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Medical instrument, medical material and method for making medical instrument and medical material

Medical instrument, medical material and method for making medical instrument and medical material
IPC classes for russian patent Medical instrument, medical material and method for making medical instrument and medical material (RU 2466744):
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FIELD: medicine.

SUBSTANCE: medical material is processed by ionising radiation at radiation dose 5 to 100 kGy and contains a biodegradable resin and a polycarbodiimide compound in the amount of 0.1 to 10 wt % of resin. Biodegradable resin contains at least one resin specified in a group consisting of polybutylene succinate, and a polybutylene succinate copolymer, and polylactic acid or poly(3-hydroxyalkanoate) in the amount of 0 to 50 wt % of said polybutylene succinate resin. Group of inventions refers to a sterilised medical instrument made of said material, and to methods for making the medical material and the medical instrument which involve formation of said material and its processing by ionising radiation at radiation dose 5 to 100 kGy.

EFFECT: improved thermal stability, reduced tensile elongation and maintained strength and impact resistance after ionising radiation in the made medical material and instrument.

7 cl, 3 tbl, 16 ex

 

The technical FIELD

The present invention relates to medical instruments and medical materials consisting of biodegradable resins. Medical instrument and medical material of the present invention is suitable for use, for example, in the field of medicine. The present invention also relates to methods for medical instruments and medical supplies, consisting of biodegradable resins.

PRIOR art

Medical instruments and medical supplies for use in conditions, when they can stick body fluids such as blood and urine, so they should be made from plastics in the form of products disposable for single use and disposability of their use should be carefully done by burning or the like to prevent viral or bacterial infection. However, the use of such disposable instruments and materials waste increases, which leads to an increase of carbon dioxide emitted from waste incineration.

Biodegradable resin in end-of-life product decays present in nature by microorganisms to carbon dioxide and water, creating minimal impact on the environment. Essentially it is expected that the biodegradable resins find wide application is in various fields as materials for agriculture, materials for building and construction or any other industrial material. Among other things, from the point of view of slowing global warming attract attention biodegradable resin produced from produced from plant raw materials due to the fact that carbon dioxide released by the destruction of such resins adsorbed growing plants, and, thus, the total number of carbon dioxide does not change (the status-neutral carbon).

Examples derived from plants biodegradable resins include poliatilenaksida as an elastic polymer, polylactic acid and poly(3-hydroxyalkanoate) as an example of relatively inelastic polymer and their copolymers, blends, and polymer alloys.

Due to the reduced load on the environment, biodegradable resins are very suitable as resins for use in medical instruments and medical materials, which are usually discarded after a single use.

Unfortunately, biodegradable resins have low heat resistance, mechanical strength and ductility in comparison with these versatile resins like polyethylene and polypropylene. For wide-scale use of biodegradable resins need to improve their Fizicheskaya by modifying resin by adding modifiers, etc.

Polybutylmethacrylate resin are polyethylenepolyamine resin elastic nature, whose excellent impact resistance makes them suitable for parts of medical instruments. Polybutylmethacrylate resin can be made more solid, mixing them with the resin of the polylactic acid or a resin of poly(3-hydroxyalkanoate) so that it becomes easy to develop materials from polybutylmethacrylate resin in accordance with the intended use of the resin. However, to allay polylactic acid polybutylmethacrylate the resin for modification is not possible, due to the fact that the decrease in impact resistance due to exposure to ionizing radiation is also a problem that must be solved polybutylmethacrylate resin, and a significant reduction occurs specifically in the resin mixed with her polylactic acid.

In addition, the melting temperature polybutylmethacrylate resins is approximately 110°C, which is below 115°C, the temperature defined for sterilization by autoclaving, typically used for medical instruments and medical supplies. Thus, for a medical instrument and medical material, each consisting of only polybutylmethacrylate resin or mixture polybutylmethacrylate resin with the resin of p is limonadnoy acid or resin of poly(3-hydroxyalkanoate), sterilization by autoclaving may not be held due to possible thermal deformation.

Ionizing radiation, as allowing sterilization approximately at normal temperatures, is suitable for sterilization of less heat-resistant resins, but is not suitable for sterilizing medical instrument containing liquid, such as the capacity for injection, so that such a tool is desirable sterilized by heating resin.

As a way of increasing thermal stability of polybutylmethacrylate described crosslinking by irradiation of ionizing radiation (see, for example, non-patent document 1). The intensity of the applied ionizing radiation is 210 kGy and so high that there are concerns that the resin may deteriorate.

In conditions where medical instruments due to its convenience is often used sterilization by ionizing radiation, biodegradable resins for medical instruments is not used as the irradiation of ionizing radiation, the resin is significantly reduced strength and impact resistance in comparison with universal resin.

In the described method of obtaining sterilized by ionizing radiation molded products made of biodegradable resin to the biodegradable resin type tool enabling crosslinking by irradiation, before the resin is sterilized by ionizing radiation (see, for example, patent document 1). Upon irradiation with ionizing radiation must be controlled dose of radiation to control the strength and impact resistance of the irradiated resin. Also described is a method to improve the resistance of the biodegradable resin to hydrolysis, which involves adding polycarbamide as the terminal blocker (see, for example, patent document 2). Is not yet established whether or not adding polycarbamide to the biodegradable resin to prevent the decrease in strength and impact resistance when sterilization by ionizing radiation.

Non-patent document 1: J. Macromol. Sci. - Pure Appl. Chem., A38(9), 961-971 (2001).

Patent document 1: JP 2004-204195 A

Patent document 2: JP 3776578 B

Description of the INVENTION

The problems SOLVED by the PRESENT INVENTION

The present invention is made in view of the above problems to provide medical instrument and medical material, where each use of the resin composition of the complex aliphatic polyester, which is less than the reduced strength and resistance or which has improved heat resistance after treatment with radiation dose from 10 to 60 kGy, used for sterilization by ionizing radiation.

MEANS of SOLVING PROBLEMS

The applicants of the present invention as a result of intensive studies have found that bio is anlagebau resin, containing polycarbonite as a terminal blocker, less reduced strength and impact resistance, or it is more heat-resistant, allowing sterilization by autoclaving, irradiation of ionizing radiation dose used in the sterilization of medical instruments, and thus made the invention.

The above objective of the present invention reach as described in the following paragraphs.(1)-(5).

(1) a Medical instrument and medical material, sterilized by ionizing radiation, each of which contains a biodegradable resin and polycarbamide compound in an amount of from 0.1 to 10% by weight of resin.

(2) a Medical instrument and medical material according to the above (1), where the biodegradable resin is poliatilenaksida, a copolymer of polybutylmethacrylate or a mixture of polybutylmethacrylate and copolymer polybutylmethacrylate with polylactic acid or poly(3-hydroxyalkanoates).

(3) a Medical instrument and medical material according to the above (1) or (2), each of which contains polycarbamide compound in an amount of from 0.5 to 5% by weight of the biodegradable resin.

(4) a method of obtaining a medical instrument and medical material, including molding, and then the irradiation of the composition containing a biodegradable resin and the floor of the carbodiimide compound in an amount of from 0.1 to 10% by weight of the resin, ionizing radiation.

(5) a Medical instrument and medical material according to the above (4), where the biodegradable resin is poliatilenaksida, a copolymer of polybutylmethacrylate or a mixture of polybutylmethacrylate and copolymer polybutylmethacrylate with polylactic acid or poly(3-hydroxyalkanoates).

(6) a Medical instrument and medical material according to the above (4) or (5), where polycarbamide compound is contained in an amount of from 0.5 to 5% by weight of the biodegradable resin.

The EFFECTS of the INVENTION

Adding polycarbamide to the biodegradable resin makes it possible for medical instrument and medical material, both sterilized by ionizing radiation, each of which exhibits excellent Biodegradability, strength and impact resistance as strength and impact resistance of the resin before sterilization by ionizing radiation to sterilize, you can save almost completely, or obtaining medical instrument and medical material, both sterilized by ionizing radiation, each of which exhibits excellent heat resistance. As strength and impact resistance after exposure to ionizing radiation for sterilization only slightly different from the strength and impact resistance to radiation, regardless of type and and dose of ionizing radiation, specifically, sterilization conditions can be specified in various ways, and, thus, it is possible to provide many types of medical instruments and materials. Thus, the present invention has a very high versatility.

The BEST WAY of carrying out the INVENTION

In the remainder of this document details the medical instrument and the medical material of the present invention.

As used herein, the term "medical device" means a device or instrument for use in surgery, therapy or diagnosis, made at people or animals. As used herein, the term "medical material" means material for distribution or application of medicines or medical instrument, which must be disposed after use medical devices or medical instrument, such as packaging material or auxiliary device for medical devices or medical instrument. As used herein, the term "medical tool" means a tool for use in surgery, therapy or diagnosis conducted in humans or animals.

As used herein, the term "ionizing radiation" means electromagnetic waves or corpuscular radiation (Puig is) with ionizing high energy, in other words, the term does not refer to non-ionizing radiation with low energy. Ionizing radiation later in this document for simplicity listed as "radiation".

In the present invention believe that strength is the yield strength as determined by tensile testing and impact resistance represents the elongation at break, as determined by tensile test.

In the present invention, the resistance should be understood as resistance to deformation after storage at high temperatures.

Medical instrument and medical material (hereinafter referred to in this document as "medical instrument etc") of the present invention are characterized by the fact that each of them consists of a composition based biodegradable resin and contains polymermodified, which has durability and impact resistance, effectively remaining after exposure to radiation, or resistant to heat.

Biodegradable resin, which is suitable for the present invention are not specifically limited with its examples, including poliatilenaksida, a copolymer of polybutylmethacrylate/adipate, a copolymer of polybutylmethacrylate/carbonate, copolymers of polybutylmethacrylate/polylactic acid, poly(ε-caprolactone), polylactic acid, poly(3-hydro is silkenat) and their copolymers, the copolymer poliatilenaksidna/polybutylmethacrylate/terephthalate copolymer of polybutylenepipe/terephthalate copolymer of polytetramethylene/terephthalate, a copolymer of polybutylmethacrylate/adipate/terephthalate, as well as a polymer blend or polymer alloy of these resins.

Sterilized by radiation medical instrument, etc. that demonstrate superior strength and impact resistance, suitable means get using polybutylmethacrylate resin with high flexibility and impact resistance, such as poliatilenaksida, a copolymer of polybutylmethacrylate/adipate, a copolymer of polybutylmethacrylate/carbonate and a copolymer of polybutylmethacrylate/polylactic acid, and polymer blend or polymer alloy polybutylmethacrylate resin and polylactic acid or poly(3-hydroxyalkanoate) high strength. Although the preferred dilution factor polylactic acid or poly(3-hydroxyalkanoate) depends on the interest of the product and is not specifically limited, it is desirable to mix the polylactic acid at a mass ratio of from 0 to 50% of polybutylmethacrylate resin. When the amounts of polylactic acid, the larger the upper limit, the resulting composition increases the modulus of elasticity and its application will be limited.

Polycarbamide connection, suitable what about the present invention, can be obtained in various ways, and in fact it can get in the traditional way obtain polycarbamide (U.S. patent 2941956; JP 47-33279 B; J. Org. Chem., 28, pp. 2069-2075, 1963; Chemical Review, Vol. 81, No. 4, pp. 619-621, 1981).

Examples of organic diisocyanates as substances for the synthesis of the above polycarbamide compounds include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and mixtures thereof, more specifically, 1,5-naphthalenedisulfonate, 4,4'-diphenylmethanediisocyanate, 4,4'-diphenylmethanediisocyanate, 1,3-delete the entry, 1,4-delete the entry, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, a mixture of 2,4-tolylenediisocyanate and 2,6-tolylenediisocyanate, hexamethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylenediisocyanate, isophoronediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexylamine, tetramethylcyclopentadienyl, 2,6-diisopropylaniline and 1,3,5-triisopropylbenzene-2,4-diisocyanate.

The number polycarbamide connection for mixing the biodegradable resin is preferably from 0.1 to 10% by weight, in particular from 0.5 to 5% by weight of the biodegradable resin. With quantities of less than 0.1 mass%, the effect of preserving the mechanical strength at the time of sterilization by radiation is not observed, and on the other hand, the number of more than 10 mass parts of mo is ut degrade the physical properties of the biodegradable resin.

The composition of the biodegradable resin according to the present invention can optionally contain one or more conventional additives such as an antioxidant, a pigment, a softener, a plasticizer, a lubricating agent, an antistatic agent, an anti-fogging, a dye, an oxidation inhibitor (inhibitor of aging), thermo stabilizer, light and an absorber of ultraviolet rays.

The present invention polycarbamide connection can be mixed with a biodegradable resin by mixing in the molten state in a twin-screw extruder or you can use the way in which polycarbamide connection admixed in an already synthesized biodegradable resin. It is also possible to advance was received Royal blend biodegradable resin mixed with her polycarbamide connection and one or more other biodegradable resins mixed with resin masterbatches in forming medical instrument. The type of molding is not specifically limited its examples, including injection molding, extrusion, compression molding and blow molding.

A medical instrument, etc. of the present invention is sterilized by the radiation in a specific dose or after the molding process in a particular form, sborki packaging, to ensure their use as a medical instrument, etc. Used for the irradiation of the radiation dose depends on the interest of the product and is not specifically limited, provided that it falls within the range from 5 to 100 kGy with a preferred dose is from 10 to 60 kGy.

Used for irradiation of radiation may be an electron beam, γ-radiation or x-rays. Preferred are electron beam, formed by electronic accelerator and γ-radiation on the basis of cobalt-60 as they hug industrial production, where it is preferable to have the electron beam. It is preferable to use a medium to high energy electron accelerator with an accelerating voltage of 1 MeV or more for passing inside uniform medical instrument, etc. in order to allow the irradiation parts with greater thickness.

The atmosphere in which the radioactive irradiation is not specifically limited, in other words, the radiation exposure can be performed in an atmosphere of inert gas with a remote from it by air or in vacuum. In addition, the irradiation can be performed at any temperature, typically at room temperature.

Although the required temperature sterilized by radiation, medical instrument, etc. present ademu the invention depends on the shape of the medical instrument, highly resistant to heat and excellent consider a medical instrument, etc. with preservation of the shape of 99% or higher after storage at 120°C for 30 minutes due to their lower susceptibility to deformation during sterilization by autoclaving.

The required resistance sterilized by radiation, medical instrument, etc. of the present invention also depends on the shape of the medical instrument. Specific elongation, determined by a tensile test, 450% or more, preferably 480% or more, and more preferably 510% or more, and a medical instrument, etc. with elongation at break 450% or more is considered highly resistant to tearing and functionally superior due to their lower susceptibility to damage due to shock during transport or when dropped.

The required strength sterilized by radiation, medical instrument, etc. of the present invention also depends on the shape of the medical instrument. Specific yield strength determined by a tensile test, is 26 MPa or more, preferably 28 MPa or more, and more preferably 30 MPa or more, and a medical instrument, etc. with the value of the yield strength of not lower the upper limit, consider high strength and functionally superior due to less Podgorze the property damage, even in the form of a thin layer.

According to the present invention is a medical instrument, etc. is illustrated a container for tools, a syringe filled with the injectable solution, disposable syringe, a container for injection needles, tube, catheter, tube for transfusion, valve tray, non-woven fiber, surgical gloves, medical Bathrobe, bed sheets and filter.

The present invention is illustrated on the basis of the following examples, although not limited to.

Example 1

(1) Obtaining polycarbamide masterbatches

Mixing 22.5 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 2.5 kg of carbocylic (CARBODILITE LA-1 (produced by Nisshinbo Chemical Inc.) as polycarbamide receive a composition in which a uniformly mixed two components. The composition is mixed in the molten state at 180°C using co-rotating twin screw extruder (LABO PLASTOMILL, produced by Toyo Seiki Seisaku-sho, Ltd.), then granularit with receiving 25 kg polycarbamide masterbatches (content polycarbamide 10% by weight).

(2) the Receipt containing polycarbamide resin

A mixture obtained by mixing 1.6 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.4 kg polycarbamide uterine mixture obtained in the above (1), was mixed in a molten with the being at a temperature of 190°C using co-rotating twin screw extruder (LABO PLASTOMILL, produced by Toyo Seiki Seisaku-sho, Ltd.), then granulated to obtain 1.8 kg containing polycarbamide resin (the content of polycarbamide 2% by weight).

(3) Receiving plate containing polycarbamide resin

Containing polycarbamide resin obtained in the above (2) (contents of polycarbamide 2% by weight)was pressed with a pressure of 20 MPa at 200°C using a laboratory hot press (type SA-303, produced by TESTER SANGYO CO., LTD.), then cooled to a molding in the form of plates of 150 mm in width, 150 mm in length and 0.5 mm in thickness in the form of a plate material of the tray.

(4) the radiation exposure

Obtained in the above (3), the plate was irradiated at room temperature by electron beam 55 kGy of 10-MeV electron accelerator with getting radioactively irradiated plate material of the tray.

Example 2

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.5 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.1 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 3

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that serevi and resins, as used in (2)was 1.4 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.2 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 4

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.3 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.3 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 5

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.2 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.4 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 6

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.1 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.5 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 7

Radioactively about the scientists plate tray material received, following the method of example 1, except that the raw material resins, as used in (2)was 0.7 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.5 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.8 kg polycarbamide masterbatches.

Comparative example 1

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that as the only raw material resin (2) used 1 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation).

Comparative example 2

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.5 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.5 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.).

Comparative example 3

A mixture obtained by mixing 1.5 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.5 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.04 kg of bis(2,6-diisopropylphenyl)carbodiimide (produced by TOKYO CHEMICAL INDUSTRY CO., LTD.), mixed in the molten state at a temperature of 190°C using co-rotating twin screw extruder (LABO PLASTOMILL, produced by Toyo Seiki Seisaku-sho, Ltd.), then granuloma is getting 1.8 kg containing carbodiimide resin (the content of the carbodiimide 2% by weight), then received radioactively irradiated plate material of the tray, following the method of (3) and (4) of example 1.

Example 8

Received four plate material of the tray, following the way of PP. (1) through (3) of example 1, except that the raw material resins, as used in (2)was 1.8 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.2 kg polycarbamide masterbatches. The resulting plate material of the tray were irradiated at room temperature by electron beams of 20 kGy 40 kGy of 10-MeV electron accelerator, and 20 kGy 40 kGy of γ-radiation from cobalt-60, respectively, to obtain the four different radioactively irradiated plates of material of the tray.

Example 9

Radioactively irradiated plate tray material was obtained by following the method of example 8, except that the raw material resins, as used in (2)was 1.6 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.4 kg polycarbamide masterbatches.

Example 10

Radioactively irradiated plate tray material was obtained by following the method of example 8, except that the raw material resins, as used in (2)was 1.4 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.6 kg polycarbamide masterbatches.

Example 11

Radioactively oblucheny the e-plate of the tray material received, following the method of example 8, except that the raw material resins, as used in (2)was 1.2 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 0.8 kg polycarbamide masterbatches.

(Evaluation 1)

(Tensile test)

Of the plate material of the tray as obtained in examples 1-11 and comparative examples 1-3, stamp cut handleoversize samples 5B-type defined in ISO 527-2. With the use of the dynamometer Autograph (type AG-IS produced by SHIMADZU CORPORATION), the samples were subjected to a tensile test at a speed test of 10 mm/min to measure the yield stress tensile and elongation at break.

Measurements are given in tables 1 and 2. Confirmed that adding polycarbamide provided a smaller change in yield stress tensile and elongation at break after exposure to radiation in comparison with the yield strength tensile and elongation before radiation exposure and provide only a small change in strength and impact resistance after irradiation on the strength and impact resistance to irradiation, regardless of the type or dose of radiation. Thus, it is confirmed that the properties of the materials obtained in examples such as yield strength tensile and elongation at break, when sterilization by radiation significantly n is changed, thus, it is shown that the materials of examples suitable for various types of medical instruments, etc.

Table 1
The results of tensile tests (irradiation by the electron beam 55 kGy)
Yield strength (MPa) Elongation at break (%)
Unirradiated Irradiated The rate of change (%) Unirradiated Irradiated The rate of change (%)
Example 1 35 35 100 850 770 91
Example 2 35 35 100 840 750 89
Example 3 36 36 100 750 720 96
Example 4 38 36 95 700 690 99
Example 5 38 37 97 660 670 102
Example 6 39 39 100 620 620 100
Example 7 35 35 100 540 510 94
Comparative example 1 31 33 106 910 440 48
Comparative example 2 37 38 103 540 340 63
Comparative example 3 35 34 97 490 270 55
The rate of change: the Value obtained by dividing the values for the irradiated sample value for the non-irradiated sample.

Example 12

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.0 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.6 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 13

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 0.8 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.8 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Example 14

Radioactively irradiated plate tray material received, following with the lady of example 1, except that the raw material resins, as used in (2)was 0.6 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), and 1.0 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.) and 0.4 kg polycarbamide masterbatches.

Comparative example 4

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 0.4 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation) and 1.2 kg of polylactic acid (LACEA H-100, produced by Mitsui Chemicals, Inc.).

Example 15

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 1.1 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 0.5 kg of poly(3-hydroxyalkanoate) (polyhydroxybutyrate/valerate, produced by Hayashi Corporation) and 0.4 kg polycarbamide masterbatches.

Example 16

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 0.6 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 1.0 kg of poly(3-hydroxyalkanoate) (polyhydroxybutyrate/valerate, produced by Hayashi Corporation) and 0.4 kg poly is carbodiimides masterbatches.

Comparative example 5

Radioactively irradiated plate tray material was obtained by following the method of example 1, except that the raw material resins, as used in (2)was 0.4 kg of polybutylmethacrylate (GS Pla AZ81T, produced by Mitsubishi Chemical Corporation), 1.2 kg of poly(3-hydroxyalkanoate) (polyhydroxybutyrate/valerate, produced by Hayashi Corporation) and 0.4 kg polycarbamide masterbatches.

(Evaluation 2)

(Heat resistance test): insert tray material obtained in examples 1, 5 and 12 to 16 and comparative examples 4 and 5, cut samples (50 mm long and 10 mm thick each). The samples were left in an oven at 120°C for 30 minutes, then removed from the furnace and cooled to room temperature. The length of each sample was measured before and after thermal processing for calculation of the shape retention (%) [(length after heat treatment)/(length before heat treatment)×100]. In order to compare the samples, which were obtained from wafer to radiation exposure was also evaluated in a similar manner.

The calculated values are given in table 3. Confirmed that each of radioactively irradiated samples, consisting of polybutylmethacrylate or polybutylmethacrylate mixture, shape retention was 99% or more, in other words, they probably kept their shape and, thus, possessed high thermal stability. This includes the samples, containing polylactic acid (examples 1, 5 and 12-14), and samples containing poly(3-hydroxyalkanoate) (examples 15 and 16). In the case of non-irradiated samples, the temperature was low, and the shape retention was lower as the content of polybutylmethacrylate was higher.

The effect of radiation is not shown in the samples containing polybutylmethacrylate 40% or less, because such samples do not allow significant deformation even without exposure to the radioactive radiation (comparative examples 4 and 5).

Table 3
Shape retention (%) after treatment at 120°C
The irradiated sample (Non-irradiated sample)
Example 1 99,0 (90,8)
Example 5 99,3 (97,6)
Example 12 99,0 (98,1)
Example 13 99,4 (98,1)
Example 14 99,0 (98,7)
Example 15 99,0 (98,3)
Example 16 99,5 (98,9)
Comparative example 4 99,4 (99,4)
Comparative example 5 99,7 (99,9)

1. Sterilized medical material treated with ionizing radiation with the radiation dose from 5 to 100 kGy, containing
1) biodegradable resin, including
1-1) at least one resin selected from the group consisting of polybutylmethacrylate, and copolymer polybutylmethacrylate, and
1-2) polylactic acid or poly(3-hydroxyalkanoate) in an amount of from 0 to 50% by weight of the specified polybutylmethacrylate resin; and
2) polycarbamide compound in an amount of from 0.1 to 10% by weight of resin.

2. Medical material according to claim 1, in which the specified polycarbamide compound is contained in an amount of from 0.5 to 5% by weight of the specified biodegradable resin.

3. Sterilized medical instruments, processed by ionizing radiation with the radiation dose from 5 to 100 kGy, made of a material according to any one of claims 1 and 2.

4. A method of obtaining a medical Mat is the Rial, incorporating the following stages:
the processing of ionizing radiation with the radiation dose from 5 to 100 kGy, for sterilizing compositions containing
1) biodegradable resin, including:
1-1) at least one resin selected from the group consisting of polybutylmethacrylate, and copolymer polybutylmethacrylate, and
1-2) polylactic acid or poly(3-hydroxyalkanoate) in an amount of from 0 to 50% by weight of the specified polybutylmethacrylate resin; and
2) polycarbamide compound in an amount of from 0.1 to 10% by weight of resin.

5. The method according to claim 4, in which the specified polycarbamide compound is contained in an amount of from 0.5 to 5% by weight of the specified biodegradable resin.

6. A method of manufacturing a medical instrument, sterilized by ionizing radiation, containing stage:
molding material for sterilization, where the material contains:
1) biodegradable resin, including:
1-1) at least one resin selected from the group consisting of polybutylmethacrylate, and copolymer polybutylmethacrylate, and
1-2) polylactic acid or poly(3-hydroxyalkanoate) in an amount of from 0 to 50% by weight of the specified polybutylmethacrylate resin; and
2) polycarbamide compound in an amount of from 0.1 to 10% by weight of the resin; and
the processing of molded material for sterilization by ionizing radiation with the radiation dose from 5 to 100 kGy.

. A method of manufacturing a medical instrument according to claim 6, in which the specified polycarbamide compound is contained in an amount of from 0.5 to 5% by weight of the specified biodegradable resin.

 

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