JP2885916B2 - Surgical casting tape - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

(Industrial application field) The present invention relates to a surgical casting tape for fixing and treating an affected part. (Prior Art) Conventionally, polyurethane elastomers have been widely used as sealants, adhesives, primers, paints, waterproofing materials, flooring materials, and the like. Above all, one-component moisture-curable polyurethane resins do not need to be weighed and mixed before use compared to two-component polyurethane resins, and therefore have the characteristic that there is no unevenness in physical properties due to measurement errors or insufficient mixing. is there. (Problems to be Solved by the Invention) One-part moisture-curable polyurethane resin compositions usually require a long time for curing. Therefore, when it is desired to cure in a short time, an organometallic compound, an amine compound, or the like is used as a catalyst to accelerate the curing. However, they have the problem that the storage stability of the product is impaired instead of shortening the curing time. On the other hand, there is a surgical casting tape as one of uses of the moisture-curable polyurethane resin composition. This is a casting tape in which a polyurethane resin is applied to a base cloth made of glass fiber or other material is wrapped around the affected area, and the polyurethane resin is cured by reacting with moisture.
It has recently attracted attention as an alternative to it because it has various advantages over conventional cast plaster cast gauze impregnated with coarse gauze. The polyurethane resin composition used for the hydraulic casting tape needs to be cured in about 10 minutes, and long-term storage stability is required. On the other hand, a special catalyst (JP-A-58-146351, JP-A-62-172008, JP-A-62-103071) is added to a polyurethane prepolymer comprising an aromatic polyisocyanate and a polyol.
The above-mentioned compounds have practically satisfactory values in curing time and storage stability. However, in recent years, it has been required to further shorten the curing time in order to reduce the restraining time of the patient, and the amount of the catalyst used has been increased, and the storage stability tends to be shortened accordingly. In addition, since the casting tape is required to be colored, the variety of products is increased, and the stock amount is increased. Therefore, a resin composition having more excellent storage stability is desired. Accordingly, an object of the present invention is to provide a surgical casting tape which is required to have the same properties as obtained from a one-pack moisture-curable polyurethane resin composition having excellent storage stability and short curing time. (Means for Solving the Problems) The present inventors have made intensive studies in order to achieve the above-mentioned problems, and as a result, have reached the present invention. That is, the surgical casting tape according to the present invention is a moisture-curable polyurethane resin composition containing an isocyanate group-terminated urethane prepolymer composed of a polyol and a polyisocyanate, a catalyst and a stabilizer as essential components, and at least one of the polyol components. It is obtained from a moisture-curable polyurethane resin composition containing 1% by weight of bisphenol-based diol in an amount of 2 to 3 moles by mole of ethylene oxide or 2 to 30 moles by mole of propylene oxide. Things. Hereinafter, details of the present invention will be described. The bisphenol-based diol used as a polyol component in the urethane resin composition has been conventionally used as a modifier for improving adhesion and hardness in a two-pack type polyurethane resin. Examples of the application of bisphenol-based diols to one-part moisture-curable polyurethane resin compositions are described in JP-A-61-281176.
A mixture of a hydroxyl group-containing liquid diene polymer and a polyol compound containing a bisphenol diol, an adhesive for a resin comprising a polymer obtained by reacting an excess polyisocyanate compound and a free polyisocyanate compound is described. . This publication also states that dibutyltin laurate, primary tin octoate, polyethylenediamine and the like can be added as a curing accelerator, but it is well known that these deteriorate storage stability. The present inventors have used this bisphenol-based diol as an essential component of a polyol component. When a catalyst and a stabilizer are added to a urethane prepolymer composed of the bisphenol-based diol and a polyisocyanate, a one-part liquid having excellent storage stability is obtained. Finding that a moisture-curable polyurethane resin composition can be obtained,
The present invention has been reached. Examples of the bisphenol-based diol include ethylene oxide or propylene oxide adducts of polyhydric phenols such as bisphenol A, bisphenol F, bisphenol C, and bisphenol S;
These are used alone or in combination of two or more. Of these, bisphenol A adducts of ethylene oxide and / or propylene oxide are particularly preferred. The number of moles of these adducts is 2 to 3 moles in ethylene oxide, and 2 in propylene oxide.
~ 30 moles. Any of these ranges is not preferred because the storage stability of the polyurethane resin composition deteriorates outside these ranges. The ethylene oxide or propylene oxide adduct of the polyhydric phenol can be obtained by adding ethylene oxide or propylene oxide to the polyhydric phenol at 80 to 200 ° C. in the presence of a basic catalyst. As the polyol other than the bisphenol diol used in the present invention, conventionally known polyols can be used. For example, ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, triethanolamine, pentaerythritol, low molecular polyols such as sorbitol; ethylene oxide, alkylene oxides such as propylene oxide, water, the low molecular polyol and ethylene diamine , Diethylene triamine, polyether polyol having a structure added to polyamine such as tolylenediamine; succinic acid, maleic acid, sebacic acid, adipic acid,
Polyester polyols obtained by the reaction of dicarboxylic acids such as fumaric acid, phthalic acid and dimer acid with the above-mentioned low molecular polyols; polylactone polyols obtained by ring-opening polymerization of lactones such as γ-butyl lactone and ε-caprolactone; opening of tetrahydrofuran Polytetramethylene glycol by ring polymerization; castor oil or an alkylene oxide addition modified product thereof; butadiene, a polymer of a diene compound such as isoprene, and a polydiene polyol having a hydroxyl group at a terminal or a hydrogenated product thereof; These are used as one kind or a combination of two or more kinds. The amount of the bisphenol-based diol used is 1% by weight or more, preferably 2% by weight or more, and more preferably 3% by weight or more of the total polyol components. On the other hand, as the polyisocyanate used in the present invention, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane isocyanate, p-phenylene diisocyanate, Aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate and their carbodiimide-modified polyisocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate; 3-isocyanatomethyl-
3; 5,5-trimethylcyclohexyl isocyanate, 4,
Alicyclic polyisocyanates such as 4'-dicyclohexylmethane diisocyanate; arylaliphatic polyisocyanates such as xylylene diisocyanate; and carbodiimide-modified or isocyanurate-modified polyisocyanates. Used as a combination. The mixing ratio of the above-mentioned polyol and polyisocyanate to obtain a urethane prepolymer having an isocyanate group is usually 1.2 to 5 equivalents, preferably 1.5 to 3 weight, per equivalent of the polyol. In addition, this reaction is usually achieved by heating and stirring at 30 to 120 ° C, preferably 50 to 100 ° C. As the catalyst in the composition used in the present invention, those having excellent storage stability are selected and used. Among them, bis (N, N-dimethylaminoethyl) ether , Bis (4-morpholinoethyl) ether, bis-4- (2,6-dimethylmorpholino) ethylether and the like. This catalyst is also a catalyst typified by trismorpholinoethylamine or trisdimethylmorpholinoethylamine proposed by the present applicant (Japanese Patent Application No. 1-64581).
No.) can also be used. Each catalyst is used alone or in combination of two or more. In that case, use amount is urethane prepolymer 100
Usually 0.05 to 10 parts by weight, preferably 0.05 to 10 parts by weight
5 parts by weight. As the stabilizer used in the present invention, acid chlorides such as benzoyl chloride, sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, sulfuric acid, perchlorines,
Sulfamic acid, cyclohexylsulfamic acid and the like can be mentioned. These stabilizers are used alone or in combination of two or more. The amount of the stabilizer to be used varies depending on the type thereof, the type of the catalyst and the like, but is usually 0.5 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the catalyst. Further, the composition used in the present invention may include a defoaming agent, an antioxidant, an ultraviolet absorber, a coloring agent such as a pigment and a dye, a filler such as calcium carbonate, titanium dioxide, carbon black and clay, if necessary. May be used. In the preparation of this composition, the urethane prepolymer obtained from the polyol and the polyisocyanate,
Catalysts, stabilizers, and various additives may be added.Also, when the urethane prepolymer is produced, some or all of the catalyst, stabilizer, and various additives may be added in advance together with the polyol and the polyisocyanate. . The polyurethane resin composition containing the catalyst and various additives is filled and stored in a container capable of blocking moisture. If necessary, the container can be opened, filled, applied, coated, and cured by reacting with the moisture or moisture in the air in a usual manner. In addition, a composition suitable for obtaining a surgical casting tape is a polyether polyol having a structure in which an alkylene oxide is added to water, a low-molecular polyol and a polyamine as a polyol other than the above-mentioned bisphenol-based diol; Polyether polyols which are alkylene oxide adducts of low molecular weight polyols, such as polyester polyols by the above-mentioned reaction with low molecular weight polyols; polylactone polyols obtained by ring-opening polymerization of lactones, and polypropylene diols and triols Thus, those having an average molecular weight of 200 to 3,000, particularly 200 to 2,000 are suitable. As the polyisocyanate, an aromatic polyisocyanate, particularly 4,4'-diphenylmethane diisocyanate or a partially modified carbodiimide is preferable, and the use ratio of the polyol to 1 equivalent of the polyol is 2 to 5 equivalents of the polyisocyanate. And preferably 2,5 to 4 equivalents. Other conditions may be the same as those for other uses. The method of applying the polyurethane resin composition to the base fabric of the surgical casting tape may be a conventionally known method, and for example, can be applied by a roll. EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 to 5 (Production of Urethane Resin Composition) According to the formulations shown in Table 1 (the numerical values in the table indicate parts by weight)
After dissolving and mixing the following polypropylene diol, bisphenol-based diol and antioxidant, polyisocyanate was added and the mixture was stirred at 70 to 80 ° C for 3 hours. Further, a catalyst, a stabilizer, an auxiliary for a casting tape, a silicone-based antifoaming agent, and the like were added thereto, and the mixture was stirred at 50 to 60 ° C. for 2 hours to obtain a polyurethane resin composition. This composition was measured for viscosity, NCO content, and storage stability by the following methods. (Materials) ・ Polypropylene diol: Sannics PP 2000 (manufactured by Sanyo Chemical Industries, Ltd., trade name, average molecular weight 2,000) ...... Abbreviated as “PP 2000” in the table. Sannicks PP 950 (same as above, average molecular weight 950) ...... Abbreviated as "PP 950" in the table. Sannicks PP 700 (same as before, average molecular weight 700) …… In the table, abbreviated as “PP 700”. Sannicks PP 400 (same as above, average molecular weight 400) ...... Abbreviated as "PP 400" in the table. -Bisphenol-based diol: Newpol BP-23P (previously, 2.3 mol adduct of bisphenol A with propylene oxide, average molecular weight 360) ... Abbreviated as "BP-23P" in the table. Newpol BP-3P (same as above, 3-mol adduct of bisphenol A with propylene oxide, average molecular weight 400)… In the table, abbreviated as “BP-3P”. Newpole BP-600 (same as above, adduct of bisphenol A with 7 moles of propylene oxide, average molecular weight 600) ... Abbreviated as "BP-600" in the table. Newpole BPE-23NK (same as above, 2 mol of ethylene oxide adduct of bisphenol A, average molecular weight 320) ...... Abbreviated as "BPE-20NK" in the table. Newpol BPE-40 (previously, 4-mol adduct of bisphenol A with ethylene oxide, average molecular weight of 400) ... Abbreviated as "BPE-40" in the table. Newpole BPE-100 (same as above, adduct of bisphenol A with 10 mol of propylene oxide, average molecular weight 670) ... Abbreviated as "BPE-100" in the table. -Antioxidant: Irganox 1010 (trade name, manufactured by Ciba Geigy, trade name: Tetrakis- [methylene-3-

[3 ', 5'-di-tert-butyl-4'-hydroxyphenyl] propionate] methane) Polyisocyanate: Isonate 125M (manufactured by Mitsubishi Kasei Dow Co., trade name, 4,
4'-diphenylmethane diisocyanate) ... In the table, abbreviated as "MDI". -Catalyst: Bis-4- (2,6-dimethylmorpholino) ethyl ether (manufactured by San Apro Co., Ltd.): Abbreviated as "BDM" in the table. Tris [4- (2,6-dimethylmorpholino) ethyl] amine (manufactured by San Apro Co., Ltd.): Abbreviated as "TDM" in the table. -Stabilizer: methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.): Abbreviated as "MSA" in the table. -Auxiliary agent for casting tape: Distearate of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., average molecular weight: 4,000) ... Abbreviated as "EGS" in the table. (Test method) Viscosity: A sample temperature-controlled at 20 ° C. was measured at 12 rpm using a No. 4 rotor with a B-type viscometer. NCO content: The unreacted amine after the reaction with the amine solution was determined by back titration with a hydrochloric acid standard solution by a conventional method.・ Storage stability: 100ml of each polyurethane resin composition in nitrogen gas atmosphere
Approximately 50 ml of the sample was collected in a polybin, sealed, stored in a thermostat dryer at 130 ° C., and the time until the polyurethane resin composition lost its fluidity was measured. (Preparation of Surgical Casting Tape) Each of the obtained polyurethane resin compositions had a density of 14 pieces / inch, 15 pieces / inch in width and a basis weight of 31 in a nitrogen gas atmosphere.
Impregnated into a warp knit tape made of 0 g / m ² glass fiber so that the resin application amount is 210 g / m ² , wound up in a roll, put in an aluminum laminated polyethylene bag, sealed by heat sealing, and used for surgery I made a casting tape. This was immersed in water at 20 ° C. for 10 seconds, then lightly drained, wound around a cylinder, and measured for the time until rolling could not be performed, which was defined as “pot life”. The results are shown in Table 1. As shown in Table 1, in the resin composition according to the present invention, bis-4- (2,6-dimethylmorpholino) ethyl ether (BDM) was used as a catalyst (Examples 1 to 3).
The storage stability was 1.5 to 2 times that of the resin composition not using the bisphenol-based diol (Comparative Example 3).
In addition, it was found that in Examples 1 and 2, the storage stability was further improved and the pot life was short, and the restraint time of the patient could be shortened as compared with Example 3 in which the amount of the catalyst was small. In addition, the present applicant proposed a catalyst tris [4-
In the case of using (2,6-dimethylmorpholino) ethyl] amine (TDM) (Examples 4 and 5), the storage stability was inferior to the former, but the value after about 60 hours was still practical. And a resin composition using a bisphenol-based diol having 4 moles or more of ethylene oxide in substitution (Comparative Examples 1 and 2) and a resin composition not using a bisphenol-based diol (Comparative Example 4) in a range of 1.5 to 1.5. Double storage stability was obtained. On the other hand, the resin composition not using the stabilizer (Comparative Example 5) has extremely poor storage stability, indicating that the use of the stabilizer is essential. Examples 6 to 12 Polyurethane resin compositions were prepared according to the formulations shown in Table 2 (the numerical values in the tables indicate parts by weight) in the same manner as in the previous example, and the same measurements were performed. Similarly, a surgical tape was prepared and the pot life was measured. Further, as a measure of the degree of fixation and protection of the affected part after curing of the surgical casting tape, the cylinder compressive strength was measured by the following method, and these results are also shown in Table 2. Measurement of Cylinder Compressive Strength: Surgical casting tape was immersed in water at 20 ° C. for 10 seconds, lightly drained, and wound around a 60.5 mm diameter cylinder in three layers to cure. A sampling cylinder was obtained so as not to deform it. After further storing at 20 ° C for 24 hours,
Using a compression tester, the cylinder was compressed in the diameter direction of the cylinder at a cross head speed of 25 mm / min, and the stress at the time of deformation of 5 mm was measured to obtain “cylinder compression strength”. From Table 2, it was found that the resin composition containing the bisphenol-based diol had better storage stability than the resin compositions containing no bisphenol-based diol of Comparative Examples 3 and 4 (see Table 1). In each example, the cylinder compression strength was 9 kg or more, which was a satisfactory value. (Effect of the Invention) Since the surgical casting tape of the present invention cures in ten minutes or more, the patient can be quickly released and freely move. Further, the storage stability is superior to that of the prior art. Further, the amount of the catalyst can be increased for shortening the curing time, and the restraining time of the patient can be shortened and the burden can be reduced. Conventionally, storage stability was somewhat inferior, so that use was difficult. Bisdimethylaminoethyl ether can be used in combination, and as a result, the amount of special catalyst used can be reduced.

Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C08G 18/00-18/87 A61L 15/07-15/14 A61F 13/04 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A moisture-curable polyurethane resin composition comprising an isocyanate group-terminated urethane prepolymer comprising a polyol and a polyisocyanate, a catalyst and a stabilizer as essential components, wherein at least 1% by weight of the polyol component is ethylene. 2 to 2 moles of added oxide
3 moles or 2 to 2 moles of propylene oxide added
A surgical casting tape obtained from a moisture-curable polyurethane resin composition containing 30 mol of a bisphenol-based diol.