JPS5894861A - Resin composition for medical machinery - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for medical equipment, particularly to a resin composition suitable for forming equipment for storing lanes, infusions, etc. by molding.

BACKGROUND ART Conventionally, blood bags have been used as medical equipment to transport and hold blood, for example. The blood bag must not alter the blood in any way even if it comes into contact with the blood for a period of time, and it must not allow foreign substances to migrate into the blood or absorb components in the blood. . In addition, the blood bag has transparency that allows the blood inside it to be clearly observed from the outside, flexibility that allows it to be deformed freely, rebound elasticity that allows it to immediately return to its original shape even after being bent, and a state in which blood is contained. It must have creep resistance, etc., so that almost no distortion occurs when suspended in the ice.

BACKGROUND ART Conventionally, a composition in which a large amount of dioctyl slate is added to vinyl chloride resin has been used as a blood bag. Although this composition is excellent in terms of flexibility and transparency, it is important to note that the dioxic acid contained in the composition elutes into the blood and is eventually absorbed and accumulated in the body. has been considered a drawback.

In addition, a blood bag made of a composition to which a large amount of dioctucrate is added has the property of easily absorbing and retaining ethylene oxydite during sterilization with ethylene oxide gas. -τ It also had an X point where ethylene oxide could not be removed.

The present inventors #j improve the drawbacks of the diocchi M7 tallate-containing vinyl chloride resin composition, and also provide excellent flexibility and transparency, excellent creep resistance, etc. - A medical device rich in mechanical strength and rebound resilience As a result of intensive studies on compositions suitable for resins for use in commercial applications, we found a graft copolymer obtained by polymerizing vinyl chloride to an ethylene-vinyl acetate copolymer, and a gelabbut obtained by polymerizing vinyl chloride Q to a sensitive plastic polyclekone. It was discovered that a composition made of a copolymer has desired properties, and the present invention was completed.

That is, the gist of the present invention is to graft-polymerize vinyl chloride to voliclecun per 100 parts by weight of a graft copolymer obtained by graft-polymerizing vinyl chloride to an ethylene-acetyl pyri-v co-enriched polymer. A resin composition for medical equipment is characterized in that it contains 10 to 150 parts by weight of the obtained graft copolymer.

Ethylene-acetate vinyl copolymer (hereinafter referred to as E) in the present invention
Particularly preferred as VA) are those in which the vinyl acetate content as a copolymerization component is in the range of 30 to 80% by weight.

Furthermore, EVAζ in the present invention may be obtained by any of high-pressure polymerization, suspension polymerization, and emulsion polymerization, but
Particularly preferred are those obtained by aqueous suspension polymerization. To graft-polymerize dichlorochloride in the presence of the above-mentioned EMA, an aqueous suspension containing tjEVA% vinyl chloride, water, a dispersant, etc. is mixed with a radioisotope and a polymerization initiator is used for reaction. As a dispersant, for example, a dispersant having a degree of dispersion of 70 to 9
0mo v96 partial yen version vtn-ts vinyl M, mechi se? Used are a-cease, ζ-droxyethyl M-cerose, human a-cyp-A-biremeth-cererose, polyacrylic acid trichum, polyvinyl vicritone, and the like.

As for "Shun when the radio event started", Rakuai IV/(-Ochidito, Benshii IL//(-Okinide, Azobisinobuchi Minitril, Incidentally, during the above-mentioned graft polymerization, the polymerization temperature is preferably 50 to 70°C.

In this way, vinyl chloride is graft-polymerized onto EVA in an aqueous suspension, and then the graft copolymer is precipitated, dehydrated and dried, and a composition containing the graft copolymer as a constituent component is used for medical treatment. When a device is molded, the dispersant is eluted from the molded body and causes hemolysis and ml! ! Prone to exhibit toxicity.

k, the synthetic amount of EVA in the graft copolymer Vζ is preferably 30 to 70]11%.

In addition to vinyl chloride, the graft copolymer may contain other monomers that can be copolymerized with vinyl chloride, such as acrylic acid, meccrylic acid, methyl acrylate, methacrylic acid, butylene chloride, butyl chloride, etc. Rare acrylate, buti, mec acrylate, 2-ethytrehexy? Acrylic theta acid varnish fv such as rare acrylate, 2-ethylhexyl methacrylate, stearicyacrylate, and sialicimec acrylate, methacrylic acid ester ~ α-olefins such as ethylene and propylene; Vinya acetate, stearin vinyl θ varnish f~ like vinyl M; methyl vinyl; ~nee f~, j5 & bi=-? Reethers and the like may be contained as a graft polymerization component. In addition, the monomer may be added all at once at the beginning of the graft polymerization together with the korokapinise, or
It may be added continuously or in portions during the polymerization, and as in the case described above, the graft polymerization can be carried out by suspension polymerization in the presence of EVA.

A graft copolymer is obtained by randomly polymerizing dichloride and the monomer with EVA. By glat-polymerizing the monomer together with vinyl chloride M onto EVA, a product with much better transparency can be obtained than when only vinyl chloride U is graft-polymerized onto EVA. Grafting of the monomers 111! r component position is pyrochloride W1%/
It is preferable that the ratio is α01 to 1 with respect to l.

The above-mentioned graft copolymer itself has excellent A1+1 properties and flexibility, and does not exhibit hemolysis or cytotoxicity, and is suitable as a resin for A-carving medical equipment. However, it lacks the property of quickly returning to its original shape when deformed, that is, it lacks rebound resilience.

Therefore, the present inventors conducted repeated studies in order to obtain a composition with high impact resilience without impairing the advantages of the graft copolymer. As a result, the present inventors graft copolymerized vinyl chloride to Ichimachi polymeric filletane. The obtained graft copolymer was pref! By coexisting with a copolymer, it has excellent transparency and flexibility, W, good impact repellency, and properties suitable for molding medical devices without hemolysis or S-cytotoxicity. I found out that it can be done.

Examples of the thermoplastic polycrethane used in the present invention include polynis iθ urethane obtained by reacting Méliès f4I di-9 with a diisocyanate compound, and polynys
There is a polyether phrethane obtained by reacting a Tesidio MVC diinocyanate compound. Examples of the diisocyanate compound include 4,4'-dipheny-methane diinocyanate, 4,4'-quenylene diinocyanate, 2,4-tolylene diinocyanate, 2,6-tolylene diinocyanate, 1. 5-f7 ethylene diinocyanate, o-0m-1 ethylene diinocyanate, tetramethylene diinocyanate, pentamethylene diinocyanate, and hequina single ethylene diinocyanate are used. Examples of Méliès tludio M include aliphatic dicarboxylic acids selected from d-succinic acid, gusetal acid, adipic acid, pimeline i, speric acid, azelaic acid, cepacic acid, cundecanoic acid, dodecanoic acid, etc., and 1,4-pucundio+ , 1.6-hexidendioh M.

1. Add 10-dakamethylene dichloride, 1.2-propylene dichloride, 1.3-butylene dichloride, 2.5-dimethyl-z, s-hequinane diol M1 neopentylene glycol, etc. The one obtained by reacting the most widely used aliphatic dioxins is used.

〆As another b method to obtain Jioya, β-gua
biotuctone, piva-o-fuctone, δ-pare-a-lactone,
It is also possible to react cuctone compounds such as ε-calactone, methi-M-ε-cablockone, dimethyl-ε-cablocktone, trimechal ε-cabumicton, etc. with the aliphatic dioxin described in No. 10.

Polytetrahyde 07, polyethylene glycol, melip O pyrene glycol, polyoxybu a pyrene glycol, and the like are used as the polymer.

Dio-1 to the above estersidiol and polyade
It is preferable to use a compound having a molecular weight in the range of 1'tlj60Q to 10,000, or preferably 1,
The molecular weight range is from 0.000 to 0.000.

The graft polymerization of vinyl chloride to the thermoplastic resin can be carried out in exactly the same manner as the graft polymerization of vinyl chloride A to EVA.

In the graft copolymer in which vinyl chloride θ is graft-polymerized to the Kumamachi polymeric fillet obtained in this way, it is preferable that the copolymerization content of the a-plastic polycretane is F130 to 70kl1%.

Per 100 parts by weight of a graft copolymer obtained by graft polymerizing EVAK vinyl chloride, 10 to 150 parts by weight of a graft copolymer obtained by graft polymerizing vinyl chloride to a thermoplastic resin is mixed. And EVAI
If the amount of the graft copolymer obtained by graft polymerizing tIIkqIl meliclequne VC pina is less than 10 parts by weight per 100 parts by weight of the graft copolymer obtained by graft polymerizing C vinyl chloride, Even if a medical device is obtained by molding the resulting composition, it has poor rebound properties, and a graft copolymer obtained by polymerizing vinyl chloride with 5ZEVA is
If the amount of the graft copolymer obtained by grafting 1 part by weight of vinylic acid to 1 part by weight is more than 150 parts by weight, the resulting composition will be
Even if a medical device is obtained by C-shape processing, the transparency decreases and coloration appears, making it unsuitable as a composition for medical devices.

To mix each of the graft copolymers of #1 period, the d method can be applied, which involves mixing using a RJL, for example, a Mikilen Groyer, an extrusion kneader, etc., and EvA and thermal qmm polyflexin can be mixed simultaneously with water, suspension, and an aqueous suspension. '~ as a liquid,
After reacting with a radical initiator and graft polymerizing vinyl chloride to EVA and thermo-q plastic d' +7 cretan, the resulting graft copolymer is precipitated, dehydrated, and dried using the d method. You can also.

In addition, in the present invention, in order to improve the thermal stability and aging resistance of the resulting composition, stabilizers and plasticizers are blended into the resin composition within a range that does not cause harmful effects on blood, etc. Good too. As a stabilizer, for example, stearicum, zinc stearate, stearin paricum, etc. can be used, and as a plasticizer, epoxidized soybean oil, dioctyl 7-talate, etc. can be used. Furthermore, the obtained composition may contain a vinyl chloride resin, a vinyl chloride-ethylene copolymer, an ethylene-carbon oxide-vinyl acetate copolymer, etc. that are compatible with the composition. These resins usually make up 20% or less of the graft copolymer.

According to the present invention, it is possible to obtain a composition that not only has excellent flexibility and transparency, is free from hemolysis and cytotoxicity, but also has excellent rebound resilience and is suitable for molding medical devices.

In addition, in the resin composition for medical equipment of the present invention, like the conventional soft vinyl chloride resin composition, polyvinyl chloride resin is coated with polyvinyl chloride resin, low-molecular plastic All, polyvarnish, etc.
Since it is not necessary to add a large amount of a molecular plasticizer such as V, Borikrekun, etc., the elution of the plasticizer from the molded product can be avoided, and problems in molding processing can be avoided. .

Therefore, the resin composition of the present invention can be suitably used for molding medical equipment such as catheters, tubes for blood transfusions and infusions, blood bags, and infusion bags ◆.

Hereinafter, examples of the present invention will be given. In the examples, “part”, “
%", but read "parts by weight" and "% by weight" respectively.

Each test in the Examples was conducted as follows.

K M n 04 consumption by eluate: shred tube 3
0y, distilled water 300- was boiled at 121°C for 3 minutes and then cooled to room temperature as the test solution, C test @2QTId!
1Ca01NOK M n 04 liquid 2 (1/ and reading #
Add LOj and do it for 3 minutes! After boiling and cooling, KM (Li
(LOIN thiosulfate?) and titrated with IJ cum wave.

Separately, using 3 & 20m blank tests, operate in the same way and KM of both.
Please note that the difference in consumption of nO4 liquid is the fixed value.

Furthermore, it is below the standard value LOd.

Hemolytic test: Conducted in accordance with the test method for glass containers for infusions in the Japanese Pharmacopoeia's "General Test Methods."

Deformation recovery of the clamped part: The tube was clamped with a flang and left for a certain period of time.The flang was removed and the time required for the flattened tube to return to its original shape was measured. The load when tightening with the flang is 7 along the length b direction of the tube? It was set so that 2 to 4 # loads could be seen in a 1llL width part.

Example 1 By suspension polymerization? To 100 parts of the obtained EVA with a copolymerization content of vinyl acetate of 6096, 70s of vinyl chloride and 2 parts of water were added.
After adding 90 parts and dissolving EVA in vinyl chloride VC,
Stir the inside of the autoclave to make a suspension, and heat it to 70"C for 6
At 1ffi I responded.

Thereafter, it was dehydrated, and a graft copolymer in which vinyl chloride was polymerized to EvA was separated and dried. In the thus obtained graft copolymer of EVA and vinyl chloride, the copolymerization amount of vinyl chloride is Fi409b, and g
The vaO copolymerization component was 60%.

As a diinocyanate compound, hexidemethylene diinocyanate, Méliès? 260 parts of vinyl chloride and 600 seconds of water were added to 1001K of m0Tll property obtained by reacting adipic acid and 1,4-gukundio~ as ludio~, and polyurethane was mixed with vinyl chloride; The autoclave was swollen with water, and the autoclave was vigorously stirred to form a turbid solution, and the reaction was carried out at 70° C. after opening at 6 o'clock.

A graft copolymer having a grade content of 30% was obtained by graft-polymerizing Pina chloride onto the thus-obtained ShuIT plastic Vpn.

To 100% of the graft copolymer obtained by graft polymerizing vinyl chloride I%/4r to the above EVA and 100% graft copolymer obtained by graft polymerizing vinyl chloride to thermoplastic polyurethane, j! After mixing 4 parts of stearic acid ~ Shicum α, 1 part of zinc stearate α, and 5 parts of epoxidized soybean oil at 150°C for 5 minutes using a mixing O-V, a raw M sheet was created, and a pellet was prepared from the grain. I got it. Using a grain beret, the outer diameter is 7.0 mm and the inner diameter is 4.6 mm.
Cod tubes were extruded. The test results for this tube are shown in Table 1, Example 1.

From this test result, it was found that the resulting composition had %KM
The amount of 1104 consumed passed the standard value for medical equipment, and it did not show hemolytic properties.Furthermore, the flexibility and clamp tightening showed good recovery from deformation.

Example 2 100 parts of a graft octapolymer obtained by graft polymerizing vinyl chloride to EVA in the same manner as in Example 11,
Same as Ii 11, Kumamachi plastic finish is made of vinyl chloride.
Graft copolymer obtained by graft polymerizing 1.
50 copies, l! After kneading at 150°C for 5 minutes using varnish I arinic acid power ~ Shikum α 4 parts, stearin chloride lead CL 1 part, epoxidized soybean oil 5 parts mixing a -+ at 150 ° C.
A −+ sheet was prepared and a beret was obtained from it. Using this pellet, a tube of 41710 cm (outer) and II (6 cm) was extruded. The test results for this tube are shown in the column of Example 2 in Table 1.

From this test result, the obtained composition showed that the K
The MnQ4'all quantity met the specifications and showed no hemolytic properties.Furthermore, the flexibility and recovery of the ffi shape when tightened with the clamp were good.

(Left below) Table WI1 KMnO4 consumption Hemolysis test No hemolysis No hemolysis Flexibility Shore hardness (0℃) 69 62 (20
℃) 48 43 Deformation recovery of clamp tightening part Tightening left for 1 hour 8 minutes 3 minute line left for 5:00 II 17 minutes 9 minutes Patent applicant Sekisui Chemical Co., Ltd. Representative Mototoshi Fujinuma Tokuyama Sekisui Co., Ltd. representative Toshio Nakai, Patent Attorney Hiroshi Onishi

Claims (1)

[Claims] L Graft copolymer 100 obtained by graft electrolyzing ethylene-vinyl acetate/I/co 1F combination with pinyle chloride
PVC+ is added to thermoplastic polycrethane per part by weight.
) Graft copolymer 10-15 obtained by polymerizing
Resin composition 2 for medical equipment, characterized in that it contains 0 parts by weight of ethylene-acetic acid pinice copolymer, and copolymerizes it with vinyl chloride in addition to vinyl chloride 3. TFL is made by combining other monomers.
Scope of request Item 1 Resin composition for medical equipment