JPS59189153A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has good flexibility and heat resistance, is excellent in gas permeability and has high-frequency weldability, consisting of a stabilizer and a graft copolymer obtd. by reacting vinyl chloride with a styrene/butadiene copolymer. CONSTITUTION:A resin compsn. consists of a stabilizer and a graft copolymer obtd. by reacting vinyl chloride with a styrene/butadiene copolymer and/or its derivative. The quantity of the graft copolymer and/or its derivative is 20- 200pts.wt., pref. 30-120pts.wt. When the quantity of the copolymer or its derivative is less than 20pts.wt., the flexibility of the graft copolymer is low, while when it exceeds 200pts.wt., the mechanical strength is lowered and high-frequency welding becomes difficult. Examples of the derivatives of the styrene/ butadiene copolymer are epoxidized, halogenated and maleinized products of said copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Technical Field of the Invention The present invention relates to a novel resin composition. To be more specific, flexibility and heat resistance Jr! This invention relates to a vinyl chloride-based graft copolymer composition that has good properties, is capable of high-frequency welding, and has excellent gas permeability.

As is well known, blood exerts a self-protective action, and when blood comes into contact with an interface other than the inner wall of a blood vessel, platelets stick to the other interface, 'm fJ 73 J: This occurs due to the gelation of plasma, i.e., the formation of fibrin crosslinks. In conventional blood bags, platelets in the blood aggregate to the plastic interface of the blood bag, and 6 hours after blood collection, Platelet aggregation ability decreases to about 60% of blood collection [1i'i] and further decreases to about 40% after 24 hours.On the other hand, from the point of view of effective use of current platelet products, it is necessary to store blood for a longer period of time. There is a desire for the development of storage containers made of plastics that are compatible with blood, storage containers made of plastics that are less compatible with blood, and other medical devices.

Currently, such plastic containers and other medical devices are widely made of soft vinyl chloride resin due to their good processability, flexibility, transparency, low water vapor permeability, heat resistance, etc. It is used. These soft vinyl chloride resins contain 30 to 60% of phthalic acid ester such as di-2-ethylhexyl phthalate (hereinafter referred to as DO-P) as a plasticizer. However, since phthalic acid varnish has a high migration property, it is known that when a blood storage container is made from the above-mentioned soft vinyl chloride resin, the phthalic acid ester is eluted into blood plasma. For this reason, it has been reported that phthalate ester dissolves in plasma containing shrunken platelets and causes a decrease in the aggregation ability of platelets (Journal of the Japan Society for Blood Transfusion, 2).
82 (1982)).

The above-mentioned soft vinyl chloride resin containing Nisulfalate phthalate plasticizer has insufficient gas permeability, and the shelf life of the blood bag using this resin, which shows the platelet preservation property, is only 6 days after energization. In other words, soft vinyl chloride resin has a permeability coefficient of carbon dioxide of about 2. Qx
103m1. -mm/m 2 -atm ・day P
i! The time limit for right movement of concentrated platelet plasma in the blood bag using this was 6 hours.

However, this transmission coefficient is 2.5×103-・9.0×10
37nl -mm/m2-atm-day (3.Qx103~8
．． Qx 1 0 3 77tjHnm/m
2. A [...day] increases the preservative of platelets and effectively preserves platelets.
``6 or more for 72 hours or more with 7 Gris''.

If it is less than 2.5, C02i caused by platelet metabolism
As the temperature increases, the pH decreases, and platelet preservation cannot be maintained for a long time. Also, when the number of people who hear more than 9 or 0 increases, platelet metabolism is activated too much and platelet function is damaged in a short period of time. Note that by keeping the permeability coefficient within the above range, the preservation stability of other blood cells can also be improved. For this reason, increasing the amount of plasticizer blended will improve gas permeability, but increasing the amount will actually result in a loss of practical mechanical strength. Gas permeability that enables long-term storage, Zunawara 2,
5X 103~9. OX 103m1-mm/m2
・It is difficult to obtain atm-day.

On the other hand, as non-migratory plasticizers, poly and sulfur plasticizers are used. This polyester plasticizer is
In general, it is well known that phthalate esters having a phenyl group are inferior in terms of water resistance (1) and hydrolysis resistance (1), which are mainly composed of fatty acids (esters).

On the other hand, the material for blood bags has relatively good gas permeability, and contains 10 to 40% by weight of polypropylene and 40 to 85% by weight of polypropylene.
Blend J, Rinaru resin composition with thermoplastic elastomer of Shigekawa% is known/)ζ (JP-A-55-607
16/4 Easy), such polyolefin resins have poor adhesive properties, so high frequency fusion is a national strength (
C available, molding ■ [methods are limited. Additionally, it lacks the flexibility that occurs when soft polyvinyl chloride is used. 1 1I OBJECTS OF THE INVENTION Accordingly, one object of the present invention is to provide a unique resin composition.Another object of the invention is to provide a resin composition with good flexibility J5 and heat resistance. 1) It is an object of the present invention to provide a vinyl chloride-based graph 1-9 polymer phase which is frequency fusion bondable and has excellent gas permeability.

Among these, styrene-butadiene copolymer J3
This is achieved by a resin composition consisting of Graphs 1 to No. J obtained by reacting the derivatives of J and/or J with vinyl chloride, the polymer J3, and a stabilizer.

Moreover, the present invention has a vinyl chloride portion of 100! : 20 to 200 parts of the styrene-butadiene copolymer and/or the derivative part of A to the part I, preferably 1 to 30 parts.
It is a resin composition having a weight of 120 parts by weight. In general, the present invention is a resin composition in which the derivative of the styrene-butadiene copolymer is an evoxylate, halide, or maleate of a styrene-butadiene copolymer. Also,
The present invention is a resin composition in which the stabilizer is contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the combined mold for graphs 1 to 1.

■2 Detailed Description of the Invention The graft copolymer used in the present invention is a new compound, which can be obtained by reacting vinyl chloride with a diuretic butadiene copolymer and/or its derivative. This is what will happen. The graft copolymer and/or its derivative portion is 20 to 200 parts by weight, preferably 30 to 120 parts by weight. This is because if the amount of the copolymer or its derivative is less than 20 parts by weight, the graft copolymer will have low flexibility, while if it exceeds 200 parts by weight, the mechanical strength will decrease and high frequency fusion will be difficult. Because it will be.

Such a raft copolymer can be prepared, for example, by charging vinyl chloride and a direceive butadiene copolymer or a derivative thereof into a reactor in the above-mentioned proportions, and then suspension polymerizing the vinyl chloride in the presence of a radical polymerization catalyst. NiJ: can be obtained. Graph 1 ~ copolymer obtained in this way is
If necessary, it is washed and purified with water to alcohol.

The additive used is a random or block copolymer with a styrene to butadiene ratio of 1:1 to 1:101, preferably 1:2 to 1:6; 50,000 to 200,000, preferably 70,000, 19 (1,000).

To give an example, for example, Cariflex TR-110
1 (Seal Chemical Co., Ltd.), Nokoreflex TR-11
07 (Shell Chemical Co., Ltd.), Tulubrene (Fushikasei Co., Ltd., Philips Co., Ltd.), Toughbrain (Fushikasei Co., Ltd.), Clay[・NG]
(Seal Chemical Co., Ltd.) etc. , j! Examples of derivatives include epoxidized products, halides, maleated products, etc. of the so-f-receive butadiene mercury described in v11.

Stabilizers to be incorporated into the resin composition of the present invention include metals such as calcium and zinc, and sulfuric acid, lauric acid, ricinoleic acid, and Schiffic acid.

2-■ There are metal compounds (J, etc.) with fl-contaminated nIi acids such as thylhexoic acid, and these are 1 scale or 12 scales or more based on 100 parts by weight of the graft copolymer. 0.05 to 5,000 parts by weight, preferably 0.1 to 3 parts by weight.In addition to the above-mentioned stabilizers, epoxidized soybean oil, epoxidized linseed oil, etc. are added as stabilizing aids. Vegetable oil also has -C30 for the copolymer 100 weight part from the graph 1 above.
It can be contained in an amount equal to or less than the width part, preferably 5 to 20 parts by weight.

Furthermore, in the tree 11Fft composition of the present invention, a polymer plasticizer can also be blended. Examples of polymeric plasticizers include ethylene copolymers, such as Coachrecey acid-resistant vinyl
oy) 742. E, r, du Pont
deNemours & CO), polyesters such as polycaprolactone (polystyrene), polyε-cabrolactone (e.g. I) CL
300, PCI-700 (or above, LJ n1on
Made by Carbide)], polyester (made by Carbide)
t101) IaZ 6187 (Dingellneco
CI)em i Cal S), l]arap
lex G-25゜paraplcx G
! U 4 (hereinafter, t, Rohm &
II AAS), △dmcx 761 (∆
5hland Chemicals), etc.). Among these, the above-mentioned ethylene copolymer (eg, [31valoy 742)] exhibits particularly excellent effects. These IO 1 molecule iiJ till agents are blended in an amount of τ150 parts or less, preferably 10 to 00 parts by weight, per 100 parts by weight of the graft copolymer. Furthermore, lubricants and other additives may also be used as long as they do not exhibit LB properties.

The resin composition according to the present invention can be produced using a commonly used press molding machine, an extrusion molding machine (extrusion molding machine, q4 extrusion molding machine,
- It is possible to perform molding using a molding machine, an inflatable molding machine, a calender molding machine, etc.

These molded products are made using a high-frequency melting machine, etc.
] By drying, medical tools such as blood storage containers, transfusions, etc. can be obtained.It can also be used for other purposes. Noh,
It is possible to maintain its freshness. On the other hand, if the contents prefer circulation with the outside air, good preservability can be obtained by using the resin composition of the present invention as a packaging material.

The resin composition produced in this manner has good transparency f1, is highly flexible, has good heat resistance, is capable of high frequency welding, and has a large excess coefficient (carbon dioxide) of 3 x 103 to 9 x 10".
rn, 1-mm/m 2-atm-day (3
0'C), preferably 2.5X103-8. Qxl 0
” ml-mm/m 2-atm-day (30
℃).

Next, a case in which a blood collection bag is manufactured using the resin composition of the present invention will be described with reference to the drawings. In other words, the drawing shows a blood bag, and the blood collection bag 2 made of the resin composition of the present invention, which is equipped with a plurality of outlet ports 1 and 2 with beer tabs, has a peripheral portion and a high frequency heating or other method. heat-sealed by heating means of 13
A blood collection tube 6 made of the resin composition of the present invention is connected to the internal space 5 of the blood collection bag. liquid (for example, 200 g of sodium citrate, 0.80 g of citric acid and 2 g of glucose in 10011 L!l of aqueous solution)
．． 20 (containing I), CPD liquid (e.g. aqueous solution 100
ml contains 0.327 g of citric acid, 2.63 g of 1-lium citrate (+, 0.251 g of 1-lium dihydrogen phosphate)
Contains 2.32 J of Dext[]-su), etc. In addition, a cap 8 is attached to the tip of the blood sampling forceps 6 (1).
is taken (-1 is taken.

In addition, when connecting a child bag in addition to the blood collection bag 3, the peripheral portion 10 of the beer tab (made of the resin composition of the present invention equipped with the JJI outlet 9) is heat-sealed,
A first child bag 13 equipped with a connecting tube 12 made of the resin composition of the present invention, which communicates with the internal space 11 of A, connects the blood collection bag 3 to the connecting discharge [12] via the branch pipe 1'l.
Connecting tube 1 (5) connected by connecting side 15 at the tip
are connected.

In addition, there is also a t!ji binding bucobu-corp 21 Uetako made of the resin composition of the present invention, which is equipped with a beer tab 1] 1 outlet () 17, whose peripheral portion 18 is high-frequency sealed, and which communicates with the internal space 19 of A. The connecting tube 21 of the bag 22 is connected to the connecting tube 1-socket 12.16 via the branch pipe 14.

Although the above description has been made using a blood bag as an example, the present invention can be similarly used for other blood storage containers, blood transfusion systems, catheters, blood circuits, dialysis dips, etc.

Next, the present invention will be explained in more detail by giving examples.

Examples 1 to 5 Epoxidation was carried out on 100 parts by weight of a granoid copolymer obtained by combining vinyl chloride with a polymer (1t75,000) of polymer molecules in the proportions shown in Table 1. Soybean oil (0-130P) 5 parts by weight Onibi Ca-Z
A resin composition containing an n-type stabilizer (Mark 593) with a 1Φ hanging part was extruded to obtain a 4 mm thick sheet. This Sea 1~ was transparent, and the results of the hemolytic toxicity test and cytotoxicity test were the same as those of the previous solution, and showed no hemolytic property or cytotoxicity. Further, when the carbon dioxide gas permeability was tested, it was found to be rated as J3 in Table 1. Among them,
Examples 2 to 5 exhibited particularly excellent carbon dioxide permeability compared with Comparative Example 1 J: Lee et al.

Comparative Example 1 Polyvinyl chloride with an average degree of polymerization of 1,300 100Φ hanging part was treated with Epo 1-silica, () oil (0130)) ) 5
A vinyl chloride resin composition containing Φ hanging part, 11 parts of Ca-Zn stabilizer, and 1 part of DOP 25 weight M was extruded and molded into 0.4 mm.
I bought 1q of thick sheets. Regarding this sea 1, Example 1~
5) When 41 tests were conducted as in Table 1, 85
1 Comparative Example 2 The average degree of polymerization was 1,300, and the sewage butadiene copolymer used in Examples 1 and 5 was added to 1 part of 100 parts by weight of polyvinyl chloride. 33 in the same proportions, this formulation 100! f! Add T-poxidized human soybean oil a3 to the hanging part and add 0.7 dmm/'i; This sheet had low mechanical strength and was not suitable for practical use.

Examples 6 to 10 Shown in Table 2? Epoxidized dogwood oil (0-130P) 5% to 100% ED agent part of Granotova polymer obtained by polymerizing vinyl chloride to Sujireshi butadiene copolymer (160,000 molecular weight) at a ratio of 1% Part by weight, Ca
-7n stabilizer (mark 593) 1 layer fit 1
A resin composition prepared by blending ili iJy and ethylene-acid-resistant donyl keyne copolymer Elvaloy 742) 60 parts was extruded and molded with 0.4. mm thick sheet
1! ? Ta. This sheet is transparent and flexible, and the results of the hemolytic toxicity test, J, and cytotoxicity test are the same as the control solution, and it does not show any hemolytic or cytotoxicity. It was suitable as Further, when the carbon dioxide gas permeability was tested, the results were as shown in Table 2. Among them, those of Examples 7 to 10 showed especially superior carbon dioxide sludge permeability than that of Comparative Example 3.

Comparative Example 3 The same formulation was used as in Comparative Example 1 except that J5 and Jiij of DOP were increased to 50 parts by weight, and the sheet weight was 1q. When tests similar to those in Examples 6 and 10 were conducted on these seams 1 to 1, the results were as low as those in Table 2.

Example 11 In order to see the effect of improving gas permeability of the resin composition according to the present invention, the resin composition of Example 9 and the styrene-butadiene copolymer were mixed with polyvinyl chloride and styrene-butadiene copolymer in the same ratio. Direceive butadiene coacetate was dissolved and mixed in 1 trihydrofuran, reprecipitated with methanol, and epoxidized oil, Ca-711 stabilizer and Elhalloy 742 were blended in the ratio shown in Table 3. A sheet of 4 mfl + thickness was prepared, and the carbon dioxide gas permeability coefficient was measured.The results were as shown in Table 3.Resin composition (dry I1 ratio)Resin composition (dry I1 ratio) Actual h1! ! Example'', -Ruco Genso--zu-graft co-merger ioo --
VC/5BS (weight pressure) (10 (1/130
)PVC/5BS (100/130) 10
0 Epoxidized soybean oil (0-130P) E5 5Ca
-Zn stabilizer (Mark 593) 1 1 Elhalloy 7×2 60 60 Charcoal residue permeability coefficient (mffi-+nm/m2・atm-ddy),
5.72 x 1 (1” 2.io x 103 Example 12 Regarding the sheet of Example 8 and the sheet of Comparative Example 33,
The number d3 and morphology of platelets on the C1 surface were measured, and the results were as shown in Table 4.

Teeth 34 Table Example 8 Example 33 Total number of adherents 157 257\1 Number of ■ types in total number 66 113 ■ Proportion of ■ types (%) 42 44 Experimental method 95,000 pieces on one surface / mm3 platelets f? After dripping the solution and leaving it for 30 minutes, the number of attached platelets and changes in the morphology of the attached platelets were observed. In addition, among the classification evaluations, ■
The platelets are expanded and plate-shaped.

Example 13 The resin composition of Example 8 and the resin composition of Comparative Example 3 were each made into sheets 1 to 9 with a thickness of 0.7 I...m, and furthermore, bags were made by high frequency welding. , Add 〇D-Δ solution to this bag as a storage solution and add 3 m of contracted platelet plasma!
After observing the carbon dioxide gas permeability and P11 change of the sheet when it was heated at 22°0 for 72 hours,
The result in Table 5 is 19.

Spear 5 Table Example 8 Skin vine - Carbon dioxide permeability coefficient (711,91mm/m 2.atm-day) 4.
80 x 1032.00 x H13 platelet count (X 10”/mm”) (I) 98.0
98,9 (II) 200,6 200,4
p l-1 (before storage> (1) 6.841
6.856 ([) 7.154 7.1
471) H (72 hours later (I) 7.16
1? , 2! i0(II) 7.14
4 6.515 The maintenance of p tl during storage is
τJ has important implications for platelet survival rate after transfusion
3. When sea urchin C of Example 8 of the present invention was stored in a bag with high carbon dioxide gas permeability, the +1H low temperature was smaller than that of Comparative Example 3, and the function maintenance during platelet storage was J , that is obvious.

■1 Specific effects of the invention As described above, the resin composition according to the present invention comprises a styrene-bucdiene copolymer and/or its 11
Since it is composed of a graft copolymer and a stabilizer that can be reacted with vinyl chloride in the body, it has excellent flexibility and heat resistance (1 is good and high frequency melting Z1 is possible, and gas permeability, especially It has excellent carbon dioxide gas permeability.Also, 20 parts by weight of the polyvinyl chloride part and/or its derivative part is
Since the amount is 200 parts by weight, preferably 30 to 120 parts by weight, carbon dioxide gas permeability is particularly good. Roughly,
The resin composition according to the present invention is free from hemolytic toxicity and cytotropism, and has small changes in platelet adhesion and morphology.
However, it is extremely useful as a material for medical devices such as blood bags.It is also useful as a packaging material for contents that undergo metabolism, such as vegetables.

[Brief explanation of drawings]

The drawing is a front view showing an example of a tool using the resin composition according to the present invention. 3...Blood bag, 13.22...Rice bag, 6
．． 16.21...f-j-bu1゜

Claims (5)

[Claims] (1) A resin composition comprising a graft copolymer and a stabilizer obtained by reacting a styrene-butadiene copolymer and fJ or a derivative thereof with vinyl chloride. (2) For every 100 parts of the vinyl chloride part, the styrene-butadiene combination and/or its derivative part is 2 parts.
The resin composition according to item 1, wherein the content is 0 to 200 parts by weight. (3) The resin composition according to claim 1 or 2, wherein the derivative of the styrene-butadiene copolymer is an evoxylated, halide, or maleated styrene-butadiene copolymer. (4) The resin composition according to any one of claims 1 to 3, wherein 0.05 to 5 parts by weight of a stabilizer is blended to 1 part by weight of 100 parts of the graft copolymer. thing. (5) Carbon dioxide permeability coefficient is 2.5X103~g. OX 10" 7fli -1nm/m 2"a [ll
l-day'? :"The resin composition according to any one of claims 1 to 4 rr4.