JPH0817806B2 - Hydrosetting polyurethane resin composition for plaster bandage - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a water-curable polyurethane resin composition for casts used for fixation of an affected area such as at the time of fracture, and more particularly to casts such as glass fiber. In particular, the composition does not cause gelation during storage, and when used, when contacted with water, water quickly penetrates into the interior and cures in a suitable time as a Gibbs bandage, and cures. Later, it relates to a water-curable polyurethane resin composition for casts that exhibits high strength.

[Conventional technology]

A polyurethane resin prepolymer having a terminal isocyanate group consisting of 4,4-diphenylmethane diisocyanate and polypropylene polyol is known as a water-curable polyurethane resin composition for Gibbs bandages.

[Problems to be solved by the invention]

However, the above-mentioned known prepolymers are hydrophobic, and when they are cured by contacting with water when a Gibbs bandage is put on, it is difficult for water to permeate into the inside of the Gibbs bandage, which results in a long Gibbs fixing time, and When it comes into contact with water, it cures in a short time, and therefore, not only the workability is poor, but also the storage stability is poor, and further, the strength required as a cast after curing is not exhibited.

Therefore, the object of the present invention is to prevent gelation during storage,
Upon use, water penetrates quickly into the interior and hardens as a Gibbs bandage in a suitable time, and exhibits high strength after hardening, which is a water-curable cast for Gibbs bandage, which is an improvement over the above-mentioned drawbacks in the known art. It is to provide a polyurethane resin composition.

[Means for solving problems]

To achieve the above object, according to the present invention, water having a terminal isocyanate group obtained from a difunctional and / or trifunctional copolymer polyol obtained by copolymerizing one or more alkylene oxides. It is characterized by comprising a curable prepolymer, a fatty acid-modified aminocarboxylic acid alkali metal salt, and an isocyanate compound.

The above-mentioned copolymer polyols are obtained by copolymerizing difunctional and / or trifunctional polyols with alkylene oxides, especially ethylene oxide, or by weighting ethylene oxide with other alkylene oxides such as propylene oxide, butylene oxide or styrene oxide. 2-50: 98-50, preferably 5-50: 95-50 by ratio
Is a difunctional and / or trifunctional copolymer polyol having a molecular weight of 400 to 5000, preferably 700 to 1500, which is copolymerized in the ratio of

Examples of the above-mentioned bifunctional polyol include ethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polycaprolactone polyol, polyester polyol, and the like, and as the trifunctional polyol, glycerin, trimethylolpropane, or these. Glycerin, trifunctional polyols and the like having a terminal hydroxyl group obtained by adding a propylene oxide or lactone monomer or the like to a triol such as trimethylolpropane, therefore, specifically showing the above-mentioned copolymer polyol, For example, a molecular weight of about 10 having a terminal hydroxyl group obtained by adding ethylene oxide and propylene oxide to ethylene glycol in a weight ratio of 5:95.
00, a bifunctional polyol having an OH value of 112, a trifunctional compound having a terminal hydroxyl group of about 1000 and an OH value of 168, which is obtained by adding ethylene oxide and propylene oxide to trimethylolpropane at a weight ratio of 5:95. And a copolymer copolymer polyol.

By reacting the copolymer polyol thus obtained with an isocyanate compound, the aforementioned water-curable prepolymer having a terminal isocyanate group can be obtained. Specific examples of this isocyanate compound are as described below.

Specific examples of the fatty acid-modified aminocarboxylic acid alkali metal salt include p-amic acid, stearic acid, or oleic acid-modified monosodium or potassium L-glutamic acid.

Further, as the isocyanate compound used in the present invention, 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4-tolylene diisocyanate 2, 6
-Tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, P-
Examples thereof include phenylene diisocyanate and the like, or a triisocyanate adduct obtained by adding 3 mol of MDI to 1 mol of trimethylolpropane. These isocyanate compounds can also be used for the reaction with the above-mentioned copolymer polyol.

Since these isocyanate compounds are also provided for the reaction with the above-mentioned copolymer polyol, they are used in an excessive amount, specifically NCO / OH = 2.5 to 4.0, than the amount required for this reaction. .

[Action]

In the present invention having the above-mentioned constitution, as the water-curable prepolymer having a terminal isocyanate group, a difunctional and / or trifunctional copolymer polyol obtained by copolymerizing one kind or two or more kinds of alkylene osides is used as an isocyanate. By using the one obtained by reacting with the compound, the resulting composition exhibits hydrophilicity, and therefore the water impregnation rate becomes faster and the water penetrates uniformly into the composition, and the curing rate becomes faster. Adhesion is also good.

Furthermore, in the present invention, by using an isocyanate compound, this directly reacts with water to exhibit the required strength as a cast.

Further, in the present invention, the presence of the alkylene oxide or the fatty acid-modified aminocarboxylic acid alkali metal salt causes the above-mentioned isocyanate compound to be compatible with the above-mentioned prepolymer and to be homogeneously compatible in the composition to react with water. High strength is demonstrated.

〔Example〕

Example 1 Trifunctional polyol having terminal OH groups having a molecular weight of 1000, which is obtained by adding propylene oxide and ethylene oxide to trimethylolpropane in a weight ratio of 95: 5.
300 parts by weight, 490 parts by weight of a bifunctional polyol having a terminal OH group having a molecular weight of 700, which is obtained by adding propylene oxide and ethylene oxide to ethylene glycol in a weight ratio of 95: 5, and 885 parts by weight of pure MDI are added to a reaction vessel. And a reaction was carried out at a temperature of 70 to 80 ° C. for 4 hours to obtain a propolymer having an isocyanate of 11.9%. After cooling the temperature of the prepolymer to room temperature, 84 parts by weight of oleic acid-modified monopotassium L-glutamate was added, and further 10 parts by weight of N, N-dimethylaminoethanol as a curing catalyst and 5 parts by weight of silicone oil as a defoaming agent. The composition was added to obtain a homogeneous system, and a composition according to the present invention was obtained.

Example 2 Propylene oxide and ethylene oxide were added to glycerin in a weight ratio of 95: 5 to give a molecular weight of 1000.
300 g of a trifunctional polyol having terminal OH groups, tetramethylene glycol with propylene oxide and ethylene oxide at a weight ratio of 95: 5, and a bifunctional polyol having a molecular weight of 700 and having OH groups of 490 parts by weight. , And pure MDI 718 parts by weight are charged into a reaction kettle and the temperature is 70-80.
The reaction was carried out at 0 ° C for 4 hours to obtain a prepolymer containing 9.5% of isocyanate. After cooling the temperature of this prepolymer to room temperature, oleic acid-modified L-glutamate monopotassium 84
Add 10 parts by weight of N, N-dimethylaminoethanol as a curing catalyst and 5 parts by weight of silicone oil as a defoaming agent to make a homogeneous system, and further add 3 mol of MDI to 1 mol of trimethylolpropane to add triisocyanate. 340 parts by weight of the body compound was added to obtain a composition according to the present invention.

Comparative Example 1 Polypropylene glycol (PPG, M = 700, polyol having bifunctional terminal OH) 490 parts by weight PPG (M = 1000, polyol having trifunctional terminal OH)
...... 300 parts by weight Pure MDI ...... 885 parts by weight Under the same conditions as in Example 1, after preparing a prepolymer having a terminal isocyanate group, N, N- was used as a curing catalyst.
10 parts by weight of dimethylaminoethanol and 5 parts by weight of silicone oil as an antifoaming agent were added to obtain a prepolymer. The% thesisocyanate of this prepolymer was about 11%.

Comparative Example 2 PPG (M = 700, polyol having bifunctional terminal OH) ...
… 490 parts by weight PPG (M = 1000, polyol with trifunctional terminal OH)
...... 300 parts by weight Pure MDI ...... 590 parts by weight Zinc octylate (reaction catalyst) ・ ・ ・ 4 parts by weight Under the same conditions as in Example 1, after preparing a prepolymer having a terminal isocyanate group, N as a curing catalyst, N-
10 parts by weight of dimethylaminoethanol and 5 parts by weight of silicone oil as an antifoaming agent were added to obtain a prepolymer. The% thesisocyanate of this prepolymer was about 5.6%.

Performance Evaluation Test Each of the products obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was applied to a glass fiber bandage, and the diameter thereof was about
Wrap around a 10 cm polyethylene pipe 5 times and immediately heat
When immersed in water at 30 ° C., gelation started while penetrating to the inside after 30 seconds. Then take it out of the water,
The gelation time until the tack disappeared was measured by touching with a finger when left in the air at about 25 ° C., and the results are shown in Table 1. Further, after leaving it in the air for 60 minutes to sufficiently cure it, the polyethylene pipe was pulled out to obtain a test piece. The pressure load strength and strain (%) of this test piece were measured, and the results are shown in Table 1.

As is clear from Table-1, the product according to the present invention is superior to the comparative example in pressure resistance load and strain property, and further, the gelation time is 10 to 15 minutes, which is a time suitable as a cast for dressing. It was Although not shown in the above examples, the composition of the present invention did not cause gelation even after being stored for a long time.

〔The invention's effect〕

As described above, the present invention does not cause gelation during storage,
Upon contact with water at the time of use, water quickly penetrated into the interior and hardened in a suitable time (10 to 15 minutes) as a Gibbs dressing, and after hardening, exhibited sufficiently high strength as a Gibbs bandage.

Claims (4)

[Claims] 1. A water-curable prepolymer having a terminal isocyanate group, which is obtained from a difunctional and / or trifunctional copolymer polyol obtained by copolymerizing one or more alkylene oxides, and a fatty acid-modified amino. A water-curable polyurethane resin composition for Gibbs dressing, which comprises an alkali metal carboxylic acid salt and an isocyanate compound. 2. The composition according to claim 1, wherein the copolymer polyol is a copolymer of ethylene oxide. 3. The composition according to claim 1, wherein the copolymer polyol comprises ethylene oxide and another alkylene oxide in a weight ratio of 2 to 50:98.
A composition that is copolymerized at a ratio of -50. 4. The composition according to claim 3, wherein the other alkylene oxide is propylene oxide, butylene oxide or styrene oxide.