KR100249674B1 - A water-hardening polyureathane resin composition - Google Patents

Abstract

The present invention relates to a moisture-curable polyurethane-carrying composition, and more particularly, polypolymers containing polycaprolactone, polypropylene glycol, and polypropylene triol, and pre-polymerized aromatic isocyanates and lubricating oils to form a sufficient crosslinking defect. The present invention relates to a moisture-curable resin composition useful for orthopedic bandages by making it excellent in strength that conventional moisture-curable polyurethanes do not have, and supplementing the viscous portion of the resin so that the polyurethane resin does not flow well.

Description

Moisture Curable Polyurethane Resin Composition

The present invention relates to a moisture-curable polyurethane resin composition, and more particularly, polypolymers containing polycaprolactone, polypropylene glycol, and polypropylene triol, prepolymerized with aromatic isocyanates and lubricants to form a sufficient crosslink. The present invention relates to a moisture-curable resin composition useful for orthopedic bandages by making it excellent in strength that conventional moisture-curable polyurethanes do not have, and supplementing the viscous portion of the resin so that the polyurethane resin does not flow well.

Conventionally, orthopedic surgeons have used bandages using gypsum as casts for fracture patients, but in recent years, bandages using water-curable polyurethane synthetic resins have been used for various problems.

In order to be used as an orthopedic cast, the following physical properties are generally required, which must have storage stability for a period of more than one year until use, and have a good curing time and air permeability that can be hardened quickly after the procedure. It is easy to discharge sweat and X-ray permeability is good compared with general gypsum, and it is light and excellent in strength. It is easy to catch cold on the back and there should be no harm to human body.

Among the resins satisfying the above conditions, the polyvinylacetates are hardened at room temperature by controlling the glass transition temperature (Tg) higher than the normal temperature, and the polyvinylacetates are flexible at 70 to 80 ° C, which is higher than the normal temperature. Casting products using properties are commercially available. However, in order to use this resin, there is a problem that a processing equipment capable of raising steam or temperature is required separately.

As another example, a polyurethane having moisture curability is used, and has been widely used recently because of the following advantages.

First, immerse once in room temperature water with simple vinyl gloves, squeeze it and wrap it in the patient. After 3 to 5 minutes, it is first hardened, and after 20 minutes, it is completely hardened to serve as a casting material. Because it can be performed, it is very convenient to use, and secondly, when using the existing plaster bandages, a lot of joints and muscles can be applied by weight, so that the elderly have a lot of inconvenience due to the weight, but when using a polyurethane bandage, It is very light enough to solve the problem, so the patient's activity is very convenient. Third, it has a lot of pores, so it is easy to discharge the sweat and maintain a pleasant environment. In addition, the X-ray transmission is very easy and the color is diverse. It has the advantage of being able to.

An overview of water support materials and synthetic methods for producing such water-curable polyurethane resins is disclosed in US Pat. No. 3,919,713, but this is described as being used for adhesion of building materials. Did not improve.

U.S. Patent No. 4,376,438 discloses a general part of the moisture curable polyurethane raw material as a method of manufacturing a bandage material and a supporting bandage, but has not been subjected to a special treatment to enhance strength, and also U.S. Patent No. 4,433,680. In the present invention, the water curable polyurethane resin was cured using a dimorpholinoethylether (Dimorpholinoethylether: DMDEE) catalyst, but the strength was not good, and there was a problem of insufficient lubricity.

US Pat. No. 4,667,661 uses polyethylene polyols, polysiloxanes or hydrophilic surfactants having a plurality of hydrophilic groups in a moisture curable resin as a method for improving lubricity. However, the lubricating material has a problem that the resin is exposed to the water during processing to generate carbon dioxide gas to block the surface of the glass fiber used as the base material, thereby deteriorate the appearance, and may cause water pollution due to the property of dissolving in water. .

In addition, US Pat. No. 4,937,146 uses mineral oils and natural oils to improve adhesiveness and lubricity. However, when used excessively with respect to the resin component in these uses, the adhesive force may be reduced, and when used in a small amount, the lubricity may not be obtained. At the same time, if the viscosity of the resin component is not adjusted to an appropriate range, there is a problem in that the liquid escapes from the substrate during long-term storage and the appearance becomes bad after processing.

In Korean Patent Publication No. 97-21122 of the present applicant, a method for enhancing lubricity by simultaneously adding a storage stabilizer, benzoyl chloride and dimethylolpropionic acid, without adding a lubricant to a moisture-curable polyurethane resin or undergoing a separate lubrication process. Although it is disclosed, there is no phenomenon in which the strength is particularly increased.

When the finished product prepared by applying the above-mentioned moisture-curable polyurethane resin to a substrate such as glass fiber is used, the strength is lowered, and when the time hardens or the temperature rises in the summer, the glass fiber is knitted. The coated polyurethane resin flows well because of its good flowability. Therefore, the resin flowed down to one side is hardened well during the procedure, the color cast has a problem that the appearance of the appearance is unsatisfactory, resulting in color unevenness.

Accordingly, the present inventors have made a lot of efforts to solve the problem that in the production of water-curable polyurethane resin, the polyurethane resin is reduced or flowed down after processing, or the adhesion is poor for a good lubricity product, poly The present invention was completed by adding the propylene triol component within a certain content ratio range.

Accordingly, an object of the present invention is to provide a moisture-curable polyurethane resin composition which has excellent strength and improves the viscosity of the resin to have proper resin flowability.

The present invention provides a polyurethane resin composition comprising a polyol component containing polycaprolactone, polypropylene glycol, and polypropylene triol and an aromatic diisocyanate, wherein the polyol component is 10 to 30% by weight of polycaprolactone and polypropylene. Moisture curable poly which contains 5 to 45% by weight of glycol and 40 to 75% by weight of polypropylene triol, and contains 8 to 13 parts by weight of mineral oil as a lubricant based on 100 parts by weight of the main component consisting of the polyol and diisocyanate. It is characterized by the urethane resin composition.

The present invention will be described in more detail as follows.

In the orthopedic cast having the polyol component and the aromatic diisocyanate as a main component, the polypropylene triol component having a polyfunctional group is added to the polyol component at a predetermined content ratio to sufficiently crosslink. A moisture curable polyurethane resin composition having strength and at the same time maintaining an appropriate viscosity.

Basic raw materials for producing the water curable polyurethane resin include polyols and isocyanates.

As the type of polyol, one or two or more kinds selected from polyetherdiol, polyesterdiol, polycarbonate diol, and the like may be used, and there may be slight physical property changes depending on the type of polyol used, but the same may be used in either case. The effect can be obtained. In the present invention, it is preferable to use polyetherdiol among the polyol components, and polypropylene glycol is particularly preferably used among polyetherdiol, which has good viscosity and good adhesion due to low viscosity at room temperature. Because.

In addition, polycaprolactone having a molecular weight of 1,000 to 2,000 prepared by ring-opening polymerization of ε-caprolactone is used, particularly when polycaprolactone having a molecular weight of 1,250 is used. Polycaprolactone is a solid phase at room temperature and thus may be problematic in practical use, but this problem can be solved by adjusting other synthetic parameters such as the content of isocyanates and the synthetic chain extenders. In addition, when the synthetic parameters are given, not only the weather resistance and water resistance are excellent in terms of physical properties, but also the properties of reducing the adhesive properties.

An important feature of the present invention is that polypropylene triol having a multi-functional group is used together as a polyol component, which acts as a crosslinking agent to form a sufficient crosslinking, thereby enhancing strength and improving flowability during long-term storage while maintaining an appropriate viscosity. Plays an important role in

Therefore, the composition of the most preferred polyol component that can be used in the present invention is composed of 10 to 30% by weight of polycaprolactone, 5 to 45% by weight of polypropylene glycol and 40 to 75% by weight of polypropylenetriol. The content of the polypropylene triol in the total component ratio of the polyol greatly affects the strength and flowability of the product. If the content is less than 40% by weight, it cannot play a role of strengthening the strength, 75 Exceeding the weight percent, the overall strength is strengthened, but there is a problem in the processability due to too high viscosity and the substrate is not well loosened during the procedure in the hospital.

The above-mentioned polyol component is preferably contained 30 to 45% by weight based on the total polyurethane resin composition, if the amount of use is less than 30% by weight, the viscosity is low because the viscosity is not good, if the content exceeds 45% by weight As a result, there are many problems in processing.

As the aromatic isocyanate component, a general liquid-diphenylmethane diisocyanate (L-MDI) or diphenylmethane diisocyanate (MDI) shown in US Pat. No. 4,433,680 is used. When preparing the polyurethane moisture composition, it is preferable to use 50 to 70% by weight of the diisocyanate component. If the amount of the diisocyanate is less than 50% by weight, the viscosity is high, and if the amount exceeds 70% by weight, the viscosity is too low and the aromatic diisocyanate is used. There is also a problem with stability due to excess.

In addition, a small amount of benzoyl chloride, which is generally used, was used as a storage stabilizer. Particularly, the lubricant used as a characteristic of the present invention is 8 to 13 parts by weight of mineran oil based on 100 parts by weight of the main component of the polyol component and the diisocyanate. Use in combination. At this time, if the content is less than 8 parts by weight, the lubrication property is too low to be used, and when used in excess of 13 parts by weight, the lubricity is good, but oil is excessively drained out of the resin, and the adhesive strength is reduced by making the adhesive strength low. Worse

In addition, various types of polymers, including those known in the art, may be used as prepolymerization for preparing the polyurethane resin composition of the present invention, and particularly preferably dimorpholinoethyl ether (DMDEE) is used. The content of the resin is preferably 1.0 to 1.7 parts by weight based on the total resin components. If the amount of the catalyst is less than 1.0 parts by weight, the curing time is too slow. If the content is more than 1.7 parts by weight, the curing time is too fast. There is a problem of low storage stability.

All of the substances listed above have been used in that they are harmless to the human body and are unlikely to cause dermatitis on contact with the body.

The above components are prepolymerized by a conventional polymerization method to prepare a prepolymer, which is coated on a substrate, wherein the coating amount is 30 to 50% by weight based on the total amount of the substrate and the resin.

The substrate used in the present invention may be any one made of a synthetic fiber or a natural fiber knitted or woven tape or nonwoven fabric, but in particular, the polyurethane resin composition of the present invention has excellent properties to be applied to glass fibers. .

In addition, in the present invention, the isocyanate content measuring method (NCO%) was used in preparing the prepolymer, that is, the polyurethane resin composition.

Isocyanate content measurement method shows the result of completion of the reaction. If the content of NCO is more than 14%, the synthesis is not completed yet. If it is less than 13%, many side reactions occur, which adversely affects the overall physical properties. The lower the viscosity or the higher the viscosity, the less likely it is to adhere to the substrate surface during processing. The preferred isocyanate content is therefore 13-14%.

To explain the isocyanate content measurement method in more detail, first weigh 2 to 5 g of the prepolymer synthesized in the flask to four decimal places, accurately pour 10 ml of 2N-dibutylamine and dissolve completely, and then add isopropyl alcohol. Dilute. Bromophenol blue is added as an indicator and titrated with 0.5 N hydrochloric acid to find the end point at the point where it turns yellow, and the NCO% value is obtained by the following equation (1).

[Equation 1]

In the above Equation 1, "public test" refers to the amount when tested without using a sample, and "factor" refers to an error that may occur when preparing 0.5N hydrochloric acid.

If the viscosity of the moisture-curable polyurethane resin is less than 7,000 cps / 25 ° C., the flowability of the resin tends to flow down easily from the substrate. If the viscosity is 20,000 cps / 25 ° C. or higher, the flowability of the resin is good, There is a problem that is not solved well. In the present invention, by using the above-described triol component can be obtained a good product having a viscosity of less than 10% while having a viscosity of 10,000cps / 25 ℃ ~ 13,000cps / 25 ℃.

The cast according to the present invention was obtained in the form of a tape, which should be stored in an aluminum bag protected by air and moisture to maintain storage stability, taken out during use, immersed in water at room temperature for a while, and wound around fracture and muscle injury, and In order to maintain its shape, it is rubbed by hand to form a shape similar to the body part.

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

[Examples 1-10 and Comparative Examples 1-9: Polyurethane resin composition manufacture]

While injecting nitrogen into the 1L reactor, the aromatic diisocyanate component shown in the following Tables 1 and 2 was added, the reaction temperature was maintained at 55-60 ° C, and the polyol component was added dropwise, but the temperature did not exceed 75 ° C.

All synthesis was carried out with a NCO% of 14%, and was determined to be complete when measured within synthesis and within ± 0.5% of the specified percentage range. The reaction was lowered to room temperature while stirring, a small amount of benzoyl chloride was added at room temperature, and after stirring for 30 minutes, 1.4 parts by weight of dimorpholinoethyl ether (DMDEE) was added to the entire polyurethane resin as a catalyst and stirred for 10 minutes. Thereafter, 10 parts by weight of the mineral oil Drakeo17 (Pennzoil products company) as a lubricant was added to 100 parts by weight of the polyurethane resin.

The prepared polyurethane resin composition was made of glass fiber having a 4 inch width and pores of 204 to 210 mesh after 1 day of packaging, and the polyurethane resin composition prepared above was 45 Coated with% and then sealed in an aluminum bag.

Comparative Example 10

A moisture curable polyurethane resin was prepared by the method disclosed in Korean Patent Publication No. 97-21122, and 0.36% by weight of benzoyl chloride (BC: manufactured by Nippon Kayaku Chemical Co., Ltd.) and dimethylolpropionic acid (DMPA: 0.1 wt% of Nippon Kogyo Kogyo Kogyo Kogyo Co., Ltd. and 1.18 wt% of catalyst DMDEE were prepared by adding the composition ratios of Table 2 below.

Experimental Example 1 Measurement of Compressive Strength

The polyurethane casts of Examples 1 to 10 and Comparative Examples 1 to 12 were taken out of the bags, put in water at room temperature for 3 to 5 seconds, and squeezed 2-3 times.

The casting tape layer is unrolled and a six-layer (Layer) is applied to a 5 cm cylinder by applying a constant force to form a cylinder (cylinder). At this time, the casting tape should be completely wound in the cylinder within 30 seconds. After impregnating with water for 15-20 minutes, the cured casting tape layer was removed from the cylinder. After 24 hours of storage in the air with a relative humidity of 55 ± 5%, the compressive strength was tested in a tensile tester and the results are shown in Table 3 below. However, the speed of the tension meter was 5 cm / min, and the load value received when 1 cm was reduced was calculated, and the unit was kg / cm three times, and the average was calculated.

Experimental Example 2 Resin Flow Measurement

After washing and drying the round glass bottle to weigh the cast product prepared in Examples 1 to 10 and Comparative Examples 1 to 10 and weighed out from an aluminum bag, weighed, put in a dried glass bottle and dried Nitrogen filled. At this time, the operation is performed quickly and at 25 ° C. temperature of low humidity within 1% of relative humidity.

The glass bottle was sealed and placed in a drying oven set at 70 ° C., after 5 days, only the cast was taken out, the glass bottle was weighed, and the resin flowability (%) was measured by the following Equation 2.

[Equation 2]

Experimental Example 3: Viscosity Measurement

The resins prepared in Examples 1 to 10 and Comparative Examples 1 to 10 were measured for viscosity using a Brookfield RVT viscometer having a spindle # 4. The temperature was measured at 25 ° C., and the viscosity was measured after sealing in a 25 ° C. oven for 30 minutes so that the overall temperature of the liquid contained in the resin could be maintained uniformly.

In the results of Table 3, when the appropriate amount of triols of the present invention showed a strong strength, the viscosity is 10,000 ~ 13,000cps / 25 ℃ as the flow is less than 10% of the resin less detachment from the substrate It became a useful product.

When the content of the lubricant Drakeol 7 exceeds the range of the present invention (Comparative Example 5 and Comparative Example 6), many desorption phenomenon could be seen. In Comparative Examples 4, 5, 7, and 8, the strength was excellent and the resin flow did not appear on the substrate, but there was a problem in producing the product due to the high viscosity of about 20,000 cps / 25 ° C. .

In addition, the commercially available products had a lower compressive strength and poor resin flowability compared to the present invention. In addition, in the case of Comparative Example 10 (Korean Patent Publication No. 97-21122), it has an appropriate viscosity, but the content of polypropylene triol in the polyol component is too small to form sufficient crosslinking, so that the strength reinforcing effect is not obtained. It can be seen that the compressive strength is not good.

In the moisture-curable polyurethane resin composition coated on the porous knitted sheet according to the present invention, the polypropylene triol having a polyfunctional group is used as a crosslinking agent to strengthen the strength, and to control the viscosity of the resin by appropriately adjusting the polyol content. It is very suitable for orthopedic cast because the flowability is improved by preventing the polyurethane resin from flowing down well.

Claims (3)

In the polyurethane resin composition mainly comprising a polyol component containing polycaprolactone, polypropylene glycol and polypropylene triol and an aromatic diisocyanate, the polyol component is 10 to 30% by weight of polycaprolactone and 5 to 5 polypropylene glycol. 45% by weight and 40 to 75% by weight of polypropylene triol, and water curable, characterized in that the mineral oil is mixed with 8 to 13 parts by weight with respect to 100 parts by weight of the main component consisting of the polyol and diisocyanate Polyurethane resin composition. Orthopedic cast, characterized in that formed by coating the moisture-curable polyurethane resin composition of claim 1 on a substrate. 3. The orthopedic cast of claim 2, wherein the substrate is glass fiber.