JP2016113532A - Dialyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dialyzer by molding a polycarbonate resin composition less in color tone change even with conducting an irradiation treatment of an ionization radiation for sterilization and excellent in thermal stability and releasability.SOLUTION: There is provided a dialyzer by blending a polycarbonate resin composition containing 100 pts.wt. of a polycarbonate resin, 0.1 to 5 pts.wt. of polyether polyol or alkyl ether, 0.5 to 6 pts.wt. of an organic halogen compound in terms pf halogen atom, 0.01 to 1 pts.wt. of a specific phosphorus-based antioxidant and 0.01 to 1 pts.wt. of a mold release agent.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polycarbonate resin dialyzer that has little change in color tone and is excellent in thermal stability and releasability even when an irradiation treatment with ionizing radiation for sterilization is performed.

Polycarbonate is an engineering plastic having excellent mechanical and thermal properties and excellent impact resistance, and is used in various fields such as the vehicle field, general equipment field, food field, and medical field. In particular, polycarbonate resin is excellent in transparency, hygiene, toughness, and excellent heat resistance. Therefore, in the medical field, for example, it is a container that contains and packages syringes, surgical tools, intravenous syringes, surgical instruments, etc. It has been used as a packaging device, a medical device such as an oxygenator, an artificial kidney, an anesthesia inhaler, a vein connector and accessories, a blood centrifuge, and a medical part such as a surgical tool and a surgical tool.

An application of such medical parts is a dialyzer.
Conventionally, treatment by artificial dialysis has been performed on patients whose kidney function has declined and blood cannot be purified by themselves. Artificial dialysis refers to a treatment in which blood drawn outside the patient's body is purified by flowing it through a dialyzer (artificial kidney) and the purified blood is returned to the body. As a dialyzer, the inside of the main body consisting of a cylindrical container is filled with a separation membrane such as a hollow fiber in order to remove the target component from the body fluid, and a dialysate connection part for allowing the body fluid to enter and exit is provided at both ends thereof. A dialysis part having a structure to which a cap part is attached is used. (For example, refer to Patent Document 1).

Medical parts such as dialyzer are usually completely sterilized. Specific examples include contact treatment with ethylene oxide, heat treatment in an autoclave, or irradiation with ionizing radiation such as gamma rays and electron beams. Of these, the use of ethylene oxide is not preferred because of the toxicity and instability of ethylene oxide itself and environmental problems related to waste disposal. In addition, when using an autoclave, there are disadvantages that the resin may be deteriorated during high-temperature treatment, the energy cost is high, and moisture remains in the treated parts so that they need to be dried. . Therefore, sterilization with ionizing radiation that can be processed at low temperatures and is relatively inexpensive is used instead of these methods.

However, when the polycarbonate resin is irradiated with ionizing radiation, the originally optically transparent polymer turns yellow. For this reason, a method of mixing a blue colorant into the resin and a method of suppressing this yellowing by adding various additives have been proposed. For example, polyesters represented by polyesters composed of 1,4-cyclohexyldimethanol and 6-membered carbocyclic dicarboxylic acids, methods of blending copolyesters as additives (see Patent Documents 2 and 3), and thioglycols (See Patent Documents 4 to 6) A method of adding a polycarbonate derived from halogenated bisphenol A, a method of adding a halogen compound typified by a copolycarbonate (see Patent Documents 7 to 9), etc. is there.

However, the polycarbonate resin compositions obtained by using these conventional methods still have insufficient heat stability, and there is a problem in that discoloration or heat degradation occurs during the heat molding of the polycarbonate resin composition. It was.

Further, since the dialyzer has a cylindrical shape, it is desired that the die design has a draft angle as small as possible. This means that the mold release resistance is increased, and thus the mold release resistance is reduced. For this reason, there is a high demand for materials with improved releasability.

JP-A-9-66225 JP-A-60-199051 Japanese Patent Laid-Open No. 62-187755 JP-A-2-49058 JP-A-2-115260 JP-A-4-36343 JP-A-2-55062 Japanese Patent Laid-Open No. 2-68068 JP-A-2-174850

The present invention has solved the above-mentioned problems, i.e., while maintaining the transparency inherent in polycarbonate resin, there is little change in color tone even when ionizing radiation treatment for sterilization is performed, and thermal stability and separation are improved. An object of the present invention is to provide a dialyzer having excellent moldability.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention incorporated a polyether polyol or an alkyl ether thereof, an organic halogen compound, a specific phosphorus-based antioxidant and a release agent into a polycarbonate resin. While maintaining the transparency inherent in the polycarbonate resin, a resin composition having little change in color tone and excellent thermal stability and releasability can be obtained even when irradiated with ionizing radiation. The present invention has been found to be suitable for use as a dialyzer, and the present invention has been completed.

That is, according to the present invention, 0.1 to 5 parts by weight of a polyether polyol or an alkyl ether (B) thereof and an organic halogen compound (C) in an amount of 0. A resin composition containing 5 to 5 parts by weight, 0.01 to 1 part by weight of a phosphorus-based antioxidant (D) represented by the following general formula 1 and 0.01 to 1 part by weight of a release agent (E) The present invention provides a dialyzer characterized by being molded.
General formula 1

（一般式１において、Ｒ１〜４は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を示す。）

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)

  The dialyzer of the present invention has excellent thermal stability and releasability while maintaining the transparency inherent in the polycarbonate resin, with little change in color tone even when irradiated with ionizing radiation. Moreover, improvement of the moldability of the dialyzer body is expected, and its practical utility value is extremely high.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

The dialyzer of the present invention is, for example, a component for artificial dialysis, such as a hollow fiber in order to remove a target component from a body fluid inside a main body composed of a substantially cylindrical or cylindrical container having openings at both ends. Cap parts that are filled with separation membranes and have connection parts for allowing body fluid to enter and exit are attached to the headers (lids) provided at the openings at both ends, or to the side walls of the openings. It means a dialysis part structured to be connectable with the apparatus. When dialysis is performed, for example, a predetermined separation membrane is accommodated in the dialyzer body, sealed with a header, and body fluid is injected through the connection portion. And after dialysis, it is comprised so that it may be guide | induced to the exterior from a connection part.

The polycarbonate resin (A) used in the present invention is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate 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 bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) 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 ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4 ' -Dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy- Dihydroxy diaryl sulfones such as 3'-dimethyl diphenyl sulfone and the like. These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.

Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include 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 can be mentioned, and one or more can be used.

Although there is no restriction | limiting in particular in the viscosity average molecular weight of polycarbonate resin, It is 10,000-100000 normally from the surface of moldability and intensity | strength, Preferably it is 15000-35000. Moreover, when manufacturing this carbonate resin, a molecular weight regulator, a catalyst, etc. can be used as needed.

Polypropylene glycol is preferred as the polyether polyol or alkyl ale (B) used in the present invention. Moreover, 0.1-5 weight part of polyether polyol or its alkyl ether is contained with respect to 100 weight part of polycarbonate resin. Using 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 an alkyl ether thereof. Thus, a synergistic effect can be obtained.

As the organic halogen compound (C) used in the present invention, a copolycarbonate of bisphenol A and tetrabromobisphenol A is preferable. The organic halogen compound (C) is contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the carbonate resin in terms of halogen atoms.

The phosphorus-based antioxidant (D) used in the present invention is a compound represented by the following general formula 1.
General formula 1

（一般式１において、Ｒ１〜４は炭素数１〜２０のアルキル基、またはアルキル基で
置換されてもよいアリール基を示す。）

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)

Examples of the compound of the general formula 1 include commercially available Sandstub P-EPQ manufactured by Clariant Japan.

The phosphorus-based antioxidant (D) used in the present invention is contained in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.

Moreover, the mold release agent (E) used by this invention is a glycerol fatty acid ester, Rikenmar S-100A by Riken Vitamin Co., Ltd., etc. are commercially available. The release agent (E) is contained in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.

As a method of blending a polycarbonate resin, a polyether polyol or an alkyl ether thereof, an organic halogen compound, a specific phosphorus-based antioxidant, and a release agent, at any stage up to immediately before molding the final molded product, Can be performed by well-known means. For example, the carbonate resin obtained by polymerization and the compound (and the compound polyol (and the polyether polyol or its alkyl ether and organic halogen compound) before, during, or immediately after the polymerization of the polycarbonate resin). And a polyether polyol or an alkyl ether thereof and an organic halogen compound) are mixed with a tumbler, ribbon blender, high-speed mixer or the like, and melt kneaded with a single-screw or twin-screw extruder or the like.

There are no restrictions on the order of blending the polycarbonate resin, the polyether polyol or its alkyl ether, the specific organic halogen compound, and the release agent, and simultaneous blending and blending in any order are possible.

In addition, the dialyzer of the present invention is a polycondensate of other resin materials such as polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol and terephthalic acid and / or isophthalic acid, or the like, as long as the effects of the present invention are not impaired. A small amount of a copolymer with polyethylene terephthalate can be added and used.

Furthermore, other well-known various additives, for example, hydrolysis inhibitors such as epoxy compounds, ultraviolet absorbers, halogen-based and phosphoric acid-based flame retardants, and coloring agents such as pigments and dyes may be blended.

As a method for molding the dialyzer of the present invention, methods well known to those skilled in the art, for example, injection molding or rotational molding are used. There is no restriction | limiting in particular also in a processing method, It can shape | mold on the conditions similar to a conventionally well-known carbonate resin. In the injection molding, a mold capable of forming a molded product and an injection molding machine of 100 to 200 T class are used. The molding processing temperature is preferably 230 to 260 ° C.

Examples of the ionizing radiation include alpha rays, heavy electron rays, proton rays, beta rays, electron rays, neutron rays, gamma rays, and X-rays. Industrially, gamma rays are used. There is no particular limitation on the amount of ionizing radiation to be emitted, but it is usually about 25 KGray.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily changed or modified without departing from the spirit of the present invention. Unless otherwise specified, “%” and “parts” in the examples indicate “% by weight” and “parts by weight” based on the weight standard, respectively.

The raw materials used are as follows.
Linear polycarbonate resin (A): hereinafter abbreviated as “PC” Caliber 200-13 (viscosity average molecular weight: 21000) manufactured by Sumitomo Dow
Polypropylene glycol (B): hereinafter abbreviated as “PPG” POLYGLYCOL P-2000 manufactured by Dow Chemical
Tetrabromobisphenol A (C): hereinafter abbreviated as “TBBPA” BC-52 manufactured by Chemtura Corporation
Phosphorous antioxidant (D): hereinafter abbreviated as “AO” Sandstub P-EPQ manufactured by Clariant Japan
Glycerin fatty acid ester (E): hereinafter abbreviated as MR Rikenmar S-100A manufactured by Riken Vitamin
The blending ratios of Examples and Comparative Examples are shown in Tables 1 and 2.

(Preparation of polycarbonate resin composition pellets)
The additive shown above was added to 100 parts by weight of a carbonate resin (viscosity average molecular weight 21000) pellet, and then sufficiently mixed by a tumbler, and pelletized by a conventional method using a 40 mm single screw extruder.

(Discoloration evaluation by ionizing radiation)
Each of the obtained pellets was dried in advance at 120 ° C. for 4 hours, and then a test piece was prepared using an injection molding machine (J100E2P manufactured by Nippon Steel) at a cylinder set temperature of 300 ° C. . As the mold, a plate mold having a length of 50 mm, a width of 50 mm, and a thickness of 3 mm was used. The yellowness YI of the plate was measured with a high-speed color analyzer CMS-35SP manufactured by Murakami Color Research Laboratory. YI of this initial plate is YI ₀ and YI of the plate after being treated with a 25 kGy gamma ray is YI ₁ , and the yellowing degree ΔYI is calculated using the equation: ΔYI = YI ₁ −YI _0. Indicated. As a criterion for evaluation, a case where ΔYI was less than 7 was judged as good (◯), and a case where it was 7 or more was judged as bad (x).

(Evaluation of releasability)
Each of the obtained pellets was dried in advance at 120 ° C. for 4 hours, and then using an injection molding machine, the cylinder set temperature was 280 ° C., the mold temperature was 50 ° C., and the cooling time was 20 seconds. Release properties were evaluated. Using a cup-type mold release resistance mold (molded product shape: 70 mm in diameter, 20 mm in height, 4 mm in thickness), the protruding load applied to the protruding pin when molding a cup-shaped molded product is measured. The release resistance values (N) were determined and shown in Tables 1 and 2. As a criterion for evaluation, a case where the release resistance value was less than 3000 (N) was judged as good (◯), and a case where it was 3000 (N) or more was judged as defective (x).

(Evaluation of thermal stability)
Each of the obtained pellets was dried in advance at 120 ° C. for 4 hours, and then the thermal stability of the residence was maintained using an injection molding machine (J100E2P manufactured by Nippon Steel) under a cylinder set temperature of 360 ° C. Evaluated. As the mold, a plate mold having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm was used. YI was determined by a high-speed color analyzer CMS-35SP manufactured by Murakami Color Research Laboratory Co., Ltd. using the first shot plate before dwelling and the second shot plate after dwelling for 15 minutes. Tables 1 and 2 show the yellowing degree ΔYI calculated using the equation: ΔYI = YI ₁ -YI ₀ where YI before residence is YI ₀ and YI after residence for 15 minutes is YI ₁ . As a criterion for evaluation, a case where ΔYI was less than 2 was judged as good (◯), and a case where it was 2 or more was judged as bad (x).

(Comprehensive judgment)
In the above evaluation, a sample satisfying all of the results was accepted (◯), and a sample not satisfying the criteria was rejected (x).

As shown in Table 1, when the configuration of the present invention was satisfied (Examples 1 to 5), all the evaluation items had sufficient performance.

On the other hand, as shown in Table 2, when the configuration of the present invention was not satisfied (Comparative Examples 1 to 6), each case had some defects.
Comparative Example 1 was a case where the blending amount of PPG was less than the specified amount, and although the release property and thermal stability were good, the discoloration due to ionizing radiation was inferior.
Comparative Example 2 was a case where the blending amount of PPG was larger than the prescribed amount, and although the discoloration and release properties due to ionizing radiation were good, the thermal stability was poor.
Comparative Example 3 was a case where the amount of TBBPA was less than the specified amount, and although the release property and thermal stability were good, the discoloration due to ionizing radiation was inferior.
Comparative Example 4 was a case where the amount of TBBPA was greater than the specified amount, and although the discoloration and releasability by ionizing radiation were good, the thermal stability was poor.
Comparative Example 5 was a case where the blending amount of AO was less than the prescribed amount, and although the discoloration and release properties by ionizing radiation were good, the thermal stability was inferior.
Comparative Example 6 was a case where the blending amount of MR was less than the prescribed amount, and although the discoloration and thermal stability due to ionizing radiation were good, the releasability was poor.

  The dialyzer of the present invention is a useful one that maintains the transparency inherent in the polycarbonate resin, has little color tone change even when irradiated with ionizing radiation, and has excellent thermal stability and releasability, Its industrial utility value is extremely high.

Claims (2)

0.1 to 5 parts by weight of a polyether polyol or an alkyl ether (B) thereof, and 0.5 to 6 parts by weight of an organic halogen compound (C) in terms of halogen atom, relative to 100 parts by weight of the polycarbonate resin (A), It is formed by molding a resin composition containing 0.01 to 1 part by weight of a phosphorus-based antioxidant (D) represented by the following general formula 1 and 0.01 to 1 part by weight of a release agent (E). A characteristic dialyzer.
General formula 1

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.) The dialyzer according to claim 1, wherein the release agent (E) is a glycerin fatty acid ester.