JP3413297B2 - Ionizing radiation-resistant carbonate resin composition and medical component comprising the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ionizing radiation resistant carbonate resin composition and a medical part comprising the same. More specifically, the present invention relates to a carbonate resin composition that causes little color tone change and physical property deterioration even after irradiation treatment with ionizing radiation for sterilization, and a medical component comprising the composition.

[0002]

BACKGROUND OF THE INVENTION Carbonate resins have excellent mechanical and thermal properties and are used in a wide variety of applications. In addition, since it is excellent in transparency and hygiene, is tough and has excellent heat resistance, for example, a container-shaped packaging tool for accommodating and packaging a syringe, a surgical instrument, an intravenous syringe, a surgical instrument, an artificial lung, an artificial kidney. , Anesthetic inhalers, venous connectors and accessories, blood centrifugal separators and other medical devices, and surgical instruments, surgical instruments and other medical components. These medical components are usually completely sterilized. Specific examples include contact treatment with ethylene oxide, heat treatment in an autoclave, and irradiation with ionizing radiation such as gamma rays and electron beams. Among them, the use of ethylene oxide is not preferable due to toxicity and instability of ethylene oxide itself and environmental problems related to waste treatment. Further, when using an autoclave, there are drawbacks that the resin may be deteriorated at the time of high temperature treatment, the energy cost is high, and moisture remains in the treated component, which requires drying. . Therefore, sterilization treatments by ionizing radiation, which can be treated at low temperature and are relatively inexpensive, are used instead of these methods.

[0003]

However, when the carbonate resin is irradiated with ionizing radiation, the originally optically transparent polymer turns yellow. Therefore, a method of mixing a blue colorant into the resin and a method of adding various additives to suppress the yellowing have been proposed. For example, a method in which a polyester or a copolyester represented by a polyester composed of 1,4-cyclohexyldimethanol and a 6-membered carbocyclic dicarboxylic acid is blended as an additive (JP-A-60-199051, 62-187)
755), and a method of blending a mercapto compound typified by thioglycols (JP-A-2-49058, 2-11).
5260, 4-36343), and a method of adding a polyether polyol typified by polypropylene glycol or an alkyl ether thereof (JP-A-62-135656).
64-22959, JP-A-1-311165, 2-38.
450, 2-71752, 1-161050, 2-30
0257, 4-339857), a method of adding an epoxide compound (JP-A 63-213553), a method of adding a boron compound (JP-A 61-215651), and an aliphatic double bond in the molecule. A method of adding a polyfunctional monomer containing one or more (JP-A-3-33115) and a method of adding a halogen compound represented by a carbonate or a copolycarbonate derived from halogenated bisphenol A (JP-A-2-55062, 2). -6806
8, 2-174850) is already known, but even with these methods, yellowing of the carbonate resin when irradiated with ionizing radiation cannot be sufficiently suppressed.

Further, various methods of adding the above-mentioned additives or functional groups in combination have been proposed. For example,
A method of adding a halogenated bisphenol A type epoxy compound (JP-A-4-7356) and a method of adding a halogenated bisphenol A and a thioether (JP-A-2-23).
2259), a method of adding a polyester containing a halogen atom (JP-A-4-11653), and a method of adding a compound containing two or more aliphatic unsaturated bonds and a halogen compound together (JP-A-2-163156). ), And a method of using a halogen compound and a polyalkylene glycol or a derivative thereof in combination (JP-A-2-71752, 2-129261, 2-238049, 2-265957,
4-7356, 4-11653, 4-13759) and the like. However, the carbonate resin obtained by using these methods is also insufficient in the effect of preventing yellowing, or the strength of the carbonate resin itself is remarkably impaired if an amount sufficient to exhibit the effect is added. It has drawbacks.

Therefore, it has been the actual situation that a material which has very little yellowing during sterilization treatment by ionizing radiation and which retains sufficient strength and toughness and a medical part using the same have not been obtained.

As a result of extensive studies in view of the above problems, the present inventor has found that a carbonate resin has a compound having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups in the molecule, and a polycarboxylic acid. Ether polyol or its
The present inventors have found that by adding an alkyl ether , it is possible to obtain a material and a medical component which have a small change in color tone even when they are irradiated with ionizing radiation and retain excellent physical properties, and arrived at the present invention.

[0007]

[Means for Solving the Problems] That is, the present invention is
With respect to 100 parts by weight of the carbonate resin, 0.1 to 10 parts by weight of a compound having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups in the molecule and polyether polyol or its alkyl ether are added. 0.1-
It is intended to provide an ionizing radiation resistant carbonate resin composition containing 5 parts by weight and a medical part comprising the same.

The present invention will be described in detail below. The carbonate resin used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. A typical example is a carbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl), in addition to bisphenol A.
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3′-dimethyldiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Examples include dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, and dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone. To be These may be used alone or in combination of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like may be mixed and used.

Further, the above-mentioned dihydroxyaryl compound may be mixed with a phenol compound having a valence of 3 or more as shown below. As trihydric or higher phenol, phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-Hydroxyphenyl) -heptene-2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like, including 1 type or 2
More than one type can be used.

The viscosity average molecular weight of the carbonate resin is not particularly limited, but it is usually 100 in view of moldability and strength.
00-100,000, preferably 15,000-3500
It is 0. Further, in producing such a carbonate resin, a molecular weight modifier, a catalyst and the like can be used if necessary.

Compounds having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups in the molecule used in the present invention include pentaerythritol diallyl ether, pentaerythritol triallyl ether, and trimethylolporopandialyl. Examples thereof include ethers and glycerin diallyl ethers, and one kind or two or more kinds can be used.

The compound having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups in the molecule used in the present invention is used per 100 parts by weight of the carbonate resin.
0.1 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight. If it is less than 0.1 parts by weight, the effect of improving the resistance to ionizing radiation cannot be sufficiently obtained, and if it exceeds 10 parts by weight, the resin is deteriorated during molding and the physical properties of the final product are deteriorated.

The polyether polyol or its alkyl ale used in the present invention is described in JP-A-62-135.
56, 64-22959, JP-A-1-311165, 2
-38450, 2-71752, 1-161050, 2
The compounds disclosed in the respective publications such as -300257, 4-339857 and the like can be mentioned. Polypropylene glycol is particularly preferable. Further, the polyether polyol or its alkyl ether is contained in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the carbonate resin. To use 0.1 to 10 parts by weight of a compound having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups in the molecule and 0.1 to 5 parts by weight of a polyether polyol or its alkyl ether. A synergistic effect is obtained.

[0015]

As a method of blending the above-mentioned compound, the compound and a polyether polyol or an alkyl ether thereof, at any stage until just before molding the final molded product,
This can be done by means well known to those skilled in the art. For example, as well as a method of blending the compound (and polyether polyol or its alkyl ether) before, during, or immediately after the polymerization of the carbonate resin, the carbonate resin obtained by the polymerization and the compound (and the polyether polyol) are added. Or its alkyl ether) is mixed with a tumbler, a ribbon blender, a high-speed mixer or the like, and melt-kneaded with a single-screw or twin-screw extruder or the like. There is no limitation on the compounding order of the compound and the polyether polyol or the alkyl ether thereof, and it is possible to mix them simultaneously in any order.

Further, the ionizing radiation-resistant carbonate resin composition of the present invention, to the extent that the effects of the present invention are not impaired,
Other resin materials such as polyethylene terephthalate, polybutylene terephthalate, polyester polycarbonate, a polycondensate of cyclohexanedimethanol and terephthalic acid and / or isophthalic acid, or a copolymer of it and polyethylene terephthalate are used in a small amount. be able to.

Further, other known ionizing radiation resistance improvers (polyester, mercapto compound, epoxide compound, boron compound, polyfunctional monomer, halogen compound)
In addition, various additives, for example, hydrolysis inhibitors such as epoxy compounds, lubricants such as paraffin wax and fatty acid esters, antioxidants such as hindered phenols, phosphoric acid esters and phosphorous acid esters, triazine compounds, etc. A weather resistance improver, a flame retardant such as a halogen-based or phosphoric acid-based agent, or a coloring agent such as a pigment or a dye may be added.

The ionizing radiation resistant carbonate resin composition of the present invention is processed into medical parts by a method well known to those skilled in the art. Examples of medical parts include container-shaped wrapping tools for accommodating and packaging syringes, surgical tools, intravenous syringes, surgical instruments, etc.,
Artificial lungs, artificial kidneys, anesthesia inhalers, intravenous connectors and accessories, medical devices such as blood centrifuges, surgical tools,
For example, surgical tools. The processing method is also not particularly limited, and for example, injection molding, extrusion molding, blow molding, press molding, etc. are applied, and molding can be performed under the same conditions as the conventionally known carbonate resin and ionizing radiation resistant carbonate resin. .

Examples of the ionizing radiation include alpha rays, heavy electron rays, proton rays, beta rays, electron rays, neutron rays, gamma rays and x rays, and gamma rays are industrially used. The amount of ionizing radiation emitted is not particularly limited, but is usually about 25 KGray.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples without departing from the gist thereof.

Example 1 and Comparative Examples 1 to 3 Additives shown below were added to 100 parts by weight of pellets of carbonate resin (viscosity average molecular weight 21000), thoroughly mixed with a tumbler, and then a 40 mm uniaxial extruder was used.
Pelletization was carried out by a standard method. The pellet was processed by injection molding to obtain a test plate having a size of 45 mm × 55 mm and a thickness of 3 mm. Table 1 shows the YI value of this initial plate and the YI value of the plate after the plate was treated with 25 KGray of gamma rays. Additive A: pentaerythritol diallyl ether additive B: polypropylene glycol having a molecular weight of 2000

Table-1

[0024]

The ionizing radiation-resistant carbonate resin composition of the present invention and the medical parts comprising the same show very little yellowing during sterilization treatment by ionizing radiation and still retain sufficient strength and toughness. It is useful as a medical part material that is sterilized by ionizing radiation.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (2)

(57) [Claims] 1. To 100 parts by weight of carbonate resin,
0.1 to 10 parts by weight of a compound having two or more carbon-carbon unsaturated double bonds and one or more hydroxyl groups and one or more ether structures in a molecule, and 0.1 to 10 parts of a polyether polyol or its alkyl ether. An ionizing radiation-resistant carbonate resin composition, characterized by being mixed in an amount of up to 5 parts by weight. 2. A medical part comprising the ionizing radiation-resistant carbonate resin composition according to claim 1.