JPH0341116A - Polyurethane resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyurethane resin composition which can give an interlaminar adhesive strength when used for an orthopedical casting tape and is not sticky when it is moistened by mixing a urethane prepolymer with a catalyst, a stabilizer and an ester compound of polyethylene glycol. CONSTITUTION:This polyurethane resin composition comprises a urethane prepolymer comprising a polyol and a polyisocyanate, a catalyst, a stabilizer and an ester compound of polyethylene glycol. As the polyol, a polyester polyol comprising a low-molecular polyol/alkylene oxide adduct is desirable. As the polyisocyanate, 4,4'-diphenylmethane diisocyanate or a product obtained by partially modifying is particularly desirable. Examples of the catalyst include bis(N,N-dimethylaminoethyl) ether, and examples of the stabilizer include acid chlorides such as benzoyl chloride and sulfonic acids such as methanesulfonic acid.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the production of polyurethane resin & 1lrti products, more specifically to the production of orthopedic casting tapes for fixing and treating affected areas in the surgical and orthopedic fields. It relates to particularly suitable polyurethane resin compositions.

[Conventional technology]

As an alternative to a cast bandage, which is made by impregnating coarse gauze with plaster of paris, a casting tape made of polyurethane resin applied to a base cloth made of glass fiber or other material is wrapped around the affected area, and the polyurethane resin reacts with moisture and hardens. It is already known that hydraulic casting tape has various advantages over plaster of paris casts. The polyurethane resin used in this hydraulic casting tape is one containing dimorpholino diethyl ether as a catalyst in a polyurekne prebolimer made of aromatic polyisocyanate and polyol, which has a practically satisfactory curing time and storage stability. It is excellent in that it has a value that should be
Publication No. 51).

However, this polyurethane resin & IITfc product,
Until it hardens, the resin has extremely strong adhesiveness, so it sticks to the gloves the practitioner is wearing, making it extremely difficult to perform the procedure.As time passes, the resin begins to harden.
The drawback is that thorough casting and modeling are not possible.

In order to reduce the tackiness of this resin, and in particular to obtain a resin composition with almost no tackiness when wet, a lubricant is contained in the hydraulic resin, and the dynamic Fj friction coefficient of the surface of the casting tape is made smaller than 1.2. (Japanese Patent Application Laid-Open No. 62-87162). When this resin composition is used, the stickiness is almost eliminated, so the difficulty of winding due to the stickiness mentioned above is eliminated, but on the contrary, the stickiness Because of this, the adhesive strength between the layers is weak and peeling occurs easily, and because it is extremely slippery, there are problems in that practitioners often slip their hands and remove the casting tape, and it is difficult to apply appropriate tension to the tape.

[Problem to be solved by the invention]

In view of the above-mentioned problems with conventional resins and acids, the object of the present invention is to provide a material that does not have tackiness when wet, has appropriate interlayer adhesion strength for orthopedic casting tape, and is easy to use during treatment. The object is to obtain a poly-urethane resin m-acid that does not slip on the hands.

[Means to solve the problem]

In order to achieve the above object, the polyurethane resin composition of the present invention comprises a urethane prepolymer consisting of a polyol and a polyisocyanate, a catalyst, a stabilizer, and an ester compound of polyethylene glycol.

Common polyols can be used as the polyols used in the present invention. For example, alkylene oxides (ethylene oxide, propylene oxide, etc.), low molecular weight polyols (ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, triethanolamine, etc.) can be used. (pentaerythritol, sorbitol, etc.) and polyamines (ethylene diamine, diethylene triamine trilene diamine, etc.), polyether polyols, polycarboxylic acids (
Examples include polyester polyols produced by reacting (cuccinic acid, maleic acid, sebacic acid, adipic acid, fumaric acid, phthalic acid, dimer acid, etc.) with the above-mentioned low-molecular-weight polyols. These polyols can be used alone or in combination of two or more.

Among these, polyether polyols, which are alkylene oxide adducts of low-molecular-weight polyols, are preferred. Particularly preferred are polypropylene ether diols and triols, with an average molecular weight of 200 to 2000.
, preferably 400 to 1000.

As the polyisocyanate used in the present invention, ordinary polyisocyanates can be used. Among them, aromatic polyisocyanates are preferable, e.g. 2.4
-Toluene diisocyanate, 2.6-toluene diisocyanate, 4.4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDT), 2.4'-diphenylmethane diisocyanate, 2.2'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and these Examples include carbodiimide-modified polyisocyanates. These polyisocyanates can be used alone or in combination of two or more. Particularly preferred is MDI or a part of MDI modified with carbodiimide.

The ratio of polyol to polyisocyanate is usually 2 to 5 equivalents of polyisocyanate per 1 equivalent of polyol,
Preferably it is 2.5 to 4 equivalents.

Urethane prepolymer is made of polyol and polyisocyanate, usually at 30-120°C, preferably at 50-100°C.
It can be obtained by heating and stirring at C.

As the catalyst in the present invention, a catalyst having excellent storage stability is selected. (dimethylmorpholino)ethyl)ether, etc. These catalysts can be used alone or in a mixture of two or more.

The amount of catalyst used is usually 0.05 to IO parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer.
Parts by weight.

Examples of the stabilizer of the present invention include acid chlorides such as benzoyl chloride, and sulfonic acids such as methanesulfonic acid. These stabilizers can be used alone or in a mixture of two or more.

The amount of the stabilizer used varies depending on the type of stabilizer and the type of catalyst, but is usually 1 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the catalyst.

The polyethylene glycol (hereinafter abbreviated as PEG) ester compound of the present invention has a molecular weight of 1000 to 50000.
PEG (7) A fatty acid ester compound having 10 to 3 carbon atoms, which may be a monoester compound or a diester compound, but a diester compound is particularly preferred.The ester compound is a compound formed by combining PEG and a fatty acid having 10 to 30 carbon atoms in the presence of an acid catalyst. Obtained by heating and esterification.

PEG is 1 part ethylene oxide in ethylene glycol.
It is obtained by addition at 90-200°C.

Examples of fatty acids having 10 to 30 carbon layers include saturated fatty acids (octyl acid, stearic acid, etc.) and unsaturated fatty acids (oleic acid, linoleic acid, etc.). These fatty acids can be used alone or in a mixture of two or more.

The amount of the PEG ester compound used is usually 2 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the urethane prepolymer.

In the present invention, antifoaming agents, antioxidants, colorants (pigments,
collection) may also be used.

The polyurethane tree Il1 composition of the present invention may be prepared by adding a catalyst, a stabilizer, a PEG ester compound, an antifoaming agent, and an antioxidant to the urethane prepolymer, or by adding a catalyst, a stabilizer, and a stabilizer to the urethane prepolymer in advance. A PEG ester compound, an antifoaming agent, and an antioxidant may be added.

The polyurethane resin of the present invention may be applied to the base fabric of the orthopedic casting tape by any conventionally known method, for example, by using a roll.

[Effect]

The polyurethane resin of the present invention is used as an orthopedic casting tape by impregnating it into a base fabric. By soaking it in water, the viscous urethane prepolymer reacts with water to become a polymer, which increases rigidity. It becomes a resin with a high hardness and hardens together with the base fabric between the layers of the wound tape, creating a fixing force for the affected area.

The catalyst has the function of adjusting the rate at which the urethane prepolymer reacts with water; the urethane prepolymer does not harden during the time it takes to wind the tape onto the affected area and remains flexible; The time from the start of the reaction to curing is adjusted so that it quickly hardens to a strength that allows it to be fixed.

The stabilizer has the function of suppressing self-hardening of the urethane prepolymer. Urethane prepolymers have the property of self-reacting and curing when affected by moisture other than water, oxygen, etc., so this self-curing reaction can be suppressed using a stabilizer.
To improve the storage stability of the tape from the time it is manufactured to the time it is used in hospitals.

The PEG ester compound reduces the tackiness of the urethane prepolymer. The urethane prepolymer is hydrophobic and tends to stick to the gloves worn by practitioners when working with orthopedic casting tapes.The ester compound of PEG is hydrophilic and activates especially when it comes in contact with water, causing it to become slimy. , the stickiness of rubber gloves and polyethylene gloves is reduced, and operability is improved. On the other hand, the ester compound of PEG is highly compatible with the urethane prepolymer, and when the base fabric is immersed in water, the water that adheres to the surface of the ester compound of PEG is consumed by the reaction of the urethane prepolymer, and when the water content decreases, the PEG The hydrophilic activity of the ester compound is reduced, the glabella adhesive strength of the cured orthopedic casting tape is not affected, and sufficient interlayer adhesive strength is obtained.

〔Example〕

The present invention will be explained below with reference to Examples.

Viscosity 25゜ooo from polyisocyanate and polyol
Prepare cps urethane prepolymer, add 2.6g of Irganox 1010 (Ciba Geigy) as an antioxidant, 49g of NrAX A-1 (manufactured by UCC) as a catalyst, 44g of benzoyl chloride as a stabilizer to 2472g of this urethane prepolymer. .9g was blended to prepare a base polyurethane & Il kaimono. PEG4000 distearate was added to this base polyurethane composition in the following amount to prepare four examples and two comparative examples, and another comparative example not containing PEG4000 distearate was prepared.

Example 1 50g 2% W/W Example 2
75g 3%W/W Example 3 100g
4%W/W Example 4 200g 8%W/
W Comparative Example 1 25g 1% W/W Comparative Example 2
300g 12% W/W Comparative Example 3 0g Each of the above-mentioned polyurethane resins & Illuminants was mixed in a nitrogen gas atmosphere with a density of 14 vertical lines/r n ch % 15 horizontal lines/
An orthopedic bandage was prepared by impregnating a 1-inch vertical tape made of glass fiber with a basis weight of 310 g/m' with a resin coating amount of 210 g/m' and winding it into a roll.The prepared bandage In order to evaluate the physical properties (ease of winding and strength between layers), the friction strength and peel strength were measured using the following methods.

(1) Spread out a bandage with a friction strength of 20°C on a horizontal table, fix both ends, and immediately spray 20°C water on top of it.
A sled weighing 450 g with two stainless steel rods with a diameter of 0 m and 6.3 m in diameter as legs was placed on it, and 20 seconds after the water spray, it was pulled horizontally at a speed of 250 m/win using a tensile tester to determine the initial stress. The stress change of the difference between the stress and the initial stress at the time when the sled moved 100 steps was measured.

The frictional strength measured here represents the force required to unwind the roll during the bandage winding operation and the adhesion to the glove.

(2) Cut two pieces of bandage adjusted to a peel strength of 20°C to a size of 1100mm wide and 200cm long, overlap them, spray with 20°C water, leave 50cm of overlap, and cut one end. After separating into a T shape and applying a load of 1150g for 15 minutes, 20
After 24 hours at °C, test at 200 m/sin using a tensile tester.
The peel strength was determined.

The peel strength measured here represents the adhesive force between the wound layers when the bandage is wound.

(3) Operability When handling a rolled bandage soaked in water with gloved hands, the friction strength mentioned above is one evaluation measure, but in actual use there are subtle differences. This is affected by various factors, so try wrapping the bandage around your hand while wearing gloves (latex, polyethylene, vinyl acetate, etc.) and make sure that the gloves, bandage, and bandage layers are not too sticky or too slippery. First, a sensory test was conducted to determine whether it was easy to roll with a moderate amount of friction. If it is extremely good, it is ◎, and if it is very good, it is 0. Those that were not very good were rated Δ, and those that were poor were rated ×.

The above measurement results are shown on the skin surface.

As can be seen from the table, Comparative Example 1, in which the content of the PEG ester compound was as low as 1% W/W relative to the urethane prepolymer, had good peel strength, i.e., glabellar adhesion, but had poor adhesive strength with gloves. The adhesiveness between the bandage and the layers of the bandage was still strong, and the overall evaluation was poor.

In addition, in Comparative Example 2, in which the content of the PEG ester compound was as high as 12% W/W relative to the urethane prepolymer, the adhesion between the glove and bandage and the bandage layers was considerably reduced, and on the contrary, it became slightly slippery. The peel strength also decreased and the interlayer adhesion strength became low, resulting in an overall evaluation that was not very good, meaning that there were practical problems. Comparative Example 3, which does not contain any ester compound of PEG, has no problem with interlayer adhesion, but has a large adhesive strength, has a big problem with operability, and has a poor overall evaluation.

On the other hand, Examples 1 to 4 containing an appropriate amount of PEG ester compound had good operability and interlayer adhesion, and the overall evaluation was very good or very good.

〔Effect of the invention〕

According to the present invention, by blending a polyethylene glycol ester compound into an orthopedic casting tape that uses a hydraulic resin, it is possible to significantly reduce the adhesion of the resin to the gloves worn by the practitioner, and furthermore, the adhesiveness of the resin to the gloves worn by the practitioner is significantly reduced. When untying the bandage and wrapping it around the affected area, it does not require much force to unravel; it can be rolled up by rolling it around the affected area, and even after being rolled up, it is easy to make small adjustments, and it can be accurately modeled into the desired shape. Furthermore, the interlayer adhesion after curing can be maintained at a sufficient value as before, and by using the polyurethane resin composition of the present invention, it has excellent both operability and fixability. An orthopedic fixation bandage can be obtained.

hand Continued Neho Positive book (spontaneous) 1989 August 29th ], Displaying N items Tokuwarahira 1-176735 2゜ name of invention Polyurethane resin composition person who makes corrections (1 other person) teenager Reason Man Hanging 1 5゜ Date of amendment order none 6. Number of inventions increased by amendment none 7. Subject of correction Column for detailed description of the invention in books M. & III The description is amended as follows.

(1) On page 4, line 8, "-Luamine Pentaerythritol J was corrected to "-Luamine, Pentaerythritol 1.

(2) On page 4, line 10, "Cylene triamine tolylene diamine 1" was corrected to "Cylene triamine, tolylene diamine."

(3) “Cuccinic acid” in line 12 of page 4 has been corrected to “succinic acid 1.”

(4) “TI is corrected to r7.” on page 5, line 10.

Claims (1)

[Claims] 1) A polyurethane resin composition comprising a urethane prepolymer consisting of a polyol and a polyisocyanate, a catalyst, a stabilizer, and an ester compound of polyethylene glycol.