• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a process for producing a supporting bandage for surgical or veterinary surgical use comprising covering the part of the body which is required to be supported with an air-permeable dressing and then applying a self-hardening bandage over this dressing, characterized in that the self-hardening bandage comprise strips of air-permeable, flexible fabric coated and/or impregnated with about 50 to 300% by weight, based on the uncoated fabric, of an isocyanate prepolymer which contains free isocyanate groups and is based on aromatic polyisocyanates and polyols containing tertiary amino nitrogen atoms, the prepolymer having an isocyanate content of about 5 to 30% by weight and a tertiary amino nitrogen content of about 0.05 to 2.5% by weight, the coated fabric being soaked with water immediately before it is applied. The present invention also relates to lengths of bandaging material which comprise pieces of flexible, air-permeable fabric coated with about 50 to 300% by weight, based on the uncoated fabric, of an isocyanate prepolymer based on aromatic polyisocyanates and polyols containing tertiary amino nitrogen atoms, the isocyanate prepolymer having an isocyanate group content of about 5 to 30% by weight and a tertiary amino nitrogen content of about 0.05 to 2.5% by weight.
    公开号:SU741779A3
    申请号:SU782650049
    申请日:1978-08-21
    公开日:1980-06-15
    发明作者:Альфред Штраубе Франц；Ленерт Гюнтер
    申请人:Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of medicine, immobilization transfer material. A dressing material for immobilization is known, consisting of two breathable textile fabrics impregnated with water-curable prepolymer 1. However, the known dressing material takes a long time to cure. The aim of the invention is to accelerate the curing of the material. This goal is achieved by the fact that, as a prepolymer, it contains 5-300 wt.% Of the polyisocyanate-based N-CO prepolymer and polyols, the isocyanate groups in it being 5-30 wt.% And the tertiary nitrogen groups 0.05- 2.50 wt.%. To obtain a dressing material for immobilization, a part of the body is initially cooled with an air-permeable, non-impregnated lining. Suitable materials for such a lining are, for example, porous paper, nonwovens or textile binder materials. It is preferable to use as a base material materials with limited hydrophilicity, for example, materials based on polyester or polypropylene webs. The part of the body covered with such a lining is then wrapped with material, soaked in “1 pre-water. The material is impregnated with water immediately before use. The fabric is an air-permeable textile fabric impregnated with isocyanate prepolymers. Textile fabric should have a weight per unit surface of 20-100, preferably 30-500 g / m. Such suitable textile fabrics are fabrics, knit or crocheted fabrics with a surface weight of 20-200, preferably 40-100 g / m, in which there are 2-20 threads per centimeter of fabric in the length and width directions. A textile fabric or fabric can be made from any natural or synthetic yarns, but fabrics or knitwear made from mixed yarn obtained from hydrophobic yarns, respectively, fibers with a large modulus of elasticity, such as polyester fiber and hydrophilic natural or synthetic fibers, can be used. yarns such as wool and polyamide.
    The fabric, knit or crocheted fiberglass cloth should be one unit in weight, the surface should be 60-500, preferably 100-400 g / m, preferably 2-20 threads should be used for every centimeter of fabric in the length and width directions, preferably fabrics from glass fibers with hydrophilic dressing, loose or bonded or needle-punched on the basis of inorganic and preferably organic fibers weighing 30-400, preferably 50-200 g / m, per surface, also suitable for weights up to 1000 g / m.
    N-CO-polymers suitable for impregnating flat textiles are prepolymers containing 5-30, preferably 10-25 wt.%, Of isocyanate groups included in aromatic cycles, and 0.05-2.5, before: respectfully 0.1-1.5 wt.%, Nitrogen tertiary yominogroup.
    In addition, the use of e11 1e N-CO-form polymers should have a viscosity of between 5000 and 50,000, preferably between 10,000 and 30,000 cP, for which it is necessary to select the appropriate starting materials.
    N-CO-Poropolymers are prepared in a known manner, by reacting an excess of aromatic polyisocyanates with polyols containing nitrogen atoms of the tertiary amino groups. .
    Suitable aromatic polyisocyanates are any aromatic polyisocyanates, preferred are toluene-2,4-diisocyanate, 2, b-diisocyanatotoluene, mixtures of their isomers, 4,4-diisocyanatodiphenylmethane, 2,4-diisocyanatodipiphenylmethane, mixtures of isomers, which may be used as mixes , 2-diisocyanato, diphenylmethane, or any mixtures of the mentioned polyisocyanates, which are obtained by phosgenating the condensation product of aniline and formaldehyde and which, along with 2,2-, 2,4-, and 4,4-di-zociaAtodiphenylmethane, contain a lot of polymeric zotsianaty diphenylmethane series. Mixtures of diphenylmethane polyisocyanates are most preferred.
    Suitable polyols containing nitrogen atoms of the tertiary amino groups are underneath the molecular molecule polyol alcohols with free ether groups containing the nitrogen atoms of the tertiary ailyl groups, mol%. weighing 105-300, such as N-methyldithanololamine ,. N-ethydiethanolamine, N-methyldipropanolamine, triethanolamine or tripropanolgmine, polyesters of polyspires containing tertiary amino nitrogen atoms. irpynn with mol. weighing 300-2000, preferably 800-1500, which can be obtained by the interaction of polyosulfuric acids with amino alcohols of the type mentioned. Nitrogen-containing polyhydric alcohols can be used. Suitable polyacid acids are adipic, phthalic or hexahydrophthalic acids. Suitable polyhydric alcohols that do not contain nitrogen atoms are ethylene glycol, tetramethylene glycol, hexamethylene glycol or trimethylol propane, as well as polyether polyethers containing nitrogen atoms of tertiary amino groups with mol. weighing 3002,000, preferably 800-1500, which can be obtained by alkoxylation of the starting nitrogen-containing compounds. Suitable starting nitrogen compounds include the amino amino alcohols or amines having at least 2Y-H bonds, such as ethylenediamine, aniline, or He KC methyl e and Nn.
    Alkene oxides suitable for the preparation of polyethers are ethylene oxide or propylene oxide. It is most preferable to use products obtained by reacting propylene oxide with nitrogen-containing starting compounds.
    The impregnation of the material is carried out in any way. The process of impregnating the material or applying a layer of prepolymer on it is carried out in conventional apparatuses, for example by soaking with a doctor blade and subsequent squeezing on rollers or in a centrifuge or by spraying. The L-CO-Prepolymer is used in the form of a solution, with highly volatile solvents, for example, methylene chloride.
    At the same time, selecting the appropriate weight per unit surface, cell size and amount of applied N-CO prepolymer ensure that only the fiber itself is coated with prepolymer, and the cells remain free to allow air to breathe in the skin.
    When using solvents, the impregnated material is discharged from them by vacuum treatment. After impregnation, the material is stored in sealed devices in the absence of moisture, if necessary, they are removed and impregnated with water. In order to increase the stiffness of the dressing, it is possible to introduce chemically inert or water-hardening inorganic additives, such as chalk, glass fiber or gypsum, into N-CO prepolymers used for impregnation.
    Example 1 .. A bandage made of bleached cotton gauze with a width of .12 cm, a length of 4 m, a weight, per unit surface area, equal to 31 number of threads in the direction of the length of 11 threads / cm, in the direction of the width of 8 threads / cm, impregnated on rolling - impregnating machine with the lowest possible moisture content of 24 g of N-CO-prepolymer. The prepolymer was obtained from a substance formed during the phosgenation of the condensation product of aniline and formaldehyde, containing 30% by weight of N – CO groups and having a viscosity of 200 cP at 25 ° C, and a trihydroxypolyether with a carboxyl number of 146 and a viscosity of 1200 cP at 25 ° C obtained by the interaction of propylene oxide with triethanolamine, with a weight ratio of 3: 1 (mpeTi-N 0.3 wt.%, free N — CO-groups 18.7 wt.%, viscosity 21,300 cP at 25 ° C). Wrap the bandage on the polyethylene core, placed in a three-layer bag of polyester, aluminum and polyethylene and sealed bag with welding.
    After storage for 1 week at about 25 ° C, the impregnated bandage is removed from the package, immersed. For 3-5 seconds in water having a temperature of 25 ° C, and kneaded slightly. Then a tubular body about 12 cm long and with an inner diameter of 42 mm is wrapped with a bandage for about 3 minutes.
    Over the next 5 minutes, the support bandage hardens with: a small heat release (maximum surface temperature, turning into a stable body of a certain shape, capable of withstanding a load. At the same time, excellent adhesion is observed between the layers of the sheath.
    Example 2. As in Example 1, 30 impregnated bandages were obtained, their use was tested after storage for 3.6 and
    9 months at a temperature of about 25C. The maximum deformation of the specimens obtained as in Example 1 for bending tests (the distance from the support to the point of application of a load of 40 mm, the maximum bending load of 50 kpond), depending on the load, is + 10% and is within acceptable limits during manufacture. in such a manual way of samples. Even up to the maximum loads, the destruction of the described samples did not occur.
    Example 3. The process for obtaining bandages is the same as in Example 1, but instead of gauze bandages with a length of 4 m, bandages are used with a length of 2 m and a width
    10 cm of fabric obtained in a rashelmachine of mixed yarn consisting of 65% polyester fiber and 35% cotton yarn. The weight, the arrival rate per unit of surface, is 97 g / m, the number of threads in the direction of length 4 threads / cm, in the direction of width 10 threads / cm. The weight ratio between the L-ZO-prepolymer described in the example and the weight of the fabric is. 1.4: 1. Obtained in accordance with example 1, the sample is hardened for 6-7 minutes The stiffness determined during the mechanical tests is the same as that of the sample obtained in Example 1 using a bandage twice as long.
    Example 4. A 12 cm wide gauze bandage made from mixed yarn consisting of 40% cotton and 60% viscose, with a weight per unit /. the surface is 30 g / m, with the number of threads at the base of 12 threads / cm, and in the weft in the threads / cm, impregnated
    5 in the absence of moisture 25 g of the N-CO prepolymer described in Example 1, used as a solution in methylene chloride (the weight ratio of prepolymer and solvent is 1: 1). Removed
    0 solvent in a vacuum created by an oil pump. The resin-impregnated bandage is packaged as in Example 1 and stored for about 1 month at a temperature of about. After this, the packing is opened and a sample is made from the bandage as described in Example 1. The hardening time and strength are the same as in the case of the sample from Example 1.
    0
    Example 5 In accordance with example 4, 45 bandages were made and packaged. For 3 months, bandages were used in clinical trials to obtain hardened dressings on the painful fractures of the large tubular bones of the upper and lower extremities. As the material of the lining used polyester webs or cotton wool ne cotton thickness of about 0.4 SE4. The packs hardened to a maximum after 10 minutes and after 1 h) “they had to carry the load.
    Shedding bandages could be used without harming the clinic premises. Do they allow precisely to divide the shape of the {ligation They are not. You need to take a bapo to take a X-ray control of the fracture site, since there were no obscurations on the X-rays.
    0
    The same tools were used to remove the supporting straps as the n {Zhrabote with plaster straps (plaster shears, vibrating
    5 saws). The amount of dust generated in all cases was extremely small compared to gypsum masons. The very low weight of supportive dressings and good skin breathing conditions are beneficial for all patients.
    In all cases, the condition of the covered skin areas was quite satisfactory. Allergic reactions were absent.
    five
     Example b. Glass fiber cloth bandages with a length of 1 m and a width of about 10 cm with a weight per unit surface area of 285 g / m, with a number of threads at the base of 20 threads / cm, and in the weft 6 threads / cm, impregnated with the process described in example 1 The N-CO prepolymer according to the method of Example 4. The amount of prepolymer applied is 150 g / m. Analogously to example 1, samples of a tubular shape of the specified dimensions are made by hand and tested in a bend. At a load of 50 kpd, the samples did not break. The maximum deflection under the test conditions of Example 2 was 4 mm.
    Example 7. According to the method in accordance with Example 4, binTg made of glass silk cloth, 2.3 m long, 10 cm wide, with a number of threads at the base of 30 threads / cm, there are 6 threads / cm, and with a weight the arrival of Ecims per surface unit, with a uniform 290 g / m, is impregnated with 69 g of the prepolymer described in example 1. After impregnation, the bandage is placed in a book, the length of which is about 8 cm, and sealed in a plastic box. At this, measures are taken to prevent moisture from entering the box. After storage for several months, the bandage is removed from the package (no changes were observed), immersed for 2 minutes in water at a temperature and decomposition: put a plastic film in 6 layers one above the other layers of equal length. After about 3 times, the viscosity of the applied polyurethane resin rises dramatically (with a slight increase in temperature). In this state, the stop screws are formed in the foretitle in such a way that the result is a fozha support, open at the top, for the beam and the forearm and forearm. After another 2 minutes, the curing reaction basically ended. For final hardening, preserving their own grinding, I will stir into a round tough knife.
    Example 8. According to the method of impregnation in the solution described in example 4, “stitched polyester fiber webs with a height of about 4 mm with a BeccH 1 and a stroke per unit surface equal to 820 g / m in the form of stripes sized 10 X 25 C.M. impregnated is described 1m in example 1 polyurethane form | polymer (the amount of prepolymer was 240 wt.% Based on the weight of textiles). The impregnated batting is immersed for about 1 minute in warm water heated to about 40 ° C and then immediately simulated over the usual underlay on the forearm of a person into a form open from above. Cure is almost complete in about 5 minutes.
    In the form obtained, a hole is made mechanically for air passage and is then used as an outer splint for a forearm.
    Example 9. According to the method of impregnation in solution described in example 4, the bandages are impregnated in accordance with Example 3 with a prepolymer containing groups obtained by reacting the substance formed during the phosgenation of the condensation product of aniline and formaldehyde with a viscosity of 100 cP at 25 ° C and containing approximately 30% by weight of N-CO-groups, and a pro-stable polyester formed by the interaction of propylene oxide and ethylene diamine, mol. weighing 1140 and carboxyl number 196; at a weight ratio of 4: 1 (the viscosity of the prepolymer is 15,400 cP at 25 ° C / the amount of free N-CO-1 group is 20.4% by weight, the amount of nitrogen of the tertiary amino groups is 0.24% by weight
    The solidification time of the samples obtained in accordance with Example 1 is approximately 8 minutes. The samples obtained have a particularly high impact strength.
    Example 10. In the method according to Example 4, several hardening bandages are obtained, and test samples are then made from Kotoxix. Each of the 4 samples (bandage length 4 m, width 10 cm) was kept in 1 liter of double distilled water first for 4 hours at, then for 2 hours at 50 ° C, after which the aqueous extracts were filtered and determined carbon content. The carbon content found ranges from 0.002 to 0.007% by weight. This indicates that when wetted, the hardened bandages are practically free of organic matter.
    Example 11. According to the method in accordance with Example 1, several bandages are obtained, from which samples are then made for testing. After 24 hours, some samples are tested for flexural strength and fracture resistance. Another part of the samples is placed in water for about 2 hours at a temperature of about and after drying for comparison with the first batch of samples that are tested under loads up to a maximum of 50 kpd. In the I limits of statistical errors, the decrease in strength after exposure of the samples to water was not detected. This means that bathing and soul dressing with solid dressing is permissible.
    Example 12. In analogy with the method according to example 1, cotton gauze bandage, 12 cm wide, with the same impregnation parameters, according to the method according to example 4, is an N-CO prepolymer which is a mixture of 4/4 diphenylmethane diisocyanate and 2,4-diphenylmethane isocyanate (weight ratio 1: 1.5) with the product of the interaction of propylene oxide with triethanolamine with mol. weighing about 1200 and carboxyl number 146 with a weight ratio of 1.25: 1. The content of free N-CO groups in the preplicator is about 12 wt.%, The viscosity of the prepolymer is 19,000 cP at 25 ° C. The test specimen manufactured as in Example 1 hardens already after 5 minutes, it is strong enough for use in medicine and has a very good permeability to air and moisture. Example 13. According to the method in accordance with example 4 a bandage 4 m long and 10 cm wide made of mixed yarn consisting of 65% polyester and 35% cotton yarn, with a weight per unit of 60 g / m, 12 yarns / cm b basis, respectively 8 double yarns / cm weft, impregnate the description {in example 12 with N-CO-prepalimero {the amount of prepolymer is 160% by weight based on the weight of textiles packaged in aluminum box covered with polyethylene. After storage for 9 months at an average temperature of 23 ° C, a sample was made from the bandage for testing in the same way as in measure 1. During processing and during mechanical tests, no differences were noted compared with the properties of freshly prepared bandages and samples. Example 14. According to the method in accordance with Example 4, a 50 cm wide round knit made from non-textured polyacrylonitrile yarn 10.5 cm wide, having a cell size of about 1 weight per unit surface of 238 g / m (doubled), is impregnated 12 g of the prepolymer described in example 1. Samples were then made from it for testing in accordance with Example 1, with the tricoteic being used as a two-layer bin: ta. The solidification time is approximately 7 minutes. As a result, we obtain samples that provide good skin breathing conditions and have excellent adhesion, so that unwinding of the bandages is possible only if the structure of the tissue is destroyed. Example 15. According to the method in accordance with example 4, several 4 m bandages with the same parameters as in example 13 are impregnated with the new prepolymer described in example 1 polyurethane, the amount of the applied polymer is 104, 156 and 208 wt.% In the calculation on the weight of dry untreated bandages. A transparent tube 30 cm long and 0.9 cm in diameter was glued onto test specimens made in accordance with Example 1, after which the flow time of water through them with a column height of 10 cm was measured. For samples impregnated at 104 and 156 wt.% the time is about 3 seconds, and in the case of impregnated samples and 208% by weight, it increases to about 10 minutes. This experience indicates excellent skin breathing conditions using bandages impregnated with prepolymer, the optimal amount of which is 150-160%. With the use of bandages with minimal impregnation (104%), the specimen under flexural tests was destroyed even at a load of 35 kpd, while a specimen with a higher degree of impregnation remained celiac at a load of 50 kpd. Their deformation is only about 2 mm. Example 16 (comparative). According to the method in accordance with Example 4, several gauze bandages described in Example 4 are impregnated with 25 g (deposited) trimerohexamethylene diisocyanate. Impregnated bandages are kneaded for 10 seconds in water at 20 ° C and then test samples are made from them for testing a tubular shape with a length of about 12 cm and an inner diameter of 42 mm. At a temperature of about 23 ° C, the samples are hardened after about 48 hours. In another series of experiments, 0.3 wt.% Of nitrogen of the tertiary amino groups is added to the polyisocyanate in the form of the N, N-dimethylaniline as an activator. There was no noticeable reduction in the hardening time of the respective samples, however, they showed an unpleasant odor due to unbound amine. In the next series of experiments, K, K-dimethylaminoethane is used as an activator instead of H, M-dimethylaniline. Samples made from these bands also harden slightly faster than the starting material, and smell also appears. Example 17 (comparative). According to the method in accordance with Example 4, gauze bandages with the same parameters are impregnated with N – CO prepolymer obtained by the interaction of a substance formed during fs generation of the condensation product of aniline and formaldehyde with a viscosity of 100 JV at 25 ° C and containing about 30 wt. % N-CO-groups, and triggered by wet glycerol simple
    polyester polypropylenglycol with karooksilshl number 159 and mol. weighing 920, whose specific functionality is 2.62. The weight ratio is 3: 1. The viscosity of the forme olimer at 12,600 cP, the content of free N – CO – rpynn in it. 20.4 wt.% After storing the bandages for some time in a sealed JHOM by welding a bag of poly | ethylene-aluminum-polyester, samples are made from them for testing using the method described in example I and the solidification time is determined. In all cases, it exceeds 45 minutes, which means that the prepolymer composition, which does not contain an activator, is not suitable for obtaining a support band.
     The proposed dressing has good water resistance, breathability, low weight, good permeability.
    x rays. The curing of the proposed material, at which its maximum load is possible, occurs within 10 minutes.
    权利要求:
    Claims (1)
    [1]
    1. ChemicaC Orthopedics and jRelated Research, 1974, 103, 109-117.
    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    JPS6048184B2|1985-10-25|
    NO143129B|1980-09-15|
    AU3045277A|1979-05-17|
    CS222238B2|1983-05-27|
    FI65707B|1984-03-30|
    FR2369830A1|1978-06-02|
    NO773658L|1978-05-10|
    DE2651089B2|1979-09-06|
    NL182861B|1988-01-04|
    ATA794077A|1979-12-15|
    DD133519A5|1979-01-10|
    SE7712606L|1978-05-10|
    NL7712248A|1978-05-11|
    IT1106242B|1985-11-11|
    AT357683B|1980-07-25|
    BR7707480A|1978-06-20|
    ES463943A1|1978-07-01|
    BE860638A|1978-05-09|
    DE2651089C3|1980-06-12|
    NO143129C|1980-12-29|
    FI65707C|1984-07-10|
    US4376438A|1983-03-15|
    FR2369830B1|1982-03-12|
    DE2651089A1|1978-05-11|
    CA1160519A|1984-01-17|
    AR218045A1|1980-05-15|
    DK148801B|1985-10-07|
    PL109491B1|1980-06-30|
    FI773323A|1978-05-10|
    JPS5361184A|1978-06-01|
    DK148801C|1986-03-24|
    AU505816B2|1979-12-06|
    NL182861C|1988-06-01|
    DK495277A|1978-05-10|
    CH633718A5|1982-12-31|
    SE426289B|1982-12-27|
    PL201981A1|1978-07-17|
    MX148040A|1983-03-08|
    GB1578895A|1980-11-12|
    引用文献:
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    BE790976A|1971-11-06|1973-05-07|Bayer Ag|SILYL DERIVATIVES OF UREA AND THEIR PREPARATION|
    BE790977A|1971-11-06|1973-05-07|Bayer Ag|PROCESS FOR THE PREPARATION OF SILICY POLY-ADDITION PRODUCTS|
    DE2357931C3|1973-11-20|1980-06-26|Bayer Ag, 5090 Leverkusen|Curable dressing material|
    US4020832A|1974-12-24|1977-05-03|Reichhold Chemicals, Inc.|Package and method for preparing orthopedic cast-making materials|
    CH589447A5|1975-03-14|1977-07-15|Eschmann Peter|
    US4046744A|1976-07-28|1977-09-06|Rohm And Haas Company|Thermosetting coatings based on ketoxime-blocked isocyanates and oxazolidines|US4676234A|1980-09-06|1987-06-30|Bayer Aktiengesellschaft|Moisture-hardenable bandaging materials|
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    US4502479A|1979-09-04|1985-03-05|Minnesota Mining And Manufacturing Company|Water-activated casting material|
    DE3033659C2|1980-09-06|1987-07-02|Bayer Ag, 5090 Leverkusen, De|
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    US4442833A|1981-03-27|1984-04-17|Cutter Laboratories, Inc.|Casting or splinting package|
    US4427002A|1981-11-18|1984-01-24|Hexcel Corporation|Cold water curable orthopedic cast|
    FR2519992B1|1982-01-20|1986-04-04|Lhd Lab Hygiene Dietetique|PROCESS FOR THE PREPARATION OF A NEW MEMORY THERMOPLASTIC COMPOSITION FROM POLYCAPROLACTONE AND POLYURETHANE, PRODUCT OBTAINED ACCORDING TO THIS PROCESS AND ITS USE IN PARTICULAR IN ORTHOPEDICS|
    US4498467A|1982-01-20|1985-02-12|H. B. Kirkpatrick|Orthopedic cast, device and method for forming same and package therefor|
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    US4672956A|1982-05-06|1987-06-16|Smith And Nephew Associated Companies P.L.C|Bandages, components thereof and use|
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    US4609578A|1984-11-06|1986-09-02|Minnesota Mining And Manufacturing Company|Resin-coated extensible heat-set fiberglass knit tape|
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    优先权:
    申请号 | 申请日 | 专利标题
    DE2651089A|DE2651089C3|1976-11-09|1976-11-09|Self-retaining material for support bandages|
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