JPH07164604A - Base material for medicare container - Google Patents

Abstract

PURPOSE:To provide satisfactory heat sealing properties by using a multilayer laminate consisting of a crystalline polypropylene layer A, a layer B containing a polymer composition of polypropylene amorphous polymer, and a low-density polyethylene layer C, which are positioned as an outermost layer, an intermediate layer and an innermost layer respectively. CONSTITUTION:A multilayer laminate is composed of a crystalline polypropylene copolymer layer A, a layer B containing a polymer composition of polypropylene or polybutene amorphous polymer, and a low-density polyethylene layer C as main components. In addition A, B, C are positioned as an outermost layer, an intermediate layer and an innermost layer respectively. Further, a base material for a medicare container is not only a multilayer laminate of three different kinds and three layers but also can be, for example, the form of a laminate composed of three different kinds and three layers type of A/B/A/C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base material for a medical container, which is suitable for a container for storing liquids such as blood and medical liquids used in the medical field, a tube for transporting (connecting pipe) and the like.

[0002]

2. Description of the Related Art Materials for containers and tubes used in the medical field such as blood sampling, blood transfusion, and liquid transfusion are required to have various performances in addition to safety and hygiene. Among them, flexibility, transparency, heat resistance and The balance of is an important item.

As a polymer material for the above-mentioned use, polyethylene-based polymers such as soft polyvinyl chloride, ethylene-vinyl acetate copolymer, and low-density polyethylene have hitherto been representative examples. In soft polyvinyl chloride, elution and coloring of a plasticizer, May cause problems in disposal.

In the case of polyethylene, the balance between flexibility, transparency and heat resistance is lacking, and low density products have relatively good flexibility and transparency, but the softening point is inevitably low, resulting in a decrease in heat resistance. However, it cannot withstand high-pressure steam sterilization usually performed at 100 to 130 ° C., and is likely to cause blocking, devitrification (whitening), avatar-like unevenness, and deformation. Chemical crosslinking, radiation crosslinking and the like are available as methods for increasing heat resistance, but the manufacturing process is inevitably complicated.

Crystalline polypropylene is also a polymer that is widely used in medical containers, and although its good heat resistance is far more advantageous than polyethylene, it has high rigidity (poor flexibility). Moreover, since the melting point is high, it is difficult to perform heat sealing, and the bag-making property is difficult. It is said that blending styrene elastomer or amorphous polypropylene (atactic polypropylene) is a good way to soften crystalline polypropylene. The sandwiched sandwich type multilayer body (multilayer sheet) is effective as a means for obtaining a flexible sheet while suppressing the tackiness (blocking property) of the blend (proposed in, for example, JP-A-5-77371). .

However, in such a structure, since the crystalline polypropylene still forms the sealing layer and the soft and fluid blend is contained in the intermediate layer, the problem of difficulty in heat sealing becomes more remarkable.

[0007]

DISCLOSURE OF THE INVENTION In order to provide a substrate for medical containers in which the above-mentioned problems of the prior art are solved, the present inventors have focused on improving the sealing property in a multilayer body to which amorphous polyolefin is applied. I examined it.

[0008]

The gist of the present invention is to include a layer (A) made of crystalline polypropylene or a crystalline copolymer containing the crystalline polypropylene as a main component, and a polypropylene-based or polybutene-based amorphous polymer as a polymer composition. Layer (B) and layer consisting of low density polyethylene (C)
And (A), (B) and (C) are present in the outermost layer, the intermediate layer and the innermost layer, respectively. By adopting the constitution, it becomes a medical container base material excellent in sealing property while maintaining transparency, flexibility and heat resistance.

That is, since the innermost layer (inner wall layer of the container) does not come into direct contact with steam during high-pressure steam sterilization, even polyethylene having relatively low heat resistance can withstand sterilization, and the outermost layer (outer wall layer of the container). Due to the heat resistance of polypropylene, the transparency and flexibility of the amorphous polyolefin-containing layer of the intermediate layer, the balance of transparency, flexibility and heat resistance is excellent,
Moreover, since the low-density polyethylene is the sealing layer, it becomes a base material having good processability.

In the present invention, the crystalline polypropylene constituting (A) or a crystalline copolymer containing the crystalline polypropylene as a main component (hereinafter referred to as a polypropylene-based crystalline polymer) is a polypropylene having an ordinary stereoregular structure, that is, isotactic or It is a syndiotactic type polymer.

Although these are appropriately selected, copolymers, particularly random copolymers, are advantageous in terms of transparency and flexibility. As the comonomer, ethylene, butene-1, pentene-1, hexene-1, octene-1, decene-
The amount of α-olefin having 2 to 12 carbon atoms such as 1, dodecene-1, 4-methylpentene-1 is good, and the amount of comonomer is preferably about 3 to 40 mol%, more preferably about 5 to 30 mol%.

A particularly preferred polypropylene-based crystalline polymer has a flexural modulus (JISK7203) of 9,000 k.
Vicat softening point below g / cm ² (JISK7206)
Is 100 ° C. or higher, which is preferable from the viewpoint of the balance of flexibility, transparency and heat resistance.

The polypropylene-based crystalline polymer has a temperature of 2 in consideration of moldability and mechanical properties of the molded product.
MFR (melt flow rate) at 30 ° C. and a load of 2,160 g is preferably 0.3 to 20, more preferably 0.5 to 10
It should be

Next, among the polymers constituting a part of (B), a polypropylene type amorphous polymer (hereinafter referred to as A
(Referred to as PP) is an amorphous atactic polypropylene or a polymer containing the same as a main component, which is produced as a byproduct in the production process of the polypropylene-based crystalline polymer described in (A), and can be produced by radical polymerization or the like. .

In the case of copolymers, the same comonomers as in (A) are used. APP used in the present invention
As a property of, the melt viscosity at 190 ° C. is 300 to 1
0,000 CPS, more preferably 500-80,0
00 CPS, and the softening point measured by the ring and ball method is 100 to
The temperature is preferably 160 ° C, more preferably 110 to 150 ° C.

Among the polymers forming part of (B), polybutene-based amorphous polymers (hereinafter referred to as APB
Is referred to as) means an amorphous polybutene-based polymer containing butene-1 and / or isobutylene as a main component, and can be obtained by a generally known method.

Particularly preferred among these are polymers containing isobutylene as a main component and butene-1 as a comonomer in an amount of about 5 to 30%.

From the viewpoint of moldability and mechanical properties of the base material, APB has a kinematic viscosity at 100 ° C. of 2,000 to 2.
10,000 cst, more preferably 2,500 to 10,
It is suitable that the pour point is about 000 cst and the pour point is 10 to 50 ° C, more preferably about 15 to 45 ° C.

(B) is a polymer composition layer containing the above-mentioned APP or APB. That is, the moldability and sheet forming ability of APP and APB have problems in practical use, and it is necessary to use them in the form of a polymer composition with "other polymer".
The "other polymer" may be the above-mentioned polypropylene-based crystalline polymer because it has excellent compatibility with APP and APB. Isotactic polybutene-1 can also be used because it is crystalline and has good compatibility with APP and APB.

The polymer composition of APP or APB and "other polymer" (polypropylene-based crystalline polymer or isotactic polybutene-1) is flexible,
APP in terms of formability, sheet forming ability, mechanical properties, etc.
Alternatively, APB is 10 to 80% by weight in the polymer composition,
More preferably, it should be 15 to 70% by weight.

Next, as the low density polyethylene (hereinafter referred to as LDPE) constituting (C), so-called linear low density polyethylene (hereinafter referred to as LLDPE) is preferable. This is because it has an excellent balance of transparency, flexibility, heat resistance, etc., as compared with the high-pressure LDPE.

As is well known, LLDPE is a small amount of ethylene (preferably 1 to 10 mol%, more preferably 2 to 8).
Mol%) propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1,
It can be obtained by copolymerizing α-olefins such as dodecene-1,4-methylbenten-1 by a low pressure method or an intermediate pressure method, but considering transparency, flexibility, heat resistance, moldability, mechanical properties, etc. The density is preferably 0.910 to 0.930, the MFR at a temperature of 190 ° C. and a load of 2,160 g is 0.1 to 10, and more preferably 0.5 to 5.0.
It should be

As described at the beginning, the medical container substrate of the present invention comprises a layer (A) made of a polypropylene crystalline polymer, a layer (B) containing APP or APB as a polymer composition, and a layer made of LDPE. It is a multilayer body formed by (C), and (A), (B) and (C) are located in the outermost layer, the intermediate layer and the innermost layer, respectively. With such a form, excellent transparency, flexibility, heat resistance and heat sealability are exhibited.

The medical container base material of the present invention does not necessarily mean only a 3 type, 3 layer type multilayer body.
That is, it is sufficient that at least the above requirements are satisfied, a three-kind four-layer type (eg (A) / (B) / (A) / (C)) or a four-kind four-layer type (eg (A) / (C ₁ ) / (B) /
(C ₂ )) and various other forms.

In some cases, between (A) and (B) and between (B) and (C), an adhesive polymer (eg, polyethylene modified with maleic anhydride, vinyl acetate, methyl methacrylate, etc.) is used. Needless to say, polypropylene or polypropylene) may be used.

The thickness of the above-mentioned multi-layered body depends on the flexibility, transparency, heat resistance and strength required for the use of the substrate for medical containers.
Generally, in the case of a sheet, the total thickness is 0.10 to 1.0 mm, more preferably 0.1 to 0.8 mm, although it depends on the gas barrier property, etc. (A),
The thickness of each of (B) and (C) is 0.0
05-0.15 mm, 0.08-0.7 mm and 0.0
05-0.08 mm, more preferably 0.008-0.
12 mm, 0.1-0.4 mm and 0.008-0.0
About 5 mm is good.

Note that an increase in the thickness of (A) tends to impair the flexibility of the sheet, and an increase in the thickness of (C) tends to decrease the transparency.

In the case of a tube, the total thickness is 0.5 to
The thickness is preferably 3.0 mm, more preferably 0.8 to 2.0 mm, and the thickness of each layer of (A) and (C) may be set to the same level as that of the sheet. The thickness per layer of (B) is preferably 0.1 to 2.5 mm, more preferably 0.2.
About 1.5 mm is preferable. The inner diameter of the tube is 1
It is generally 20 mm, and more preferably 2 to 15 mm.

In the present invention, the term "medical container" means a container or tube for storing or carrying a liquid such as blood or medical liquid used in medical treatment, and such a product can be obtained by a generally known method.

In the case of a container, the (A) layer, the (B) layer and the (C) layer (in some cases, other polymers may be used) are extruded through a multi-layer T die or a multi-layer circular die. (The melting temperature is preferably 180 to 250 ° C., more preferably 190 to 230 ° C.), the obtained flat sheet, tubular sheet, parison, etc. are subjected to thermoforming, blowing, stretching, cutting and fusing (heat sealing). ) Or the like may be used as appropriate to process into a predetermined shape and form.

Considering the heat sealability, the sheet is preferably in a non-stretched state. Heat seal is 170-210 ℃, pressure is 5k
g / cm ² or less, and the time may be 2 to 7 seconds. (In contrast, when the innermost layer (sealing layer) is a polypropylene-based crystalline polymer, a temperature of 210 to 250 ° C. or so is required. Defects are likely to occur in the state).

Addition of a styrene-based elastomer or an olefin-based elastomer to any of the layers (A), (B) and (C) within a range not impairing the gist of the present invention,
In order to prevent blocking between the sheets, the inner surface or outer surface of the container may be roughened. The tube is manufactured in the same manner.

The base material of the present invention is particularly useful as a container for blood components and as a container for physiological saline, electrolyte solution, dextran preparation, mannitol preparation, saccharide preparation, amino acid preparation, fat emulsion and the like.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Examples 1 to 4, Comparative Example 1) (1) Polymer Raw Material and Sheet Raw Material Polymer: The raw material polymers used are shown in Table 1.

Preparation of polymer composition for forming layer (B): Using polypropylene-based crystalline polymer and APP (or APB) as raw materials, a biaxial melt-kneading extruder having a diameter of 45 mm and a predetermined ratio of 190 to 190. The extruded strands kneaded and kneaded in the temperature range of 200 ° C. were water-cooled, cut and dried to obtain pelletized polymer compositions shown in Table 1.

Sheet preparation: 21 from multi-layer T-die
A three-layer sheet was extruded at 0 to 220 ° C., cooled by a casting roller kept at 20 ° C., trimmed, and a sheet having a thickness of 0.36 mm and a width of 200 mm was wound at a speed of 5 m / min. Table 2 shows the structure of the multilayer sheet.

(2) Evaluation method of sheet: Evaluation of flexibility of multilayer sheet: The sheet obtained in (1) -is cut into a dumbbell shape, and the tensile elastic modulus is measured according to JIS K7113 to obtain a measure of flexibility. And

Evaluation of Transparency of Multilayer Sheet: (1)-
The sheet obtained in (1) was cut into a size of 150 mm × 250 mm, and heat-sealed so that the layer (C) became a sealing layer (for the sealing conditions, described in (2)-) to prepare a bag, 600 ml of physiological saline was added and sealed.
Put this chemical solution container in a retort type high pressure steam sterilizer,
Temperature 110 ° C, gauge pressure 1.8 kg / cm ² , time 45
It was processed under the condition of minutes. After cooling to room temperature and leaving it for 48 hours, the sheet was cut out and the transmittance in water at a wavelength of 450 nm was measured by Shimadzu double beam type self-recording spectrophotometer UV-300.
Was used as a measure of transparency.

Evaluation of heat sealability of multilayer sheet: (1)
Two sheets obtained in step (-) were combined so that the layer (C) became a sealing layer, and the sealing dimensions were 10 mm width × 20 mm length, the pressure was 2 kg / cm ² , and the temperature was 17 seconds.
Heat sealing was performed in the range of 0 to 230 ° C. Then, the heat-sealed sample was measured for peeling strength at 180 ° C using a tensile tester to secure a strength of 2 kg / cm, and the temperature when "burr" (flesh pool or humpback) was small Seal temperature ". (The container of (2)-was manufactured within this proper sealing temperature range).

Heavy metal and eluate test: According to the Japanese Pharmacopoeia general test method “Plastic container test method for infusion”,
A test was conducted on the sheet obtained in (1)-.

[0042]

[Table 1]

(2) Experimental results (see Table 2) Extrusion molding of the sheet was performed smoothly, and no foreign matter, foaming, blocking, etc. were observed in any composition,
A highly uniform sheet was obtained.

It was confirmed that the results of the heavy metal and eluate tests were compatible with the Japanese Pharmacopoeia in any of the compositions.

As shown in Table 2 which shows the relationship between the sheet composition and the flexibility, transparency and heat sealability, the crystalline polypropylene polymer is the outermost layer ((A) layer) and the amorphous polyolefin-containing polymer composition is the intermediate layer. The performance of the sheet including the layer ((B) layer) and the low density polyethylene as the innermost layer ((C) layer) was good.

On the other hand, when the innermost layer is made of a crystalline polypropylene polymer, the sealing temperature has to be raised to a high temperature, so that the flexible (B) layer protrudes from the sealing portion and heat sealing cannot be performed in a good state. It was

[0047]

[Table 2]

[0048]

As described above, the medical container substrate of the present invention is produced by skillfully utilizing the heat resistance of crystalline polypropylene polymer, the flexibility of amorphous polyolefin and the good heat sealability of low density polyethylene. Since it is excellent in transparency, flexibility, heat resistance and bag-forming property and has good moldability, it has a high industrial value.

[0049]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Ochiai 818 Sanendaira, Fujinomiya-shi, Shizuoka Terumo Co., Ltd.

Claims (1)

[Claims] 1. A layer (A) made of crystalline polypropylene or a crystalline copolymer containing it as a main component, a layer (B) containing a polypropylene-based or polybutene-based amorphous polymer as a polymer composition, and low-density polyethylene. A multilayer body formed by layer (C), wherein (A), (B) and (C) are present in the outermost layer, the intermediate layer and the innermost layer, respectively.