curing speed.

Generally, the fast-curing polyurethane resin composition has a polyol component and a diisocyanate as main components.

The present invention is the polyol component which is the biggest feature in the fast curing polyurethane resin composition containing 10 to 25% by weight of polyether glycol, 6 to 13% by weight of polyester glycol and 0.2 to 7% by weight of the amino polyol represented by the formula (1) It is desirable to. If the content of the polyether glycol is less than 10% by weight, there is a problem of poor storage stability, and if it exceeds 25% by weight, the viscosity is high and there is a problem in processing. In particular, the polyether glycol is preferably used by mixing a high molecular weight polypropylene triol having a weight average molecular weight of 2,000 to 3,000 and a low molecular weight polypropylene triol of 200 to 1,000 in a weight ratio of 1: 1 to 7: 1. Do. If the mixing ratio of the high molecular weight polypropylene triol and the low molecular weight polypropylene triol is out of the above range, there is a problem in that the compressive strength is weak.

In addition, if the content of the polyester glycol is less than 6% by weight, there is a problem in that the compressive strength is weak due to the lack of adhesion between the substrates, and when the content of the polyester glycol exceeds 13% by weight, the viscosity is high and the workability and storage stability are poor. In particular, it is preferable that the said polyester glycol goes into two or more hydroxyl groups in a molecule | numerator, and has a weight average molecular weight of 1,000-2,000. If the weight average molecular weight of the polyester glycol is less than 1,000, the viscosity is high, there is a problem in processing, if it exceeds 2,000 there is a problem that the compressive strength is lowered.

In addition, it is preferable to mix and use said polyether glycol and polyester glycol in the weight ratio of 1: 1-3: 1. If the mixing ratio of polyether glycol and polyester glycol is out of the above range, there is a problem that the storage stability is not good.

In addition, the present invention provides the hydrophobicity to the polyurethane resin by containing the amino polyol represented by the formula (1) as a polyol component to improve the penetration rate of water when the resin is in contact with water and induce rapid curing by acting as a catalyst itself Done. If the content of such amino polyol is less than 0.2% by weight, there is a problem in that fast curing cannot be induced, and if it exceeds 7% by weight, there is a problem of poor storage stability.

The polypropylene triol of high molecular weight (Mw 2,000 to 3,000) in the polyol component acts as a soft segment in the fast curing type polyurethane resin to impart elasticity to the resin, and has a low molecular weight (Mw 200 to 1,000). Polypropylenetriol improves the compressive strength by acting as a hard segment in the resin. In addition, polyester glycols act as soft segments in the resin, increasing adhesion between substrates. In addition, the amino polyol imparts hydrophilicity to the polyurethane resin, thereby inducing fast curing properties by improving the penetration rate of water when the resin contacts water and acting as a catalyst.

As described above, the present invention is used as a polyol component by mixing a specific range of polypropylene triol, polyester glycol and amino polyol in a specific ratio to improve the lubricity, molding and strength to the fast curing polyurethane resin as well as orthopedic When used in a casting tape for reducing the phenomenon that the resin is localized. In addition, when the fast curing polyurethane resin composition according to the present invention is used as an orthopedic casting tape to improve the penetration rate of water to induce fast curing properties.

And it is preferable to contain 50-65 weight% of diisocyanate compounds in all the resin compositions, and if the content is less than 50 weight%, it will become high viscosity, and if it exceeds 65 weight%, there exists a problem of becoming low viscosity. The diisocyanate compound is a polyurethane [Polyurethanes; Chemistry and Technology II, p453-607, p 609-659, Interscience Publishers] may be used any of the diisocyanate known. Especially, it is preferable to use liquid diphenylmethane diisocyanate (L-MDI), diphenylmethane diisocyanate (MDI), etc. preferably.

It is preferable to contain 0.5 to 3% by weight of the chain extender in the total resin composition, and if the content is less than 0.5% by weight, there is a problem of low compressive strength. have. Examples of the chain extender include 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, propylene glycol, ethylene glycol, and the like having two or more hydroxyl groups in a molecule. Reserol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbose, sorbitol, and the like may be used alone or in combination, preferably 1,3-butanediol, 1,4 Butanediol, ethylene glycol, glycerol or trimethylolpropane may be used. The chain extender improves compressive strength by acting as a hard segment in the resin.

In the present invention, it is preferable to contain 0.01 to 1% by weight in the total resin composition of a stabilizer that serves to prevent premature curing reaction of the fast curing polyurethane resin during storage of the casting tape, if the content is less than 0.01% by weight Stabilization effect of the resin cannot be obtained during storage, and when it exceeds 1% by weight, there is a problem of reducing the reactivity of the resin and water. As the stabilizer, benzoyl chloride and triethylphosphate or tributyl phosphate may be used. Preferably, triethylphospate or phosphoric acid based on phosphoric acid is used, rather than benzoyl chloride, which is highly toxic and odorous. It is preferable to use tributyl phosphate.

In the present invention, the fast curing catalyst which serves to promote the reaction between the polyurethane resin and water is preferably contained in the total resin composition of 0.7 to 2% by weight, if the content is less than 0.7% by weight, the curing time is slow, If it exceeds 2% by weight, there is a problem in the work hardening too fast, the long-term storage stability is bad. Examples of the fast curing catalyst include amine compounds such as triethylamine, dimethylethanolamine, tetramethyl-1,3-butanediamine, bis-2-dimethylaminoethyl ether and triethylenediamine, stenosoctoate and dibutyl tin di. Metal compounds such as laurate and dibutyl tin acetate, N-methyl morpholine, N-ethyl morpholine, dimoporn diethyl ether, dimoporn diethoxyethane, bis (2,6-dimethylmorpholino) ethyl ether, and mortar Morpholine compounds such as linoethyl- (2,6-dimethylmorpholinoethyl) ether and 1- (2-morpholinoethoxy) -2-2- (2,6-dimethylmorpholinoethoxy) ethane; It can be used, it is preferable to use dimorpholino diethyl ether (DMDEE).

The lubricant is preferably contained in the total resin composition of 2 to 15% by weight. If the content is less than 2% by weight, the lubricity is poor. If the content is more than 15% by weight, the lubricant is good. There is a problem in that the compressive strength is worsened by lowering the adhesion between the substrates. The lubricant may be a natural low-viscosity liquid low viscosity mineral oil (hydrogenated butylene ethylene stylene copolymer), hydrogenated ethylene propylene styrene styrene copolymer (hydrogenated ethylene propylene propylene) High viscosity mineral oil containing stylene copolymer) can be used. In addition, the lubricant is preferably used by mixing a low viscosity mineral oil having a viscosity of 100 to 200 cps and a high viscosity mineral oil having a viscosity of 18,000 to 22,000 cps at a weight ratio of 1: 9 to 9: 1 at 25 ° C. The present invention is used by mixing the low viscosity mineral oil and high viscosity mineral oil in the above range to impart lubricity in the resin to provide a convenient and soft feeling to the patient when applied to the casting tape to improve the physical fitness, the detachment of the resin from the substrate The phenomenon can be improved.

Since the resin composition which consists of said component has a viscosity of 40,000-60,000 cps / 30 degreeC, it has the favorable characteristic of resin flow.

On the other hand, the present invention includes an orthopedic casting tape molded by coating the fast curing type polyurethane resin composition according to the present invention containing the above-mentioned composition on a substrate in a conventional manner. At this time, the content of the fast-curing polyurethane resin composition to be applied to the substrate is preferably 35 to 60% by weight, more preferably 45 to 55% by weight based on the total casting tape. When the content of the fast-curing polyurethane resin composition is less than 35% by weight, the crushing strength is lowered after curing. When the content of the fast-curing polyurethane resin composition is less than 35% by weight, the resin is localized when stored due to the excessive amount of resin and bubbles are generated on the surface. Not desirable In addition, the substrate is environmentally friendly to use polyester having an elongation of 20 to 50%, and may be harmful to the human body.

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Preparation of Fast Curing Polyurethane Resin

Next to the composition as shown in Table 1 was prepared a fast curing type polyurethane resin composition in the following manner.

The isocyanate component was added while nitrogen was injected into the reactor, the reaction temperature was maintained at 55 to 60 ° C., and then the polyol component was added dropwise. The reaction was assumed to be complete when the NCO% reached 14%. After the reaction was completed, the temperature was lowered to room temperature, a stabilizer was added, followed by stirring for 30 minutes, and then a catalyst was added and the mixture was stirred for 10 minutes. Then, a lubricant was added to prepare a final fast curing type polyurethane resin.

Examples 4-6 and Comparative Examples 5-10. Casting Tape Preparation

A fastening type polyurethane resin composition prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was applied to a polyester substrate in an amount shown in Table 2 to prepare a casting tape. Casting tape was manufactured by coating a fast-curing polyurethane resin while not being subjected to excessive tension on the substrate using a one-roll coating device and then wrapped with aluminum wrapping paper.

As a comparative example, Scotch Cast Plus (US 3M, Comparative Example 9) and Shinto-Cast (Kirschner Medical, Comparative Example 10), which are conventional casting tapes, were used.

Test Example 1.

Physical properties of the casting tapes of Examples 4 to 6 and Comparative Examples 5 to 10 were measured by the following methods, and the results are shown in Table 2 above.

1. Measurement of elongation of substrate

The casting tape was opened, cut about 10 cm, and pulled with normal force to calculate the elongation of the substrate by the following equations (1) and (2).

Length elongation (%) = (length-initial length when extended) / initial length * 100

Width elongation (%) = (length-initial length when it increased) / initial length * 100

2. Measurement of resin flow

The casting tape was opened and weighed, placed in a dried glass jar and filled with dry nitrogen to seal it. The sealed glass bottle was placed in a drying oven at 70 ° C., and after 5 days, only the casting tape was taken out to measure the glass bottle weight, and the resin flowability was calculated by the following equation (3).

3. Compressive strength measurement

The casting tape was opened, immersed in water at room temperature for 5-10 seconds, squeezed 2-3 times to remove excess water, and then wound 6 times in a 5 cm diameter cylinder to form a cylinder. After 5 minutes, the cured casting tape was removed from the cylinder and stored for 24 hours in an atmosphere with a relative humidity of 55 ± 5%. Then, the compressive strength was measured by a tensile tester. At this time, the crosshead descending speed of the tensile tester was 5 cm / min, and the load value received when the casting tape was pressed 1 cm was calculated and the unit was kg / cm.

4. Resin solubility measurement

The casting tape was opened, immersed in water at 23 ° C., squeezed three times to remove excess water, dried in an oven at 80 ° C. for 4 hours, and then calculated by Equation 4 below.

5. Measurement of coating amount of resin

Open the casting tape, cut it into 10 cm lengths, put it in a PE bottle containing 500 ml of acetone, squeeze it 10 times, dissolve the polyurethane resin coated on the surface, and wash it again with acetone 4 to 5 times to dry the weight of the substrate. Was measured and calculated by the following equation.

6. Measurement of setting time

The casting tape was opened, immersed in water at room temperature for 5-10 seconds, squeezed 2-3 times to remove excess water, and then wound 6 times in a 5 cm diameter cylinder to form a cylinder. Within 2 minutes, the cured casting tape was removed from the cylinder and then pressed with a finger to measure the time it no longer enters.

As shown in Table 2, the casting tapes of Examples 4 to 6 according to the present invention exhibited strong strength by using polypropylene triol, polyester glycol and amino polyol in a specific ratio as a polyol component. It was confirmed that the flowability is less than 8% to improve the detachment phenomenon of the resin from the substrate, and the lubricity of the casting tape is imparted by appropriately mixing the low viscosity mineral oil and the high viscosity mineral oil as a lubricant. In addition, by using an amino polyol as a polyol component, hydrophilicity was imparted to the polyurethane resin composition to improve the penetration rate of water and promote the reaction with water, thereby confirming that the setting time was short.

However, Comparative Example 5, Comparative Example 6 and Comparative Example 7, which is a casting tape coated with a polyurethane resin when the polyol component is outside the scope of the present invention, have a problem of low compressive strength and slow setting time. The setting time is fast but there is a problem of low compressive strength. In addition, Comparative Examples 9 and 10, which are conventional casting tapes, were harmful to the human body due to the generation of glass fiber dust when cutting the glass fiber using the substrate, and the resin component was completely incinerated when incinerated, but the glass fiber substrate remained as a residue. Could.

Test Example 2.

The viscosity of the polyurethane resins prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was measured using a Brookfield RVT viscometer having a spindle # 4. The temperature was measured at 30 ℃, the viscosity of the resin contained in the container was sealed in a 30 ℃ oven and stored for 30 minutes in order to maintain a uniform temperature, the results were shown in Table 3 below.

As shown in Table 3, the polyurethane resins of Examples 1 to 3 according to the present invention has a viscosity of 40,000 to 60,000 cps, it can be confirmed that the flow of the resin does not flow down from the substrate, the scope of the present invention The comparative example deviated from the low viscosity was confirmed that there is a problem that the resin detached from the substrate.

As described above, the fast-curable polyurethane resin composition for casting tape according to the present invention is used as a polyol component by mixing polyether glycol, polyester glycol and amino polyol in a specific ratio in a certain ratio, the strength is strengthened, long-term It reduces the localization of resin due to resin flowability during storage, and improves the problems of lubricity and water pollution, as well as excellent molding property on curved areas and fast curing speed, making it useful for orthopedic casting tapes. Can be used.

Claims (5)

In the polyurethane resin composition mainly comprising a polyol component and an aromatic diisocyanate, 10 to 25% by weight of polyether glycol and 6 to 13% by weight of polyester glycol and 0.2 to 7 aminopolyol represented by the following general formula (1) as the polyol component: A fast-curing polyurethane resin composition for a casting tape, characterized in that the weight percent contained. Formula 1 In Chemical Formula 1; a + b represents the integer of 5-42. The method of claim 1, wherein the polyether glycol is used by mixing a weight average molecular weight of 2,000 to 3,000 and a polypropylene glycol of 200 to 1,000 in a weight ratio of 1: 1 to 7: 1, the polyester glycol is a weight average molecular weight The thing of 1,000-2,000 is used, The fastening type polyurethane resin composition for casting tapes characterized by the above-mentioned. The fastening type polyurethane resin composition for a casting tape according to claim 1 or 2, wherein the polyether glycol and the polyester glycol are mixed and used in a weight ratio of 1: 1 to 3: 1. Orthopedic casting tape, characterized in that formed by coating the fast curing polyurethane resin composition according to claim 1 on a substrate. The orthopedic casting tape according to claim 4, wherein the substrate is polyester having an elongation of 20 to 50%.