JPH06254146A - Hydraulic casting member - Google Patents

Abstract

PURPOSE:To obtain the hydraulic casting material which possesses the excellent conservation stability and the between-layer adhesiveness after hardening, and can suppress the tuck of a hardened resin according to the necessity in casting. CONSTITUTION:A hydraulic casting member consists of a hydraulic casting body which is formed by impregnating a fiber basic cloth having each opened mesh with a hydraulic resin composition containing the urethane prepolymer consisting of a polyol and the excessive polyisocyanate as main component and sealed into an airtight container and a tuck-free agent which suppresses the tuck of the hydraulic resin composition and is separated from the hydraulic casting body, and the tuck-free agent contains a surface active agent having a reacting group which reacts with the isocyanate group in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hydraulic cast material used for treating orthopedic diseases such as fractures, sprains, dislocations and deformations, and more specifically, an isocyanate functional resin which cures upon contact with water. The present invention relates to a cast material made of a base material that carries

[0002]

As a cast material used for the treatment of orthopedic diseases such as fractures, sprains, dislocations and deformations, it is lightweight, breathable, has good X-ray permeability, water resistance and durability. Ideal for high, non-bulky, isocyanate-functional resin that cures in contact with water is impregnated into a relatively open tape woven with glass fiber or polyester fiber, and the tape is wound into a roll. There is a method in which an item is hermetically sealed in a moisture-impermeable bag, the bag is opened at the time of use, the tape is dipped in water, and the tape is wrapped around the prepared affected area and cured.

Various cast materials of this kind have been proposed, and the second liquid component is made into the same liquid as the core portion of the fibrous porous tape impregnated with the first liquid component of the two-component curing agent. On the other hand, an orthopedic material inserted into a container which is impermeable and can be destroyed by pressure (Japanese Patent Laid-Open No. 58-17556).
No. 1), a cast material composed of a cloth impregnated with a compound having two or more hydroxyl groups or a polyvalent isocyanate compound, and a polyvalent isocyanate compound or a compound having two or more hydroxyl groups (JP-A-60-31760). Gazette), an orthopedic material comprising a fibrous base cloth having open eyes coated with a urethane prepolymer containing no component that accelerates curing, and a curing agent for the urethane prepolymer separated from the material (Saikai Sho 63 -130031), containing a water-soluble polyamine compound in which a water-curable resin containing a urethane prepolymer composed of a polyol and a polyisocyanate as a main component is applied to a fiber-forming material and sealed in a moisture-impermeable bag. A hydraulic cast using a curing agent for curing (Japanese Patent Application No. 3-45696) to accelerate curing to a fibrous base fabric having openings. To that coated with the urethane prepolymer water activity comprising the partial therewith hydraulic cast using a foam curing agent consisting mainly of separated water (JP-A-3
-202068).

The resin used for these hydraulic casts adheres to gloves made of polyethylene, polyvinyl chloride, vinyl acetate, rubber, etc., which are put on the skin or practitioner's hand at the time of use, and their tack is strong. When applied to the affected area, there are drawbacks such as accurate modeling, crimping and end treatment for increasing the interlayer strength, and expensive gloves must be disposable. In order to improve this point, a flexible sheet material coated with a curable resin containing a lubricant has been proposed (JP-A-62-87162). As the lubricant, a hydrophilic group covalently bonded to the curable resin, an additive that is non-reactive with the curable resin,
An additive that chemically bonds to the curable resin is used, and is added in an amount such that the coefficient of dynamic friction of the surface of the sheet material is less than about 1.2. However, among these lubricants, the first and third lubricants have high reactivity with the curable resin, so that the sheet material undergoes a self-curing reaction during storage and becomes unusable, and long-term storage is impossible. Since the second lubricant has poor compatibility with the curable resin and bleeds to the surface, the interlaminar adhesiveness when cast is weak and the strength of the obtained cured sheet becomes lower than a predetermined value. May cause interlayer separation during use. In addition, the sheet material containing any of the lubricants has a disadvantage that the unwound portion of the roll is unwound because the unwinding is too light during the casting operation, and the operation for modeling is impossible on the way. ing.

[0005]

The object of the present invention is to provide excellent hydraulic stability, high interlaminar adhesive strength obtained after curing, and hydraulic property capable of suppressing tack of a curable resin during casting as required. To get cast material.

[0006]

In order to achieve the above-mentioned object, in the present invention, a hydraulic fibrous base fabric having an open mesh is mainly composed of a urethane prepolymer consisting of a polyol and an excess of polyisocyanate. A hydraulic cast body impregnated with a resin composition enclosed in an airtight container, and a tack-free agent that is separated from the hydraulic cast body and suppresses tack of the hydraulic resin composition. In addition, it contains a surfactant having a reactive group that reacts with an isocyanate group.

As the fibrous base cloth with open eyes, materials such as glass fiber thread, polyester fiber thread and cotton thread are knitted,
A tape formed by weaving or non-woven fabric can be used, the thickness thereof is preferably 0.1 to 5 mm, and the basis weight is preferably about 50 to 500 g / m ² , and those having a visible opening are suitable. There is.

As the polyol which forms the urethane prepolymer which is the main component of the hydraulic composition, usual polyols can be used. For example, alkylene side (ethylene oxide, propylene side, etc.) is used as a low molecular weight polyol (ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, etc.)
And a polyether polyol having a structure added to polyamine (ethylenediamine, diethyltriamine, tolylenediamine, etc.), polycarboxylic acid (succinic acid, maleic acid, sebacic acid, adipic acid, fumaric acid, phthalic acid, etc.) and the above Examples thereof include polyester polyols obtained by reaction with low molecular weight polyols. These polyols may be used alone or in combination of two or more. Among them, preferred are polyether polyols which are alkylene oxide adducts of low molecular weight polyols, and particularly preferred are polypropylene ether diols and triols having an average molecular weight of 200 to 2
500, preferably 400 to 1000.

Ordinary polyisocyanates can be used as the polyisocyanate. Of these, aromatic polyisocyanates are preferred. For example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4'-diphenylmethane diisocyanate, 2,
Examples thereof include 2'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and carbodiimide-modified polyisocyanates thereof. These polyisocyanates can be used alone or in combination of two or more. Especially preferred is 4,
4'-diphenylmethane diisocyanate or 4,4 '
-A part of diphenylmethane diisocyanate is carbodiimide-modified.

The ratio of polyol to polyisocyanate is usually 1 equivalent of polyol to 2 parts of polyisocyanate.
~ 5 equivalents. The urethane prepolymer is a polyol and a polyisocyanate, and is usually 3 while flowing a nitrogen gas.
It is obtained by heating and stirring at 0 to 120 ° C.

The water-curable resin composition contains a catalyst, a stabilizer, a defoaming agent and the like in addition to the urethane prepolymer as a main component.

A catalyst for polyurethane can be used as the catalyst, but in order to improve the storage stability, for example, (N, N
-Dimethylaminoethyl) ether, bis (4-morpholinoethyl) ether, bis (4- (2,6- (dimethylmorpholino) ethyl) ether, etc. These catalysts may be used alone or in combination of two or more. May be.
The amount of the catalyst used is usually 0.05 to 10 parts by weight based on 100 parts by weight of the urethane prepolymer.

Examples of the stabilizer include sulfonic acids such as methanesulfonic acid and benzoyl chloride, and acid chlorides. These stabilizers can be used alone or in combination of two or more. The amount of the stabilizer added varies depending on the type of catalyst used, but is usually 1 to 30 parts by weight with respect to 100 parts by weight of the catalyst.

As the defoaming agent, a silicone type or nonionic type surfactant can be used, and the addition amount is 0.01 to 5 parts by weight based on 100 parts by weight of the urethane prepolymer.

The viscosity of the hydraulic resin composition is 150 at 20 ° C.
00-30000 cps, preferably 20000-25
000 cos. If the viscosity is lower than this value, it will flow easily when impregnated into the base cloth, and it will not be evenly distributed on the base cloth.
When cured, the interfacial adhesion and thickness of the base cloth are not uniform. Further, if the viscosity is higher than this value, it is difficult for the base cloth to flow backward when impregnated into the base cloth, and similarly, the base cloth is not uniformly distributed. When the viscosity in the above range is used, the hydraulic resin composition is uniformly impregnated into the base fabric, and when cured, the interlayer adhesive force and thickness of the base fabric become uniform. Does not give resistance when stroking the surface by hand.

The amount of the hydraulic resin composition impregnated into the base cloth varies depending on the type of the base cloth (material, weight per unit area, structure, etc.), but is generally in the range of 50 to 800 g / m ² , and the base cloth is generally wet with water. The amount obtained by immersing the resin in the hard resin composition, allowing the composition to sufficiently blend, then pulling it up and removing the excess composition with a pressure roll is preferable.

As an airtight container for the hydraulic cast body,
For example, a material formed using a moisture impermeable material having a multilayer structure such as polyethylene / aluminum / polypropylene can be used.

The tack-free agent used in the present invention contains a surfactant having a group which reacts with an NCO group in the urethane prepolymer molecule which is the main component of the hydraulic resin composition. As a group which reacts with an NCO group, a hydroxyl group (-OH), an imino group (= NH), an amino group (-NH)
₂ ), a carboxyl group (—COOH) and the like. As a surfactant having these groups in the molecule,
Examples include nonionic surfactants, silicon-based surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.

As the nonionic surfactant, polyethylene glycol type (higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct,
Fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, ethylene oxide adduct of oil and fat,
Polypropylene glycol ethylene oxide adduct, etc., polyhydric alcohol type (fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, fatty acid of alkanolamines Amide and the like). Examples of the silicon-based surfactant include polyether modified silicon, alcohol modified silicon, amine modified silicon, phenol modified silicon, and carboxy modified silicon. Examples of anionic surfactants include castor oil soap, funnel oil (low-sulfated castor oil), and the like. As the cationic surfactant, amine salt type (laurylaminopropionate, triethanolamine monostearate acetate, stearamidoethyldiethylamine acetate, 2-peptatecenylhydroxyethylimidazoline, etc.), quaternary ammonium salt type (Catanack S
N (manufactured by American Cyanamide) and the like).
Examples of the amphoteric surfactant include amino acid type (methyl lauryl aminopropionate hydrochloride, thorium lauryl amino propionate, etc.), betaine type (lauryl dihydroxyethyl betaine, etc.) and the like. These surfactants can be used alone or in combination of two or more. Among these surfactants, nonionic surfactants and silicon-based surfactants are particularly preferable. If the concentration of the tack-free agent is small, there is no tack-free effect, and if it is high, the tack-free agent is less likely to be uniform.
-20% is preferable.

An antifoaming agent can be added to the tack-free agent to improve operability. Examples of the antifoaming agent include lower alcohol antifoaming agents (methanol, ethanol, isopropanol, sec-butanol, n-butanol, etc.), organic polar compound antifoaming agents (amyl alcohol, diisobutylcarbinol, tributylphosphate,
Oleic acid, tall oil, metal soap, sorbitan lauric acid monoester, sorbitan oleic acid triester, polyethylene glycol fatty acid ester, pluronic nonionic surfactant, polypropylene glycol, polypropylene glycol derivative, etc.), mineral oil-based defoaming agent ( Mineral oil surfactant compound, mineral oil and fatty acid metal salt surfactant compound, etc., silicone resin defoamer (silicon resin, silicone resin surfactant compound, silicone resin inorganic powder compound) Etc.) and the like.
These tack-free agents can be used alone or in admixture of two or more.

The tack-free agent may be used in various forms. A liquid-type tack-free agent is filled in a pump-type container, a necessary amount is pumped up at the time of use, and the cast body is wound around a glove attached to a hand. How to extend to,
A method of impregnating a thin leaf material such as a tissue with a liquid tack-free agent and applying it to the surface of the glove worn on the hand or the rolled cast body, or filling the spray container with the tack-free agent and rolling it onto the glove surface or rolled up. There is a method in which it is blown into a foam on the cast body and is used by extending it.

[0022]

In the present invention, the hydraulic cast body obtained by impregnating the fibrous base fabric with the hydraulic resin composition and the tack-free agent are separated from each other, and the reaction between the hydraulic resin composition and the tack-free agent during storage. , The water-soluble cast body is allowed to contain water for the first time to promote the reaction of the hydraulic resin composition when used, and a tack-free agent is applied to the surface of the cast body rolled up when the adhesion and curing between layers have progressed to some extent. By applying, it becomes possible to smoothly model without being hindered by the tackiness of the resin composition, the tack-free agent remaining on the surface reacts with the hydraulic resin composition on the surface and disappears,
It does not penetrate into the interior and cause delamination.

[0023]

EXAMPLES Next, examples and comparative examples of the present invention will be described.

To obtain the hydraulic resin composition used in the present invention, polypropylene ether diol and 4,4'-
Diphenylmethane diisocyanate was mixed in an equivalent ratio of 1: 2.5, and heated and stirred at 80 ° C. while flowing nitrogen gas to prepare a polyurethane prepolymer, on which bis (morpholinoethyl) ether was used as a catalyst, and methanesulfone was used as a stabilizer. A silicon type was added as an acid and an antifoaming agent. By changing the average molecular weight of the polypropylene ether diol, the viscosity has an intermediate value of 17,000 cps, 2
4300cps, a relatively low value of 12500cps
And 4 types with a relatively high value of 35000 cps were created.

[0025] Next, glass fiber (ECG-75 _^1/0 1.0
Z) yarn using warp 13.5 / inch, weft 14.0 /
Raschel knitted base fabric with an inch density (320 g /
m ² ), respectively, were impregnated and coated with the hydraulic resin compositions having the above-mentioned four types of viscosities to prepare four types of hydraulic cast bodies (Examples I to IV). Viscosity 17,000 cps,
In the hydraulic cast bodies of Examples I and II using the 24300 cps composition, the coating amount of the hydraulic resin composition was 210 g / m ² and 200 g / m ² . Even when this hydraulic cast body was left in a constant temperature heater at 60 ° C. for 2 days, the hydraulic resin composition was kept uniformly impregnated. Example I with a composition having a viscosity of 12,500 cps
The hydraulic cast body of II is made up of 180 hydraulic resin composition.
Although the coating amount of g / m ² was sufficient for the entire impregnation, when left in a constant temperature heater at 60 ° C. for 2 days, the hydraulic resin composition was scarcely present on the upper part of the base fabric and migrated to the lower part. However, it is not preferable as a hydraulic cast body. Further, the hydraulic cast body of Example IV using the composition having a viscosity of 35,000 cps was not well compatible with the base fabric of the resin composition, and the impregnation time had to be lengthened in order to apply it evenly. There was a problem.

As the tack-free agent, a nonionic surfactant, Pluronic nonionic surfactant (ethylene oxide content 80%) (manufactured by Asahi Denka Co., Ltd.) nonylphenol ethylene oxide adduct, anionic surfactant laurin Acid diethanolamide, cationic surfactant lauryl trimethyl ammonium chloride, amphoteric surfactant lauryl aminopropyl dimethyl betaine, silicone surfactant SH3771 (having a silicone glycol copolymer structure manufactured by Toray Dow Corning Silicone Co., Ltd. The following tack-free examples A to E were prepared using nonionic surfactants). These tack-free agents were used by being filled in a pressure resistant container and ejected in the form of foam.

Example A (nonionic surfactant formulation) Pluronic nonionic surfactant 25 parts (ethylene oxide content 80%) nonylphenol ethylene oxide 10 parts water 65 parts Example B (anionic surfactant formulation) laurin Acid diethanolamide 3 parts Roth oil 10 parts Ethanol 10 parts Water 77 parts Example C (cationic surfactant formulation) Lauryl trimethyl ammonium chloride 10 parts Lauric acid diethanolamide 5 parts Propylene glycol 5 parts Ethanol 10 parts Water 70 parts Example D (amphoteric surfactant formulation) Uralylaminopropyl dimethyl betaine 10 parts Polyethylene glycol (molecular weight 1000) 5 parts Ethanol 10 parts Water 75 parts Example E (silicone surfactant formulation) SH3771 (Toray Dow Corni) Grayed manufactured Silicone Co., Ltd.) 5 parts Ethanol 10 parts Water 85 parts

Next, the above-mentioned Example I was used as a representative example of the hydraulic cast body of the present invention, and casts were actually prepared using the tack-free agents Examples A to E, and various items were evaluated. It was Also, for comparison with the conventional one,
As Comparative Example 1, a cast was prepared using only the above-mentioned Example I and no tack-free agent, and as a Comparative Example 2 was contained in the hydraulic resin composition used in the above-mentioned Example I- Casting was performed using a hydraulic cast body in which 5% of a silicone-based surfactant (Silicone oil SH-3746 manufactured by Toray Dow Chemical Co., Ltd.) was added as a tack-free agent that is non-reactive with the NCO group and the base cloth was impregnated. It was created and the same evaluation was performed. As the evaluation items, operability, interlayer adhesion strength, compressive deformation strength and extraction test were used.

As for operability, the hydraulic cast body was taken out of the airtight container, soaked in tap water, sufficiently contacted with water, then pulled up and wound up on a 75 mmφ pipe, and a sticky feeling, a slippery feeling, a bonding state between layers, Also, the finished state at the end of winding was evaluated by feeling. The operation was carried out by putting a glove on the hand, and in the examples of the present invention, the tack-free agent was evenly spread over the glove and used from the beginning of winding.

To evaluate the interlaminar adhesive strength, the hydraulic cast body was taken out of the airtight container, and the width was 75 mm and the length was 100 m.
The two sheets cut into m were soaked in tap water, sufficiently contacted with water, and then pulled up, except for Comparative Examples 1 and 2, a tack-free agent was applied to the surface of this sheet, and the two sheets were bonded together. Was peeled off and opened to 180 ° for curing, left standing in a dryer at 20 ° C for a whole day and night, and then measured by a tensile tester.

The compression deformation strength was evaluated by taking out a 75 mm wide hydraulic cast body from an airtight container, immersing it in tap water, bringing it into sufficient contact with water, and then pulling it up, the same as that used in the operability evaluation test on a 60 mmφ pipe. It was wound by the method described above, removed from the pipe after curing, further left in a dryer at 20 ° C. for a whole day and night, and the strength at 5 mm compression was measured by a tensile tester.

In the extraction test, the sample used for the evaluation of the interlayer adhesion strength was used, and this was extracted with a large amount of ethanol to measure the presence or absence of a solute.

The evaluation results are shown in the following table.

[Table 1]

As can be seen from the table, in terms of operability, all of the present invention had an appropriate sticky feeling and could be operated satisfactorily, but Comparative Example 1 had a large stickiness and was extremely difficult to operate. On the contrary, No. 2 had a small stickiness and had a problem in operation. Regarding the interlaminar adhesive strength and the compressive deformation strength, the one according to the present invention has only a strength decrease of about 4% and has no practical problem at all, whereas in Comparative Example 2, the interlaminar adhesive strength is 45% and the compressive deformation strength. The decrease in the adhesive strength to 89%, and particularly the significant decrease in the interlayer adhesive force, leads to deterioration of the cast over time, loosening of the bond between the layers, and loss of strength. Also, in the present invention, there was no extraction at all, whereas in Comparative Example 2, there was extraction, which increased slippage when wet with water, and there was a risk of slipping when cast was applied to the foot. .

In addition to the above, in order to evaluate the storage stability which is an important condition of the hydraulic cast material, the tack-free agent and the pluronic nonionic surfactant (ethylene oxide content 80%) used in Example A were used. A 2: 1 mixture of nonylphenol ethylene oxide was added to the hydraulic resin composition used in Example I of the hydraulic cast body to prepare a hydraulic cast composition for comparison using the hydraulic resin composition of 8%. As a result of evaluation by a heating acceleration test, the storage stability of Example I was 50% or more higher than that of this comparative example.

[0036]

EFFECTS OF THE INVENTION According to the present invention, when the hydraulic cast body is immersed in water and applied to the affected area, the hydraulic cast body does not contain any tack-free agent, and thus it is rolled and layered. The resulting hydraulic cast body is kept in a rolled state due to the adhesiveness between the resin compositions and does not unravel or fall due to the weight of the hydraulic cast body.
Both hands wearing gloves with a tack-free agent can be used for a sufficient modeling operation, in which a small amount of tack-free agent adheres to the surface of the hydraulic cast body, which reacts with the resin composition on the surface. It disappears and then penetrates into the interior to cause a decrease in cast strength and a decrease in interlayer adhesive strength. Further, the tack-free agent does not elute and the skin does not irritate even after bathing after hardening of the hydraulic cast body, and the hydraulic cast body can be stably maintained for a long period of time even during the storage period.

Claims (2)

[Claims] 1. A hydraulic cast main body in which a fibrous base cloth with open eyes is impregnated with a hydraulic resin composition containing a urethane prepolymer composed of a polyol and an excess of polyisocyanate as a main component is enclosed in an airtight container. And a tack-free agent that is separated from the hydraulic cast body to suppress tack of the hydraulic resin composition, and the tack-free agent contains a surfactant having a reactive group that reacts with an isocyanate group in the molecule. A hydraulic cast material characterized by being. 2. A hydraulic resin composition is a composition obtained from a polyol and an excess of polyisocyanate, and having a urethane prepolymer having two or more isocyanate groups at its end as a main component and having a viscosity of 20 ° C. 15000cps ~
The hydraulic cast material according to claim 1, which has a viscosity of 30,000 cps.