JP2002212366A - Resin composition and substrate for blood bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new resin composition having excellent mechanical characteristics, especially toughness and suitable for a nonflexible vinyl chloride substrate for a blood bag having excellent shelf life of erythrocytes and to provide the substrate for the blood bag using the resin composition. SOLUTION: This substrate for the blood bag comprises (A) 30-0.5 pt.wt. of a low-molecular organic ester plasticizer and (B) 99.5-70 pts.wt. of the following aromatic vinyl compound-ethylene random copolymer and the substrate for the blood bag comprises the resin composition as a forming layer. The component (B) is an aromatic vinyl compound-olefin random copolymer having 1 to <=99.9 mol% aromatic vinyl compound content and has a chain structure of head-tail of >=2 aromatic vinyl compound units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for a blood bag suitable for storing and preserving a blood component, particularly a liquid containing red blood cells, and a base material for a blood bag using the same.

More specifically, the present invention relates to a novel resin composition which is excellent in mechanical properties, in particular, toughness, has good hemolysis-inhibiting action, and is preferably used for a blood bag substantially free of chlorine. And a substrate for a blood bag using the same.

[0003]

2. Description of the Related Art A blood bag is transparent so that the state of a liquid content, that is, a blood component, can be observed, flexibility for easily performing operations such as blood collection, blood transfusion, and blood component separation, and strength and hygiene that can withstand these operations. , Safety and other properties are required. At present, soft polyvinyl chloride containing a plasticizer (hereinafter referred to as soft PVC) almost meets the above-mentioned required characteristics, and is therefore widely used as a base material for blood bags.

[0004] In particular, when preserving red blood cell components, the plasticizer in soft PVC leaches out to inhibit the morphological change and hemolysis of red blood cells, but such an effect is observed with other polymers such as polyethylene and polypropylene resin. For this reason, soft PVC is mainly used as a base material for blood bags. However, treatment of polyvinyl chloride waste after use has become a problem in soft PVC blood bags, and there is a great need for non-flexible PVC conversion of blood bags.
Various proposals have been made so far, but at present it has not reached a stage where it is sufficiently satisfactory.

For example, JP-A-3-502298 discloses a composition of a non-soft PVC resin (specifically, a composition composed of a styrene-based elastomer, polypropylene, etc.) and a citrate ester. Describes that it has a function of suppressing the hemolysis phenomenon of red blood cells, and JP-A-6-319785 discloses a non-soft PVC resin (a thermoplastic polyester is mentioned as a specific example).
Although a system composition is described, in the range tried by the present inventor, the plasticizer is inferior to the hemolysis-suppressing action of soft PVC, and is not practical.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel resin composition which is suitably used as a base material for a non-flexible PVC blood bag which has excellent mechanical properties, especially toughness, and excellent erythrocyte preservability. And a blood bag base material using the same.

[0007]

The present invention has solved the above-mentioned problems by a novel composition comprising a novel olefin-aromatic vinyl compound copolymer and a low molecular weight organic ester plasticizer. . INDUSTRIAL APPLICABILITY The resin composition of the present invention is suitably used as a base material for a blood bag having excellent mechanical properties, particularly toughness, and at the same time, having a good hemolysis suppressing action.

That is, the present invention relates to (A) 30 to 0.5 parts by weight of a low-molecular-weight organic ester-based plasticizer, and (B) 99.5 to 59.5 of an aromatic vinyl compound-olefin random copolymer described below.
A resin composition characterized by containing 70 parts by weight and a base material for a blood bag containing the resin composition as a forming layer. The aromatic vinyl compound-olefin random copolymer of the component (B) has an aromatic vinyl compound content of 1 to 99.
It is an aromatic vinyl compound-olefin random copolymer having a head-tail chain structure of two or more aromatic vinyl compound units of 9 mol% or less. Preferably, the aromatic vinyl compound content is 1 to 99.9 mol% or less, and the head of two or more aromatic vinyl compound units—the aromatic vinyl compound having a tail-chain structure—
It is an ethylene random copolymer. More preferably, the aromatic vinyl compound content of the aromatic vinyl compound-olefin random copolymer is 5 to 99.9 mol% or less.

This copolymer is a novel copolymer and includes an aromatic vinyl compound-ethylene random copolymer obtained by using the following transition metal compound or by the following production method. Is not limited to the transition metal compound or the production method.

Aromatic vinyl compound used in the present invention
The olefin copolymer is produced from an aromatic vinyl compound and an olefin using a catalyst composed of a transition metal compound represented by the general formula (3) and a co-catalyst.

[0011]

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In the formula, A is an unsubstituted or substituted benzoindenyl group. B is an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted fluorenyl group. When both A and B are unsubstituted or substituted benzoindenyl groups, they may be the same or different. Y is a methylene group or a silylene group having a bond to A and B and having hydrogen or a hydrocarbon group having 1 to 15 carbon atoms as a substituent. These substituents may be different or the same. Y may have a cyclic structure integrally with the substituent. X is hydrogen, halogen, an alkyl group, an aryl group, a silyl group, an alkoxy group, a dialkylamide group, or the like. M is a Group IV metal.

In the general formula (3), A is preferably an unsubstituted or substituted benzoindenyl group represented by the following general formulas 4, 5 and 6.

[0014]

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[0015]

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[0016]

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In the above formulas (4) to (6), R ₁ , R ₂ and R ₃ each represent hydrogen, an alkyl group having 1 to 20 carbon atoms,
6-10 aryl groups, 7-20 alkylaryl groups, halogen atoms, OSiR ₃ groups, SiR ₃ groups or P
An R ₂ group (each R represents a hydrocarbon group having 1 to 10 carbon atoms), R ₁ together, R ₂ and between R ₃ together may be the same or different from each other. In addition, adjacent R ₁ , R
_{The 2} and R ₃ groups may together form a 5- to 8-membered aromatic or aliphatic ring.

As unsubstituted benzoindenyl groups, 4,5
-Benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-1-indenyl and 6,7-benzo-1-indenyl are substituted benzoindenyl groups as 4,5-naphtho- 1-indenyl, 4,5-pyrene-1-indenyl, 4,5-triphenylene-1-indenyl, α-acenaphth-1-indenyl, 3-cyclopenta [c] phenanthryl, 1-cyclopenta [l]
Examples thereof include a phenanthryl group.

In the above general formula (3), B is preferably an unsubstituted or substituted benzoindenyl group similar to the above A, or an unsubstituted or substituted benzoindenyl group represented by the following general formulas 7, 8 and 9: It is a substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. When both A and B are unsubstituted or substituted benzoindenyl groups, they may be the same or different.

[0020]

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[0021]

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[0022]

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In the above formulas (7) to (9), R ₄ , R ₅ , R
₆ is hydrogen, an alkyl group having 1 to 20 carbon atoms, 6 to
10 aryl group, an alkylaryl group having 7 to 20, a halogen atom, OSiR ₃ group, a SiR ₃ group or a PR ₂ group (R represents either a hydrocarbon group having 1 to 10 carbon atoms), R ₄ to each other , R ₅ and R ₆ may be the same or different. However, it is preferable that B has a steric relationship with A in a racemic (or pseudo-racemic) form.

The unsubstituted cyclopentadienyl group is cyclopentadienyl, and the substituted cyclopentadienyl group is 4-aryl-1-cyclopentadienyl,
5-diaryl-1-cyclopentadienyl, 5-alkyl-4-aryl-1-cyclopentadienyl, 4-
Alkyl-5-aryl-1-cyclopentadienyl,
4,5-dialkyl-1-cyclopentadienyl, 5-
Trialkylsilyl-4-alkyl-1-cyclopentadienyl, 4,5-dialkylsilyl-1-cyclopentadienyl and the like can be mentioned. 1-indenyl is used as an unsubstituted indenyl group, and 4-alkyl-1-indenyl, 4-aryl-1-indenyl, 4,5-dialkyl-1-indenyl and 4,6-dialkyl-1- are used as substituted indenyl groups. Indenyl, 5,6-dialkyl-1-
Indenyl, 4,5-diaryl-1-indenyl, 5
-Aryl-1-indenyl, 4-aryl-5-alkyl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 5,6-diaryl-1-indenyl, 4,5,6 -Triaryl-1-indenyl and the like. 9-fluorenyl as an unsubstituted fluorenyl group and 7-methyl- as a substituted fluorenyl group.
9-fluorenyl, 2,3-benzo-9-fluorenyl and the like.

In the above general formula (3), Y represents A, B
And a hydrogen or hydrocarbon group having 1 to 15 carbon atoms
Or a methylene group or a silylene group. Substituent
May be different from each other or the same. Y is Shik
Cyclic structures such as rohexylidene and cyclopentylidene
May be provided. Preferably, Y is bonded to A, B
And a carbon atom having another substituent, such as hydrogen
Or a substituted methyl substituted with a hydrocarbon group having 1 to 15 carbon atoms
Is a ren group. Examples of the hydrocarbon substituent include an alkyl group,
Aryl, cycloalkyl, cycloaryl, etc.
No. Substituents may be different or identical to each other
No. Particularly preferably, Y is -CH_Two-, -CMe
_Two-, -CEt_Two-, -CPh _Two-, Cyclohexylide
And a cyclopentylidene group. Here, Me is
A tyl group, Et represents an ethyl group, and Ph represents a phenyl group.

X is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms,
A silyl group having a hydrocarbon substituent of 4 having 1 to 10 carbon atoms
Or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms. Halogen is chlorine, bromine, etc., alkyl group is methyl group, ethyl group, etc., aryl group is phenyl group, etc., silyl group is trimethylsilyl group, etc., and alkoxy group is methoxy group, ethoxy group, iso group. A propoxy group and the like and a dialkylamide group include a dimethylamide group and the like.

M is a Group IV metal, Zr, Hf, T
i and the like. Particularly preferred is Zr.

Examples of such transition metal compounds include the following compounds. For example, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride {also known as dimethylmethylenebis (benzo [e] indenyl) zirconium dichloride}, di-n-propylmethylenebis (4,5-benzo-1-indenyl) ) Zirconium dichloride, dii-propylmethylenebis (4,
5-benzo-1-indenyl) zirconium dichloride, cyclohexylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclopentylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, diphenylmethylenebis ( 4,5benzo-1-indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (4,5-benzo-
1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethyl Methylene (4-
Phenyl-1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (4,5-benzo-
1-indenyl) zirconium dichloride, dimethylmethylenebis (5,6-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (6 , 7-benzo-1
-Indenyl) zirconium dichloride, dimethylmethylene (6,7-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (α- Acenaphth-1-
Indenyl) zirconium dichloride, dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (1-cyclopenta [l] phenanthryl ) Zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium bis (dimethylamide) and the like. As described above, the Zr complex is exemplified, but the same compounds as described above are preferably used for the Ti and Hf complexes. A mixture of a racemic body and a meso body may be used, but a racemic body or a pseudo racemic body is preferably used. In these cases, D
A body or an L body may be used.

As the co-catalyst used in the present invention, a co-catalyst conventionally used in combination with a transition metal compound can be used. As such a co-catalyst, an aluminoxane (or alumoxane) or a co-catalyst is used. Elemental compounds are preferably used. Further, the present invention is a method for producing an aromatic vinyl compound-olefin copolymer in which the cocatalyst used in this case is an aluminoxane (or alumoxane) represented by the following general formulas (4) and (5).

[0030]

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In the formula, R is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m is 2 to 10 carbon atoms.
It is an integer of 0. Each R may be the same or different.

[0032]

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In the formula, R ′ is an alkyl group having 1 to 5 carbon atoms,
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R 'may be the same or different. As the aluminoxane, methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride.

The addition of the alkyl aluminum is effective for removing a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and the like, which inhibit polymerization, and rendering the polymerization reaction harmless. However, the amount of alumoxane used or the amount of alumoxane used is reduced by a known method such as distillation of styrene or a solvent in advance, or bubbling with a dry inert gas or passing through a molecular sieve. It is not always necessary to add alkyl aluminum at the time of polymerization, if it is slightly increased or added.

In the present invention, a boron compound can be used as a promoter together with the above-mentioned transition metal compound. Boron compounds used as cocatalysts include triphenylcarbenium tetrakis (pentafluorophenyl) borate {trityltetrakis (pentafluorophenyl) borate} and lithium tetra (pentafluorophenyl)
Borate, tri (pentafluorophenyl) borane, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n
-Butyl) ammonium tetra (p-tolyl) phenyl borate, tri (n-butyl) ammonium tetra (p
-Ethylphenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate,
Trimethylammonium tetra (p-tolyl) borate, trimethylammonium tetrakis-3,5-dimethylphenylborate, triethylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis- 2,4-
Dimethylphenyl borate, anilium tetrakis pentafluorophenyl borate, N, N'-dimethyl anilium tetraphenyl borate, N, N'-dimethyl anilium tetrakis (p-tolyl) borate, N, N '
-Dimethylanilium tetrakis (m-tolyl) borate, N, N'-dimethylanilium tetrakis (2,4
-Dimethylphenyl) borate, N, N'-dimethylanilium tetrakis (3,5-dimethylphenyl) borate, N, N'-dimethylanilium tetrakis (pentafluorophenyl) borate, N, N'-diethylanilium tetrakis (Pentafluorophenyl) borate, N, N'-2,4,5-pentamethylanilinium tetraphenyl borate, N, N'-2,4,5-pentaethylanilinium tetraphenyl borate, di-
(Isopropyl) ammonium tetrakispentafluorophenyl borate, di-cyclohexylammonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, tri (methylphenyl) phosphonium tetraphenyl borate, tri (dimethylphenyl) phosphonium tetraphenyl borate, triphenylcarbenium tetrakis (P-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-
Dimethylphenyl) borate, triphenylcarbeniumtetrakis (3,5-dimethylphenyl) borate,
Tropylium tetrakis pentafluorophenyl borate, tropylium tetrakis (p-tolyl) borate,
Tropylium tetrakis (m-tolyl) borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate and the like. These boron compounds and the above-mentioned organoaluminum compounds may be used simultaneously.
In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system that adversely affect the polymerization.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
Examples thereof include o-chlorostyrene, α-methylstyrene, and the like, and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Industrially, styrene, p-methylstyrene and p-chlorostyrene are preferably used, and styrene is particularly preferably used.

The olefin used in the present invention is an α-olefin having 2 to 20 carbon atoms, that is, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene or cyclic olefin. Olefin,
That is, norbornene and norbornadiene are suitable. Two or more of these olefins may be used.
As the olefin, ethylene and propylene are preferable.
In the following description, ethylene will be described as an example of olefin.

In producing the copolymer used in the present invention, an olefin, an aromatic vinyl compound exemplified above, a transition metal compound as a metal complex, and a cocatalyst are brought into contact with each other. Any known method can be used. As a polymerization method, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene,
There is a method using a single or mixed solvent of a saturated aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon such as toluene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride and chloroform. If necessary, a method such as batch polymerization, continuous polymerization, batch polymerization, preliminary polymerization, or gas phase polymerization can be used.

The polymerization temperature is suitably from -78 ° C to 200 ° C, preferably from -50 ° C to 160 ° C. -78
Polymerization temperatures below ℃ are industrially disadvantageous, and above 200 ℃ are not suitable because decomposition of the metal complex takes place. More preferably, it is 0 ° C to 160 ° C industrially.
When an organoaluminum compound is used as a cocatalyst, the ratio of aluminum atom to complex metal atom is 0.1 to 100,000, preferably 10 to 100, based on the metal of the complex.
Used at a ratio of 00. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as the cocatalyst, it is used in a ratio of boron atom / complex metal atom of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

The styrene-ethylene random copolymer which is a typical example of the component (B) used in the present invention will be described in more detail below. Its structure is determined by nuclear magnetic resonance (NMR).

The copolymer used in the present invention has main peaks at the following positions in 13 C-NMR based on TMS. Peaks derived from main chain methylene and main chain methine carbon were around 24 to 25 ppm, around 27 ppn,
Around 30 ppm, around 34 to 37 ppm, 40 to 41 p
pm and around 42 to 46 ppm, and the peaks derived from 5 carbons not bonded to the polymer main chain among the phenyl groups were bonded around 126 ppm and 128 ppm to the polymer main chain among the phenyl groups. A peak derived from one carbon is shown at around 146 ppm. The aromatic vinyl compound-ethylene random copolymer used in the present invention has an aromatic vinyl compound content of 1 in mole fraction.
９９99.9 mol% or less, more preferably 5-9
An aromatic vinyl compound-ethylene random copolymer having a structure of not more than 9.9 mol%, more preferably from 10 to 99.9 mol%, particularly preferably more than 55 mol% and not more than 99.9 mol%. The stereoregularity of the phenyl group of the alternating structure of the aromatic vinyl compound and ethylene represented by the following general formula (1) is larger than 0.75 in the isotactic dyad fraction m, and the following formula ( an aromatic vinyl compound in which the alternating structure index λ given in i) is smaller than 70 and larger than 1, preferably smaller than 70 and larger than 5
It is an ethylene random copolymer. λ = A3 / A2 × 100 Formula (i) Here, A3 is obtained by 13 C-NMR measurement, and three kinds of peaks a derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (2): , B, c. A2 is 13 based on TMS.
It is the sum of the areas of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by C-NMR.

[0042]

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(Wherein Ph is an aromatic group such as a phenyl group,
x represents the number of repeating units and represents an integer of 2 or more. )

[0044]

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(Wherein Ph is an aromatic group such as a phenyl group,
x represents the number of repeating units and represents an integer of 2 or more. )

In the styrene-ethylene random copolymer used in the present invention, the stereoregularity of the phenyl group in the alternating copolymerization structure of ethylene and styrene is defined as the isotactic structure by the isotactic dyad fraction m. (Also called the meso diad fraction) is greater than 0.75,
The structure preferably indicates 0.85 or more, and more preferably 0.95 or more. The isotactic diad fraction m of the alternating copolymer structure of ethylene and styrene is 25 pp
The peak area Ar derived from the r structure of the methylene carbon peak appearing near m, and the peak area Am derived from the m structure
From the following equation (ii). m = Am / (Ar + Am) Formula (ii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. For example, using deuterated chloroform as a solvent,
Based on TMS, the peak derived from the r structure is
The peak derived from the m-structure appears around 25.4 to 25.5 ppm, and around 25.2 to 25.3 ppm.

Further, using heavy tetrachloroethane as a solvent,
The central peak of the triplet of heavy tetrachloroethane (73.8
On the basis of (9 ppm), the peak derived from the r structure appears around 25.3 to 25.4 ppm, and the peak derived from the m structure appears around 25.1 to 25.2 ppm. Note that the m structure represents a meso diad structure, and the r structure represents a racemic diad structure.

In the styrene-ethylene random copolymer used in the present invention, substantially no peak attributed to the r structure in the alternating copolymer structure of ethylene and styrene is observed.

Further, in the styrene-ethylene random copolymer used in the present invention, the stereoregularity of the phenyl group in the chain structure of the styrene unit is isotactic. Isotacticity of the stereoregularity of the phenyl group in the chain structure of the styrene unit means that the isotactic dyad fraction ms (or also referred to as the meso dyad fraction) is larger than 0.5, preferably 0.7 or more. It preferably refers to a structure showing 0.8 or more. The stereoregularity of the chain structure of the styrene unit is determined by a peak position of methylene carbon around 43 to 44 ppm observed by 13 C-NMR and a peak position of a main chain proton observed by 1 H-NMR.

According to US Pat. No. 5,502,133,
The methylene carbon of the isotactic polystyrene chain structure appears at 42.9 to 43.3 ppm, while the methylene carbon of the syndiotactic polystyrene chain structure is 44.0.
Appears around ４４44.7 ppm. The appearance positions of the sharp methylene carbon of syndiotactic polystyrene and the broad peak of 43 to 45 ppm of atactic polystyrene are the peak positions where the other carbons of the styrene-ethylene random copolymer used in the present invention have relatively low intensity. Close to or overlap with. However, in the present invention, the methylene carbon peak is strongly observed at 42.9 to 43.4 ppm, compared with 44.0 to 44.7 pp.
No clear peak is observed near m.

Further, according to US Pat. No. 5,502,133 and a comparative example of the present invention, the peaks attributed to the main chain methylene and methine protons in 1H-NMR are 1.5 to 1.6 ppm in the case of isotactic polystyrene.
2.2 to 2.3 ppm, and in the case of syndiotactic polystyrene, 1.3 to 1.4 ppm, 1.8 to 1.9 p
pm. In the copolymer used in the present invention, the peaks are 1.5 to 1.6 ppm and 2.2 ppm.
The results of this NMR analysis indicate that the styrene chain in the copolymer of the present invention has isotactic stereoregularity.

The isotactic dyad fraction ms of the chain structure of the styrene unit is determined by the 13C-NMR measurement of the methylene carbon or 1H-NMR of the styrene chain structure.
The following formula is derived from each peak of the main chain methylene and methine protons measured. Peak area Ar ′ derived from the syndiotactic dyad structure (r structure) of each peak
And the area Am ′ of the peak derived from the isotactic dyad structure (m structure) can be determined by the following formula (iii). ms = Am ′ / (Ar ′ + Am ′) Formula (iii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent.

The random copolymer used in the present invention includes a chain structure in which aromatic vinyl compound units are bonded by a head-tail, a chain structure in which ethylene units are bonded, and a structure in which aromatic vinyl compound units and ethylene units are bonded. It is a copolymer containing. In the present copolymer, the ratio of these structures contained varies depending on the content of the aromatic vinyl compound or the polymerization conditions such as the polymerization temperature. As the content of the aromatic vinyl compound decreases, the proportion of the chain structure linked by the head-tail of the aromatic vinyl compound unit decreases. For example, in the case of a copolymer having an aromatic vinyl compound content of about 20 mol% or less, the chain structure linked by the head-tail of the aromatic vinyl compound unit shows a peak derived from the structure by ordinary 13 C-NMR measurement. It is difficult to observe directly. But,
By using the transition metal compound of the present invention or by the production method of the present invention, a homopolymer having high activity and stereoregularity can be produced by polymerization of an aromatic vinyl compound alone, that is, an aromatic vinyl compound unit Is capable of forming a head-to-tail linked chain structure, and in the copolymer, at least 1
According to the 3C-NMR method, the proportion of the chain structure linked by the head-tail of the aromatic vinyl compound unit continuously changes corresponding to the content of the aromatic vinyl compound of 20 to 99 mol%. It is clear that a small amount, if any, of a chain structure linked by the head-tail of the aromatic vinyl compound unit may exist in the copolymer. Observing the chain structure linked by the head-tail of the aromatic vinyl compound unit in the copolymer having a styrene content of 20 mol% or less by means of 13C-NMR analysis using a styrene monomer enriched with 13C. Is possible. The same applies to the chain structure of ethylene units.

Aromatic vinyl compound used in the present invention
The chain structure linked by the head-tail of the aromatic vinyl compound unit contained in the ethylene random copolymer is a two or more chain structure which can be represented by the following structure, and preferably a three or more chain structure. is there.

[0055]

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Here, n is an arbitrary integer of 2 or more. Ph
Represents an aromatic group such as a phenyl group.

On the other hand, in the case of a conventionally known pseudo-random copolymer, a head-tail chain structure of an aromatic vinyl compound cannot be found even when the content of the aromatic vinyl compound is around the maximum of 50 mol%. Furthermore, even if homopolymerization of an aromatic vinyl compound is attempted using a catalyst for producing a pseudorandom copolymer, a polymer cannot be obtained. A very small amount of an atactic aromatic vinyl compound homopolymer may be obtained depending on polymerization conditions, etc., which is different from that formed by cationic polymerization by coexisting methylalumoxane or alkylaluminum mixed therein, or by radical polymerization. Should understand.

The peak of the methylene carbon of the conventional pseudorandom copolymer having no stereoregularity derived from the hetero-bond of styrene is 34.0 to 34.5 ppm and 34.5.
It is known to be in two regions of ~ 35.2 ppm. (For example, Polymer Preprints,
Japan, 42 , 2292 (1993)) In the styrene-ethylene random copolymer used in the present invention, the peak attributed to the methylene carbon of the heterogeneous bond structure derived from styrene is observed in a region of 34.5 to 35.2 ppm. However, it is hardly observed at 34.0 to 34.5 ppm. This shows one of the characteristics of the copolymer of the present invention,
This shows that the high stereoregularity of the phenyl group is maintained even in a heterogeneous bond structure derived from styrene as shown in the following formula.

[0059]

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The weight average molecular weight of the styrene-ethylene random copolymer used in the present invention is 60,000 or more, preferably 80,000 or more when the styrene content is 1 mol% or more and less than 20 mol%, and is 20 mol% or more. 3% for less than 9 mol%
It is 10,000 or more, preferably 40,000 or more. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC with standard polystyrene. The styrene-ethylene random copolymer used in the present invention has a practically high molecular weight. Further, the styrene-ethylene random copolymer of the present invention has an alternating structure of ethylene and styrene having high stereoregularity, and simultaneously ethylene chains of various lengths,
It is characterized by having various structures such as styrene hetero bond and styrene chain. Further, the styrene-ethylene random copolymer of the present invention can variously change the ratio of the alternating structure depending on the content of styrene in the copolymer in a range of greater than 1 and less than 70 in the λ value obtained by the above formula. is there. Since this stereoregular alternating structure is a crystallizable structure, the copolymer of the present invention has a styrene content,
Alternatively, by controlling the degree of crystallinity by an appropriate method,
It is possible to provide various properties such as crystalline, non-crystalline, and partially crystalline polymer. λ value is 7
To be less than 0 is to give significant toughness and transparency while being a crystalline polymer, and to become a partially crystalline polymer or to become a non-crystalline polymer. is important.

The copolymer used in the present invention contains approximately 1
In the styrene content range of 0 mol% or more, a higher melting point (according to DSC) can be obtained as compared with a conventional styrene-ethylene copolymer having no stereoregularity and having no styrene chain.

Aromatic vinyl compound used in the present invention
Ethylene random copolymer does not necessarily have to be a pure copolymer. If the structure and stereoregularity are within the above range, other monomers may be copolymerized even if other structures are included. It can be done. Other monomers to be copolymerized include α-olefins having 3 to 20 carbon atoms, such as propylene, and conjugated diene compounds such as butadiene. Further, two or more aromatic vinyl compounds may be copolymerized. Also, depending on polymerization conditions and the like,
A small amount of an atactic homopolymer obtained by thermally, radically or cationically polymerizing an aromatic vinyl compound may be contained, but the amount is 10% by weight or less of the whole. Such a homopolymer can be removed by solvent extraction, but if there is no particular problem in physical properties, it can be used while containing it. Further, for the purpose of improving the physical properties, blending with another polymer is also possible. Blends of the copolymers of the present invention having different styrene contents can also be used.

The low-molecular-weight organic ester-based plasticizer used as the component (A) in the present invention refers to a low-molecular-weight organic ester-based compound used for plasticizing ordinary vinyl chloride resins for medical containers, and includes phthalic acid esters and trimellitates. Among acid esters, adipic esters, sebacic esters, azelaic esters, tartrate esters, citrate esters, malate esters, etc., the molecular weight is preferably from 200 to 80.
A value of 0, more preferably about 250 to 600 is suitable. If the molecular weight is too low, there is a problem of volatility, and if the molecular weight is too high, the molecules do not easily move in the composition, so it is difficult to leach out into the erythrocyte-containing solution, and as a result, the effect of suppressing erythrocyte hemolysis may be reduced. Because.

Considering comprehensively the leachability, the effect of inhibiting hemolysis, the effect on the human body, etc., preferred examples of the plasticizer (A) include di-n-decyl phthalate and di-n-adipate.
-Hexyl, tri-n-butyl acetyl citrate, tri-n-hexyl butyryl citrate, di-n-hexyl acetylmalate, di-n-octyl acetylmalate,
Examples thereof include di-n-hexyl butyrylmalate, di-n-butyl diacetyltartrate, and di-n-hexyl dibutyryl tartrate.

As described above, the base material for a blood bag of the present invention is a single layer or a multilayer containing a resin composition composed of the components (A) and (B) as a forming layer. The term “comprising as a layer” means that the (i) sheet-shaped bag base is composed of only the resin composition of the component (A) and the component (B), and that the (ii) sheet-shaped bag base is the same. This means a multilayer body having at least one layer of the composition and at least one layer of another resin. The case (ii) is employed to adjust and improve the mechanical properties (flexibility, strength), moldability, heat sealability, blocking resistance, heat resistance, etc. of the bag.

Other polymers forming the multilayer body include:
The above-mentioned ethylene-aromatic vinyl compound copolymer (B) is most desirable, but polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polypropylene, poly-4-methylpentene-1,
Polyamide, polyether amide (block copolymer of polyether and polyamide), polyurethane, thermoplastic polyester, and the like are included.

In the case of a multilayer, the thickness of the layers of the other polymers forming the multilayer is important. That is, it is important that the plasticizer component (A) leaches out inside the bag, which is the side that comes into contact with blood, and the other polymer layer should be thinner as long as it is acceptable.
More preferably, it is 0.05 mm or less.

Further, the constitution of the resin composition varies depending on the type of the component (A) or the component (B), whether the composition is a single layer or a multi-layer, etc. weight%,
More preferably, it occupies 1 to 25% by weight. In the case of a multilayer structure, the proportion of the component (A) is preferably relatively high. In consideration of strength, workability, operability, etc., the thickness of the sheet (base material) constituting the bag is 0.60 to 0.08 mm, more preferably 0.50 to 0.08 mm.
0.10 mm is desirable.

In the present invention, a blood bag means a soft plastic container for storing a liquid containing blood components, particularly red blood cells, and such a product can be manufactured by a generally known method. That is, the resin composition is extruded alone or simultaneously with another polymer through a T-die or a circular die, and the obtained flat sheet, tubular sheet, parison and the like are thermoformed, blown, stretched, cut, melted. It can be processed into a predetermined shape and form by appropriately utilizing a method such as attachment (heat sealing).

To manufacture a multilayer sheet, a laminating method can also be applied. Further, in order to prevent blocking between sheets, the inner and outer surfaces of the container may be roughened, that is, embossed, or an anti-blocking agent, a slip agent and the like may be added. In addition, within a range that does not impair the purpose of the present invention,
Other polymers can be further added to the resin composition of the component (A) and the component (B).

[0071]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. In the following description, Bind represents a bisbenzoindenyl group, Me represents a methyl group, and Bu represents a butyl group. Analysis of the copolymers obtained in each of the examples and comparative examples was performed by the following means. The 13C-NMR spectrum was measured using a deuterated chloroform solvent or deuterated 1,1,2,2-tetrachloroethane solvent using α-500 manufactured by JEOL Ltd.
S was measured as a reference. The measurement based on TMS referred to here means that the shift value of the center peak of the triplet 13C-NMR peak of tetrachloroethane is determined based on TMS first, and then each peak shift value of the copolymer is determined by comparing the peak shift value of tetrachloroethane with that of tetrachloroethane. This is calculated based on the triple line center peak. The shift value of the center line of the triplet of tetrachloroethane was 73.89 ppm. The 13C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method with NOE eliminated, using a pulse width of 45 ° and a repetition time of 5 seconds as a standard. By the way, the measurement was performed under the same conditions except that the repetition time was changed to 1.5 seconds, and the quantitative value of the peak area of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range. Determination of the styrene content in the copolymer was performed by 1H-NMR, and the equipment was α-50 manufactured by JEOL Ltd.
0 and AC-250 manufactured by BRUKER were used. Using a heavy chloroform solvent or heavy 1,1,2,2-tetrachloroethane, based on TMS, a peak derived from a phenyl group proton (6.5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 7.5 ppm). 3 ppm). For the molecular weight in the examples, a weight average molecular weight in terms of standard polystyrene was determined using GPC (gel permeation chromatography). The copolymer soluble in THF at room temperature is prepared by using HLC-8 manufactured by Tosoh Corporation using THF as a solvent.
020. The copolymer insoluble in THF at room temperature was measured using 1,2,4-trichlorobenzene as a solvent and GPC-7100 manufactured by Senshu Kagaku. D
The SC measurement was performed using a DSC 200 manufactured by Seiko Denshi Co., Ltd.
_The heating was performed at a heating rate of 10 ° C./min under _two air streams.

Synthetic Example <rac-dimethylmethylenebis (4,5-benzo-1
Synthesis of -indenyl) zirconium dichloride> rac-dimethylmethylenebis (4,5-benzo-1-
Indenyl) zirconium dichloride, also known as rac
-Isopropylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, or rac @ BIn
dC (Me) ₂ -Bind @ ZrCl ₂ ) was synthesized by the following synthesis method. 4,5-benzoindene is Or
ganometallics, 13 , 964 (199)
It was synthesized according to 4).

1) 1,1-isopropylidene-4,5-
Synthesis of Benzoindene The synthesis of 1,1-isopropylidene-4,5-benzoindene is described in Can. J. Chem. 62 , 1751 (19
The synthesis was performed with reference to the synthesis of 6,6-diphenylfulvene described in (84). However, acetone was used as a starting material instead of benzophenone, and 4,5-benzoindene was used instead of cyclopentadiene.

2) Synthesis of isopropylidenebis 4,5-benzo-1-indene In an Ar atmosphere, 21 mmol of 4,5-benzoindene was dissolved in 70 ml of THF, and an equivalent amount of BuLi was added at 0 ° C.
Was added and stirred for 3 hours. 1,1-isopropylidene-
THF in which 21 mmol of 4,5-benzoindene is dissolved
Was added and stirred at room temperature overnight. 100 ml of water and 150 ml of diethyl ether were added and shaken. The organic layer was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was washed with hexane and dried to obtain 3.6 g of isopropylidenebis 4,5-benzo-1-indene. The yield was 46%. 1H-NM
By R spectrum measurement, 7.2 to 8.0 ppm (m,
12H), 6.65 ppm (2H), 3.75 ppm
(4H) has a peak at 1.84 ppm (6H). The measurement was performed using CDCl ₃ as a solvent based on TMS.

3) rac-dimethylmethylenebis (4,
Synthesis of 5-benzo-1-indenyl) zirconium dichloride Under Ar atmosphere, 7.6 mmol of isopropylidenebis 4,5-benzo-1-indene and 7.2 mmol of zirconium tetrakisdimethylamide, also known as Zr (NMe
₂ ) ₄ was charged together with 50 ml of toluene and stirred at 130 ° C. for 10 hours. Under reduced pressure, toluene was distilled off, 100 ml of methylene chloride was added, and the mixture was cooled to -78 ° C. Dimethylamine hydrochloride (14.4 mmol) was slowly added, and the mixture was slowly warmed to room temperature and stirred for 2 hours. After evaporating the solvent, the obtained solid was washed with pentane and then with a small amount of THF, and rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium of yellow lantern represented by the following formula was obtained. 0.84 g of dichloride was obtained. The yield was 21%.

[0076]

Embedded image

According to 1H-NMR spectrum measurement, 8.
01 ppm (m, 2H), 7.75 ppm (m, 2H)
H), 7.69 ppm (d, 2H), 7.48-7.5.
8 ppm (m, 4H), 7.38 ppm (d, 2H),
7.19 ppm (d, 2H), 6.26 ppm (d, 2H)
H) It has a peak at 2.42 ppm (s, 6H). The measurement was performed using CDCl ₃ as a solvent based on TMS. Elemental analysis was performed using an elemental analyzer 1108 (manufactured by Fisons, Inc., Italy).
6% and H 3.98% were obtained. The theoretical value is C6
5.39% and H 4.16%.

<Synthesis of styrene-ethylene random copolymer> Reference Example 1 Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Dehydrated toluene 4
400 ml and 400 ml of dehydrated styrene were charged and heated and stirred at an internal temperature of 50 ° C. 7. About 100 L of nitrogen was bubbled through to purge the system, and triisobutylaluminum was added.
4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.
8.4 mmol of MMAO-3A) was added based on Al.
Immediately after introducing ethylene and stabilizing at a pressure of 10 kg / cm ² G, the catalyst obtained by synthesizing the above transition metal compound from the catalyst tank installed on the autoclave, rac
-Dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride (2.1 μmol) and about 50 ml of a toluene solution of 0.84 mmol of triisobutylaluminum were added to the autoclave. Polymerization was carried out for 4 hours while maintaining the internal temperature at 50 ° C. and the ethylene pressure at 10 kg / cm ² G (ethylene pressure 11 atm).
After the completion of the polymerization, the resulting polymerization solution was poured little by little into excessively vigorously stirred excess methanol to precipitate the produced polymer. After drying under reduced pressure at 60 ° C. until no change in weight was observed, 970 g of a polymer was obtained (P
1).

Reference Example 2 Polymerization was carried out using a 10 L capacity autoclave equipped with a stirrer and a jacket for heating and cooling. Dehydrated toluene 8
Then, 00 ml and 4000 ml of dehydrated styrene were charged and heated and stirred at an internal temperature of 50 ° C. 7. About 100 L of nitrogen was bubbled through to purge the system, and triisobutylaluminum was added.
4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.
MMAO-3A) was added in an amount of 84 mmol based on Al. Immediately after introducing ethylene and stabilizing at a pressure of 1 kg / cm ² G, the catalyst obtained by the above-mentioned synthesis A of the transition metal compound, rac, was taken from a catalyst tank installed on an autoclave.
21 μmol of -dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and about 50 ml of a toluene solution of 0.84 mmol of triisobutylaluminum were added to the autoclave. The polymerization was carried out for 8 hours while maintaining the internal temperature at 50 ° C. and the ethylene pressure at 0.15 MPa (1.5 atm of ethylene pressure). After the completion of the polymerization, the resulting polymerization solution was poured little by little into excessively vigorously stirred excess methanol to precipitate the produced polymer. When dried under reduced pressure at 60 ° C. until no change in weight was observed, 1013 g of polymer (P2) was obtained.

Reference Example 3 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. Dehydrated cyclohexane 6
0 L and 12 L of dehydrated styrene were charged and heated and stirred at an internal temperature of 33 ° C. Triisobutylaluminum 84mmo
l, Methyl alumoxane (Tosoh Akzo Co., Ltd., MMAO
-3 mmol) was added on the basis of Al. Immediately after ethylene was introduced and stabilized at a pressure of 9 kg / cm ² G, the catalyst obtained by the above-mentioned transition metal compound synthesis A, rac-dimethylmethylenebis (4,5- Benzo-1-indenyl) zirconium dichloride 78 µmol, triisobutylaluminum 2 mmol dissolved toluene solution about 100 ml
Was added to the polymerization can. Heat generation started immediately, and cooling water was introduced into the jacket. Although the internal temperature rose to a maximum of 80 ° C, it was maintained at about 70 ° C and the ethylene pressure was increased to 9 kg / c
The polymerization was carried out for 2.5 hours while maintaining the pressure at m ² G (ethylene pressure 10 atm). After completion of the polymerization, after degassing the obtained polymerization solution, it is treated by the crumb forming method as follows,
The polymer was recovered. The polymerization solution was poured into 300 L of heated water at 85 ° C. containing a dispersant with vigorous stirring over 1 hour. Then, after stirring at 97 ° C. for 1 hour, hot water containing crumbs was poured into cold water to collect crumbs. 5 crumbs
By air-drying at 0 ° C. and then vacuum degassing at 60 ° C., a polymer (P)
1) kg of 3) was obtained. The analysis values of the obtained ethylene-styrene copolymer are shown in Table 1.

[0081]

[Table 1]

Examples 1-4, Comparative Examples 1 and 2 (1) Preparation of resin composition: The styrene-ethylene random copolymer (P1) obtained by repeating the polymerization of Reference Example 1 and the polymerization of Reference Example 2 were used. Styrene-ethylene random copolymer (P2) obtained by repeating the polymerization, styrene-ethylene random copolymer (P3) obtained by repeating the polymerization of Reference Example 3, and di-n-decyl phthalate (DnDP) as a plasticizer (B
1), tri-n-hexyl butyryl citrate (BTH
C) (B2) was kneaded using a biaxial melt-kneading extruder at a rate shown in Table 2 at a temperature in the range of 160 to 170 ° C., and the extruded strand was water-cooled, cut, dried, and pelletized weight. The united compositions (D1) to (D5) were obtained.

(2) Sheet preparation: (P1), (P
2) Using (P3) and the pellets of (D1) to (D5), extrude from a single-layer or multilayer T-die at 170 ° C., cool with a casting roller kept at 20 ° C., trim, and trim. A sheet having a length of 0.28 mm and a width of 150 mm was wound at a speed of 5 m / min.

(3) Preparation of container: The sheet obtained above was used, the effective surface area was about 80 cm ² , and the inner size was 50 mm ×
An 80 mm rectangular test bag (capacity: 50 ml) was prepared by a heat sealing method and sterilized with ethylene oxide (65 ° C. ×
5 hours).

(4) Hemolysis test: 400 ml of whole blood was collected from a healthy person into a blood collection bag containing an anticoagulant, and a red blood cell concentrate (CRC) was prepared by a conventional method. The adjusted CRC was aseptically dispensed into the test bags by 50 ml each in a clean bench, stored at 4 ° C. for 3 weeks, and the amount of plasma hemoglobin in each test bag was measured by a conventional method to evaluate the hemolysis level. .

As controls in this test, the case where no plasticizer was contained (Comparative Example 1) and the case where
In the case of a soft PVC sheet containing 2-ethylhexyl (DEHP) 55PHR (Comparative Example 2), a test bag having the same shape was produced and evaluated in the same manner as described above.

[0087]

[Table 2]

(5) Evaluation results: As shown in Table 3, the hemolysis levels of the bags were compared. In Examples 1 to 5 using the base material of the present invention, a commonly used bag made of DEHP plasticized PVC was used. It can be seen that the practicality is not inferior to Comparative Example 2 described above. In addition, the bag made of DEHP plasticized PVC has a problem of waste disposal after use, whereas the blood bag of the present invention does not substantially contain chlorine and thus has no waste disposal problem. On the other hand, in Comparative Example 1 in which a bag made of only the ethylene-styrene copolymer was used, the hemolysis level was large, and it was not suitable as a container for storing red blood cells.

[0089]

[Table 3]

[0090]

As is evident from the above, the blood bag base material of the present invention has a high hemolysis suppressing effect, is versatile, and has substantially no chlorine, so that it is discarded after use. It is easy to dispose of and is expected to make an epoch-making contribution to the field of blood preservation, and its industrial value is high.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J002 BB041 BB111 BB171 BB191 BC011 BC041 BC081 BC091 BC111 BK001 EH096 EH146 FD026 GB01 4J100 AA02Q AA03Q AA04Q AA16Q AA17Q AA19Q AB02P AB03 CA0411

Claims (9)

[Claims] 1. A low molecular weight organic ester plasticizer 30
And (B) the following aromatic vinyl compound
A resin composition comprising 99.5 to 70 parts by weight of an olefin random copolymer. (B) has an aromatic vinyl compound content of 1 to 99.9 mol% or less,
An aromatic vinyl compound-olefin random copolymer having a head-tail chain structure of at least two aromatic vinyl compound units. 2. The aromatic vinyl compound-olefin random copolymer (B) having an aromatic vinyl compound content of 50.
The resin composition according to claim 1, wherein the amount is more than 99.9 mol%. 3. The resin composition according to claim 1, wherein the aromatic vinyl compound-olefin random copolymer (B) is an aromatic vinyl compound-ethylene random copolymer. 4. Stereochemistry of a phenyl group having an alternating structure of an aromatic vinyl compound represented by the following general formula (1) and ethylene contained in the structure of the aromatic vinyl compound-ethylene random copolymer (B): The isotactic diad fraction m is greater than 0.75 and the alternating structure index λ given by the following formula (i) is less than 70;
The resin composition according to claim 3, wherein the resin composition is larger than 1. λ = A3 / A2 × 100 Formula (i) Here, A3 is three peaks a derived from an aromatic vinyl compound-ethylene alternating structure represented by the following general formula (2) and obtained by 13 C-NMR measurement. , B, c. A2 is 13 based on TMS.
It is the total area of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by C-NMR. Embedded image (In the formula, Ph represents an aromatic group such as a phenyl group, and x represents the number of repeating units and represents an integer of 2 or more.) (In the formula, Ph represents an aromatic group such as a phenyl group, and x represents the number of repeating units and represents an integer of 2 or more.) 5. The aromatic vinyl compound-ethylene random copolymer (B) is a 13C-NM based on TMS.
40-41 ppm and / or 42-4 depending on R measurement
The resin composition according to claim 3, which is an aromatic vinyl compound-ethylene random copolymer having a chain structure of an aromatic vinyl compound unit assigned by a peak appearing at 4 ppm. 6. The aromatic vinyl compound-ethylene random copolymer (B) having an aromatic vinyl compound content of 1% or more and less than 20% by mole fraction and an average polystyrene equivalent weight molecular weight of 60,000 or more. 4. The resin composition according to claim 3, wherein 7. The aromatic vinyl compound-ethylene random copolymer (B) has an aromatic vinyl compound content of not less than 20% and not more than 99.9% in mole fraction, and has a weight average molecular weight in terms of polystyrene of 30,000. 3. The resin composition according to claim 2, wherein: 8. The stereoregularity of the chain structure of the aromatic vinyl compound unit contained in the aromatic vinyl compound-ethylene random copolymer (B) is isotactic. Resin composition. 9. A base material for a blood bag, comprising the resin composition according to claim 1 as a forming layer.