JPH09262948A - Resin laminate and its use - Google Patents

Abstract

(57) Abstract: A resin laminate of the present invention comprises an outer layer, an intermediate layer portion including one or more intermediate layers, and an inner layer, and the outer layer is a propylene homopolymer or a polypropylene / α-olefin. A composition formed of a random copolymer, in which at least one intermediate layer constituting the intermediate layer portion contains one material selected from an elastomer, polyethylene and polypropylene, or a composition containing two or more materials. And an inner layer formed of a propylene / α-olefin random copolymer or polyethylene, and
The resin laminate has a haze of 30% or less after the retort sterilization treatment,
It is characterized in that the deformation starting temperature is a temperature exceeding 121 ° C. The container of the present invention is characterized by using the above resin laminate as a constituent material. [Effect] The above resin laminate and container are excellent in heat resistance, transparency, flexibility, mechanical strength characteristics such as low temperature impact strength, and hygiene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a resin laminate such as a film, a sheet and a tube, and its use. More specifically, each layer is made of a polyolefin resin composition such as polypropylene and has three or more layers. And a container using the resin laminate, wherein the container is sterilized under high temperature conditions, such as a retort pouch for containing medicines and foods, an infusion bag, and the like. .

[0002]

BACKGROUND OF THE INVENTION As medical containers currently in use, a hard container made of glass, polyethylene, polypropylene or the like and a soft bag made of polyvinyl chloride containing a plasticizer are known.

However, in the above-mentioned hard container, it is necessary to introduce air by using a ventilation needle or an infusion set with a ventilation hole when dropping a content liquid such as blood or a drug solution. There is a possibility that the content liquid may be contaminated by the above. On the other hand, the soft bag, when dropping the content liquid,
Unlike the above-mentioned hard container, it is not necessary to introduce air, and since the bag itself is squeezed by the atmospheric pressure along with the dropping of the content liquid, there are advantages such as hygiene, convenience of transportation, and small volume of waste. is there. However, there are problems such as toxicity of plasticizers and residual monomers contained in polyvinyl chloride.

On the other hand, a medical bag using a polymer such as an ethylene / vinyl acetate copolymer or an elastomer as an intermediate layer has been proposed for the purpose of improving flexibility, transparency and hygiene. (JP-A-58-165866).

However, in this medical bag, the polymer used for the intermediate layer is poor in heat resistance, so that there is a problem that the bag is wrinkled during the retort sterilization process.
In addition, conventional medical bags made from polyethylene have a slightly insufficient heat resistance and cannot raise the sterilization temperature, so the sterilization time will be longer or the sterilization process will be performed in a highly clean atmosphere. Inefficiency in the sterilization process, which must be performed, is a problem.

Therefore, it has good hygiene and flexibility, does not lose transparency even after sterilization treatment of 115 ° C. or higher, particularly 121 ° C., as shown in the Japanese Pharmacopoeia, and is excellent in heat resistance and wrinkles. The appearance of a medical container that does not cause deformation or deformation is desired.

Generally, a polyolefin resin is used for a sealant film of a food laminate packaging material, and it is often sterilized under a condition of 121 ° C. or higher for retort foods. Polypropylene films with high melting points are often used.

However, impact resistance has been emphasized due to the pouching of large-scale commercial containers in recent years, and at the same time, transparency is required from the viewpoint that it is better to confirm the contents. ing.

Since the polypropylene film is generally inferior in low temperature impact resistance, it cannot satisfy the above requirements. Further, as a film having improved low temperature impact resistance, there are films such as ethylene / propylene block copolymers, but since these films have poor transparency,
It cannot be used in areas requiring transparency.

Therefore, the appearance of a resin laminate excellent in hygiene, transparency, flexibility, low temperature impact resistance and heat resistance and a container using the resin laminate have been desired.

[0011]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is heat-resistant so that there is almost no deformation even when sterilized under severe conditions of 121 ° C. or higher. To provide a resin laminate that can be used as a material for a container having excellent mechanical properties such as transparency, flexibility, low-temperature impact strength, and hygiene, as well as excellent properties, and a container using the resin laminate. I am trying.

[0012]

SUMMARY OF THE INVENTION The resin laminate according to the present invention has an outer layer [I].
And an outer layer [I], which is a resin laminate comprising an inner layer [II] and an inner layer [III] containing one or more intermediate layers.
Is a propylene homopolymer (a) or a propylene / α-olefin random copolymer (b) comprising 50 mol% or more of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms. , At least one intermediate layer [II-1] constituting the intermediate layer portion [II],
Formed of a composition containing one kind of material selected from an elastomer (c), polyethylene (d) and polypropylene (e), or a composition containing two or more kinds of materials,
The inner layer [III] is formed of a propylene / α-olefin random copolymer (f) consisting of 50 mol% or more of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms, or polyethylene (g). Becomes
Moreover, the resin laminate has (i) a haze of 30% or less after the retort sterilization treatment, and (ii) a deformation start temperature [Td
(° C.)] is a temperature exceeding 121 ° C.

The resin laminate according to the present invention preferably has a Young's modulus of 3,500 kg / cm ² or less. In the resin laminate according to the present invention, at least one of the outer layer [I], the intermediate layer [II-1] and the inner layer [III] has a density of 0.950 g / cm ³ or more and a molecular weight of It is preferably formed of a polyolefin composition containing 5 to 30% by weight of high-density polyethylene (h) having a distribution (Mw / Mn) of 4.0 or less.

When the thickness of the intermediate layer portion [II] in the resin laminate according to the present invention is 40% or more and less than 75% of the total thickness of the resin laminate, the intermediate layer [II-1] has a density of Of 0.950 g / cm ³ or more, the molecular weight distribution (Mw / M
n) is high density polyethylene (h) of 4.0 or less 5
It is preferably formed of a polyolefin composition containing an amount of not less than 15% by weight and not more than 15% by weight.

Further, the thickness of the intermediate layer portion [II] in the resin laminate according to the present invention is 7 times the thickness of the entire resin laminate.
When it is in the range of 5 to 90%, the intermediate layer [II-1]
Is formed of a polyolefin composition containing 15 to 30% by weight of high-density polyethylene (h) having a density of 0.950 g / cm ³ or more and a molecular weight distribution (Mw / Mn) of 4.0 or less. Is preferred.

The container according to the present invention is characterized by using the resin laminate according to the present invention as a constituent material as described above. The “resin laminate” in the present specification specifically refers to a film, sheet, or tube having three or more layers.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The resin laminate and the container using the resin laminate according to the present invention will be described in detail below.

Resin Laminated Body First, the resin laminated body according to the present invention will be described. The resin laminate according to the present invention comprises an outer layer [I], an intermediate layer portion [II] including one or more intermediate layers, and an inner layer [III].

<Outer Layer [I]> The outer layer of the resin laminate according to the present invention has a propylene homopolymer (a), or 50 mol% or more of propylene and ethylene or 4 carbon atoms.
A propylene / α-olefin random copolymer (b) consisting of α-olefin of 8 to 8 is used.

Specific examples of such α-olefins include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like, in addition to ethylene. Among them, ethylene and 1-butene are preferred.

These α-olefins can be used alone or in combination of two or more. Examples of the propylene / α-olefin random copolymer (b) used in the present invention include propylene / ethylene random copolymer, propylene / 1-butene random copolymer,
Propylene / ethylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene /
Examples thereof include 1-octene random copolymer.

Melt flow rate (MFR; ASTM D 1238) of the above-mentioned propylene homopolymer (a) and propylene / α-olefin random copolymer (b).
190 ° C, load 2.16 kg) is usually 0.1-20 g
/ 10 minutes, preferably 0.2 to 10 g / 10 minutes, more preferably 0.5 to 8 g / 10 minutes.

The above-mentioned propylene homopolymer (a) preferably has a melting point in the range of 150 to 170 ° C.
The propylene / α-olefin random copolymer (b) preferably has a melting point in the range of about 125 ° C to 145 ° C.

In the present invention, as the outer layer forming component,
In addition to the propylene homopolymer (a) or the propylene / α-olefin random copolymer (b) as described above, it is desirable to use a high density polyethylene (h) in combination.

The high density polyethylene used in the present invention (h) has a density, 0.950 g / cm ³ or more, preferably in the range of 0.960~0.970g / cm ^3, and a molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) is 4.0 or less, preferably 3.5 or less.

The molecular weight distribution (Mw / Mn) is GP
It is obtained by the C method. Specifically, GP manufactured by Millipore
It is measured as follows using C-150C. The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was 0-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and antioxidant. BHT [Takeda Pharmaceutical Co., Ltd.] 0.025% by weight, 1.0m
The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. The molecular weight of standard polystyrene is Mw.
For <1000 and Mw> 4 × 10 ⁶ , Toso-
Using polystyrene manufactured by Co., Ltd., 1000 <Mw <4 × 1
For No. ⁶ , polystyrene manufactured by Pressure Chemical Co. was used.

The high-density polyethylene (h) used in the present invention is an ethylene homopolymer or an ethylene / α-olefin copolymer composed of 50 mol% or more of ethylene and an α-olefin having 3 to 12 carbon atoms. Is.

Specific examples of such α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene. And so on. Among them, 1-butene,
4-Methyl-1-pentene, 1-hexene and 1-octene are preferred.

These α-olefins may be used alone or in combination of two or more. In the present invention, an ethylene homopolymer is preferably used as the high density polyethylene (h).

When high-density polyethylene (h) is used as one component of the outer layer of the resin laminate according to the present invention, the high-density polyethylene (h) is a propylene homopolymer (a).
And / or 5 to 30% by weight, and preferably 5 to 30% by weight, based on 100% by weight of the polyolefin composition (whole outer layer forming component) containing the propylene / α-olefin random copolymer (b) and the high-density polyethylene (h). It is used in a proportion of up to 20% by weight.

In the present invention, when the high density polyethylene (h) is used as a component for forming the outer layer [I] in the above proportions, heat resistance and mechanical strength are maintained without impairing the flexibility and transparency of the container. The characteristics can be further improved, and the intermediate layer and the outer layer [I] can be easily heat-welded.

<Intermediate Layer Part [II]> The intermediate layer part [II] of the resin laminate according to the present invention comprises one or more intermediate layers, and at least one intermediate layer [II-1]. Is formed of one kind of material selected from the elastomer (c), polyethylene (d) and polypropylene (e), or a composition containing two or more kinds of materials.
That is, the above components (c), (d) or (e) can be used alone, respectively, or the components (c) and (d) can be used in combination, or the components (c) and (e) can be used in combination. , Combination of components (d) and (e), components (c), (d) and (e)
It can be used together with.

Intermediate Layer [II-1] The elastomer (c) used as a component for forming the above intermediate layer [II-1] has a density of usually 0.880 g / cm ³ or more and less than 0.905 g / cm ³ , preferably Is 0.885
It is preferably an α-olefin copolymer rubber in the range of 0.900 g / cm ³ .

Specific examples of such an α-olefin copolymer rubber include propylene / 1-butene / ethylene copolymer rubber (PBER), propylene / ethylene copolymer rubber (PER), ethylene / propylene. Copolymer rubber (EPR), ethylene / 1-butene copolymer rubber (EB
R), propylene / 1-butene copolymer rubber (PBR),
Alternatively, the composition is preferably composed of two or more of these materials.

The polyethylene (d) used as a component for forming the intermediate layer [II-1] is an ethylene homopolymer, 5
It is an ethylene / α-olefin copolymer composed of 0 mol% or more of ethylene and an α-olefin having 3 to 12 carbon atoms.

Specific examples of such α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene. And so on. Among them, 1-butene,
4-Methyl-1-pentene, 1-hexene and 1-octene are preferred.

These α-olefins can be used alone or in combination of two or more. Middle layer [II-1]
Among the above-mentioned polyethylene (d), a forming component of
Linear polyethylene is particularly preferable. The density of this linear polyethylene is 0.905 to 0.940 g / cm ³ ,
It is preferably in the range of 0.910 to 0.930 g / cm ³ .

When linear polyethylene having a density within the above range is used in the intermediate layer [II-1], a resin laminate capable of providing a container having excellent flexibility, impact resistance and transparency is obtained. To be

The polypropylene (e) used as a component for forming the intermediate layer [II-1] is 50% by mole of the propylene homopolymer (a) for forming the outer layer [I] described above.
The above propylene and ethylene or 4 to 8 carbon atoms
The same propylene homopolymer as the propylene / α-olefin random copolymer (b) consisting of α-olefin, or propylene / α-olefin random copolymer is used.

Specific examples of such α-olefins include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like in addition to ethylene. Among them, ethylene and 1-butene are preferred.

These α-olefins can be used alone or in combination of two or more. Examples of the propylene / α-olefin random copolymer used in the present invention include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / ethylene / 1-butene random copolymer, propylene / Examples thereof include 1-hexene random copolymer and propylene / 1-octene random copolymer.

The melt flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) of the above-mentioned propylene homopolymer and propylene / α-olefin random copolymer is usually 0.1 to 20 g / 10 min. It is preferably in the range of 0.2 to 10 g / 10 minutes, more preferably 0.5 to 8 g / 10 minutes.

The above propylene homopolymer has a melting point of 1
It is preferably in the range of 50 to 170 ° C. Also,
The propylene / α-olefin random copolymer is
The melting point is preferably in the range of about 125 ° C to 145 ° C.

Further, the melt flow rate (MFR; ASTM D 1238, 190 ° C.) of the above elastomer (c), polyethylene (d) and polypropylene (e),
Load 2.16 kg) is usually 0.1 to 20 g / 10 minutes,
It is preferably in the range of 0.2 to 10 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes.

In the present invention, in addition to the above elastomer (c), polyethylene (d) and polypropylene (e) as a forming component of the intermediate layer [II-1], it is necessary as an outer layer forming component described above. It is desirable to use a high-density polyethylene (h) similar to the high-density polyethylene (h) used according to 1.

Intermediate layer [II-1] of the resin laminate according to the present invention
When the above-mentioned high-density polyethylene (h) is used as one forming component, the high-density polyethylene (h) is a polyolefin composition containing an elastomer (c), polyethylene (d), polypropylene (e) and high-density polyethylene (h). It is used in a proportion of 5 to 30% by weight, preferably 5 to 20% by weight, based on 100% by weight of the whole intermediate layer [II-1] forming component.

The preferable blending amount of the high-density polyethylene (h) as a component for forming the intermediate layer [II-1] depends on the ratio of the thickness of the intermediate layer portion [II] to the thickness of the entire resin laminate. (1) When the thickness of the intermediate layer portion [II] is 40% or more and less than 75% of the total thickness of the resin laminate, the high-density polyethylene (h) is 5% with respect to 100% by weight of the polyolefin composition. It is preferably used in an amount of not less than 15% by weight and not more than 15% by weight. (2) When the thickness of the intermediate layer portion [II] is within the range of 75 to 90% of the total thickness of the resin laminate, the high-density polyethylene (h) is based on 100% by weight of the polyolefin composition. Therefore, it is preferably used in an amount of 15 to 30% by weight.

In the present invention, when the high density polyethylene (h) is used as a component for forming the intermediate layer [II-1] in the above proportions, heat resistance is maintained without impairing the flexibility and transparency of the container. Further, the mechanical strength characteristics can be further improved, and the heat welding of the outer layer [I] and the intermediate layer [II-1] and the heat welding of the inner layer [III] and the intermediate layer [II-1] are easy. Is.

Intermediate Layer Other than Intermediate Layer [II-1] In the present invention, the intermediate layer portion [II] may be one layer of the above-mentioned intermediate layer [II-1] or one intermediate layer [II-1]. It is also possible to have a multilayer structure composed of the intermediate layer [II-1] and an intermediate layer made of another type of composition or simple substance. The intermediate layer may be an intermediate layer [II-1] having a composition different from the specific composition of the intermediate layer [II-1].

As the intermediate layer portion [II] of such a multilayer structure, for example, between the two intermediate layers [II-1] formed of the above-mentioned polyethylene (d), the two intermediate layers [II-
1) polyethylene of a type different from polyethylene (d), and having a thickness of 20% of the total thickness of the intermediate layer portion [II].
%, An intermediate layer portion having a three-layer structure in which one intermediate layer having a thickness of about 1% or less is provided.

Examples of the above-mentioned "other type of polyethylene" include (i) different mixing ratios of the above-mentioned polyethylene (d) and high-density polyethylene (h) in one intermediate layer [II-1]. And (ii) a polyethylene composition in which the mixing ratio of the elastomer (c) and the polyethylene (h) in the intermediate layer [II-1] is different.

<Inner Layer> The inner layer [III] of the resin laminate according to the present invention comprises a propylene / α-olefin random copolymer consisting of 50 mol% or more of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms. Polymer (f),
Alternatively, polyethylene (g) is preferably used.

Specific examples of the α-olefin constituting the propylene / α-olefin random copolymer (f) include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Among them, ethylene and 1-butene are preferred.

These α-olefins may be used either individually or in combination of two or more. Examples of such propylene / α-olefin random copolymer (f) include propylene / ethylene random copolymer,
Propylene / 1-butene random copolymer, propylene
Ethylene / 1-butene random copolymer, propylene / 1-
Examples include hexene random copolymers and propylene / 1-octene random copolymers.

The polyethylene (g) used as a component for forming the inner layer [III] is the above-mentioned intermediate layer [II-1].
Ethylene homopolymer or an ethylene / α-olefin copolymer composed of 50 mol% or more of ethylene and one or more kinds of α-olefin having 3 to 12 carbon atoms, which is the same as the polyethylene (d) used in Is.

As the forming component of the inner layer [III], linear polyethylene (polyethylene (g)) is particularly preferable.
The linear polyethylene here has a slightly different density range from the linear polyethylene preferably used as a component for forming the intermediate layer [II-1]. That is, the density of the linear polyethylene used in the inner layer [III] is 0.930 to
0.945 g / cm ³ , preferably 0.930 to 0.9
It is in the range of 40 g / cm ³ .

The inner layer [III] of the resin laminate is required to withstand high temperatures during sterilization under high temperature conditions and to be able to maintain the seal strength, but the linear polyethylene having the above density is required. The inner layer [III]
Can meet this requirement.

The melt flow rate of this linear polyethylene (MFR; ASTM D1238, 190)
C, load 2.16 kg) is usually 0.1-20 g / 10
Min, preferably 0.2 to 10 g / 10 min, more preferably 0.5 to 5 g / 10 min.

In the present invention, as a forming component of the inner layer [III], in addition to the above-mentioned linear polyethylene, the same high-density polyethylene (h) as is optionally used in the above-mentioned intermediate layer [II-1] is used. It is preferable to use high-density polyethylene (h) together.

The high-density polyethylene (h) used in the inner layer [III] has the same density and the same molecular weight distribution as the high-density polyethylene (h) used in the intermediate layer [II-1] described above. It may have (Mw / Mn) or may be different. Preferred high density polyethylene (h) used as a forming component of the inner layer [III]
Is the same as the preferable high-density polyethylene (h) which may be used in the above-mentioned intermediate layer [II-1].

When the above-mentioned high-density polyethylene (h) is used as one forming component of the inner layer [III] of the resin laminate according to the present invention, the high-density polyethylene (h) is 100 parts by weight of the total amount of the forming components of the inner layer [III]. 5 to 30% by weight, preferably 5 to 15% by weight, more preferably 5 to 5% by weight.
Used at a rate of 10% by weight.

The optimum blending ratio of the high-density polyethylene (h) used for forming the inner layer [III] is determined in consideration of the density of the linear polyethylene and the like. In the present invention, when the high density polyethylene (h) is used as a component for forming the inner layer [III] in the above proportion, heat resistance and mechanical strength characteristics are further improved without impairing the flexibility and transparency of the container. Can be improved and also the middle and inner layers [II
I] is easy to heat weld.

<Resin Laminate> The resin laminate according to the present invention comprises the outer layer [I], the intermediate layer [II] and the inner layer [III] as described above.

The thickness ratio of each layer in the resin laminate according to the present invention is as follows: outer layer: intermediate layer part: inner layer = 5 to 30:90 to 4
0: 5-30, preferably 5-20: 90-60: 5
Twenty.

Of the resin laminates according to the present invention, the following resin laminates are preferable. (1) At least one of the outer layer [I], the intermediate layer [II] and the inner layer [III] has a density of 0.950 g / cm 3.
³ or more, preferably 0.960 to 0.970 g / cm ³
And a resin laminate formed of a polyolefin composition containing 5 to 30% by weight of high-density polyethylene (h) having Mw / Mn of 4.0 or less, preferably 3.5 or less, particularly a linear polyethylene composition. body. (2) The thickness of the intermediate layer portion [II] is 40% or more and less than 75% of the total thickness of the resin laminate, and the intermediate layer [II-1]
However, the density is 0.950 g / cm ³ or more, preferably 0.
960 to 0.970 g / cm ³ and Mw / Mn of 4.0
Hereinafter, a resin laminate formed of a polyolefin composition, particularly a linear polyethylene composition, containing a high density polyethylene (h) of preferably 3.5 or less in an amount of 5% by weight or more and less than 15% by weight. (3) The thickness of the intermediate layer portion [II-1] is within the range of 75 to 90% of the total thickness of the resin laminate, and the intermediate layer [II-1]
However, the density is 0.950 g / cm ³ or more, preferably 0.
960 to 0.970 g / cm ³ and Mw / Mn of 4.0
A polyolefin composition containing 15 to 30% by weight of high density polyethylene (h), which is preferably 3.5 or less,
In particular, a resin laminate formed of a linear polyethylene composition.

The resin laminate according to the present invention has a haze (ASTM D-1003-61) after retort sterilization treatment of 30% or less, preferably 20 to 0%. The conditions for this retort sterilization treatment are usually 115 to 121 ° C. and 20 to 30 minutes.

In the resin laminate according to the present invention, the deformation start temperature [Td (° C)] is over 121 ° C.
The deformation start temperature [Td (° C)] is measured as follows.

That is, a bag or container made of a resin laminate was subjected to hot water sterilization at a sterilization temperature of 30 minutes with an RK-4016 type small retort high-pressure steam sterilizer manufactured by Alp Co., and a sample taken out from the sterilizer. Is visually observed to evaluate the deformation. Starting with a sterilization temperature of 110 ° C, 1
The sterilization temperature is increased by 1 ° C after each sterilization. This operation is repeated, and when the sample taken out from the sterilizer is first deformed, the sterilization temperature is set to [Td (° C)].

The resin laminate according to the present invention has a Young's modulus (J
IS K 7113) is preferably 3,500 kg / cm
² or less, more preferably 1,500 to 2,500 kg
Within the range of / cm ² .

The resin laminate according to the present invention is formed into a film, a sheet or a tube according to the purpose of use. Among them, as the method for producing the film and the sheet, conventionally known water-cooled or air-cooled coextrusion inflation method, coextrusion T-die method, dry lamination method, extrusion lamination method and the like can be mentioned, but especially transparency, hygiene, etc. From the standpoints of film performance and economy, the water-cooled coextrusion inflation method and the coextrusion T-die method are preferable. The manufacturing conditions in the above-described film and sheet manufacturing method are, of course, set to appropriate temperatures and speeds so as not to cause deterioration of the resin.

The above-mentioned film or sheet is formed into an appropriate thickness depending on the field of use. For example, when a film or sheet is used for medical purposes, its thickness is 50-100.
The thickness is 0 μm, preferably 100 to 700 μm, and more preferably 150 to 300 μm.

Further, as a method for producing the tube, an ordinary extrusion blow molding method can be mentioned. The tube is formed to have an appropriate thickness and diameter depending on the field of use. The resin laminates of various forms obtained as described above are excellent in hygiene, transparency and flexibility, and also excellent in heat resistance, and thus can be used as a material for various containers.

[0073] container will now be described container according to the present invention. The container according to the present invention uses the above resin laminate according to the present invention as a constituent material.

In the present invention, a container using the above-mentioned preferred resin laminate according to the present invention as a constituent material is preferable. The container generally comprises a bottom portion, a wall portion and a lid portion, but the container according to the present invention uses the resin laminate according to the present invention as a constituent material on at least the wall portion.

The container according to the present invention may be a container having one chamber or a multi-chamber container having two or more chambers. The multi-chamber container has, for example, a plurality of chambers which are separated from each other by an easily peelable partition formed by sandwiching an easily peelable tape between the resin laminates according to the present invention and heat-sealing them. A container etc. are mentioned.

The container according to the present invention is made of a resin laminate in which the thickness ratio of the outer layer [I], the intermediate layer portion [II], and the inner layer [III] is within the above range. It has excellent heat resistance, does not cause wrinkles or deformation even after retort treatment at 121 ° C. for 20 minutes, and has excellent transparency and flexibility.

Of the resin laminates according to the present invention, the film and sheet resin laminates are suitable as a material for bag-shaped flexible containers such as infusion bags. When a container is manufactured using a film- or sheet-shaped resin laminate, this resin laminate is cut and heat-welded by an ordinary method, and if necessary, a mouth member or the like is attached using a means such as heat-welding. As a result, a container having a predetermined shape and size can be manufactured. In particular, in the case of producing the multi-chamber container as described above, after the film or sheet-shaped resin laminate is cut, the easily peelable tape is inserted between the resin laminates, and the easily peelable tape is sandwiched. A plurality of chambers can be formed by forming an easily peelable partition by heat welding at an appropriate temperature.

Specific examples of the above-mentioned easily peelable tape include a two-layer film composed of a polyethylene layer and a mixed resin layer of polyethylene and polypropylene. More specifically, the polyethylene layer has a density of 0.
910 to 0.930 g / cm ³ linear ethylene / α-
The mixed resin layer is formed of a composition comprising 60 to 80% by weight of an olefin copolymer and 20 to 40% by weight of the high density polyethylene, and the mixed resin layer comprises a high density polyethylene 60.
An easily peelable tape formed of a composition comprising ˜80 wt% and polypropylene (homopolymer or a copolymer of propylene and a small amount of α-olefin other than propylene) 20 to 40 wt% is preferable. The thickness of this easily peelable tape is preferably about 50 to 150 μm.

A multi-chamber container in which each chamber as described above is partitioned by an easily peelable tape that is heat-sealed between the multilayer films, for example, in the medical field, contains two or more kinds of chemical solutions separately. , These chemicals can be mixed at the time of use.

For example, in a multi-chamber container consisting of two chambers partitioned by an easily peelable tape, when different chemicals are contained in the respective chambers, pressure is applied to one chamber to make the easily peelable tape. Is separated and the partition between this chamber and the other chamber is lost, and the two types of chemical liquids are mixed.

[0081]

The resin laminate according to the present invention is excellent in heat resistance, transparency, flexibility, mechanical strength characteristics such as low temperature impact strength, and hygiene.

Further, since the container according to the present invention is formed of the resin laminate according to the present invention having the above-mentioned effects, it has heat resistance, transparency, flexibility, mechanical strength characteristics and hygiene. Is excellent.

Therefore, the container according to the present invention can be used as a medical container such as a retort pouch used for a retort food, an infusion bag, and the like, even if it is sterilized under a severe temperature condition of 121 ° C. or higher. It is possible to prevent deterioration of seal strength, drop strength, flexibility and transparency.

Further, the container according to the present invention having two or more chambers is excellent in heat resistance, transparency, flexibility and hygiene and, moreover, easily peeled off even after the above sterilization treatment. Since the tape welding portion is stable, there is no risk that the welding portion will be peeled off during transportation, and the medicine or the like separately stored in each chamber will be mixed.

[0085]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The polypropylene, polyethylene, elastomer and high density polyethylene used in the examples and comparative examples are as follows. Polypropylene 1) Homopolypropylene [hereinafter abbreviated as HPP] Density (JIS K 7112 D method) = 0.910 g / cm ³ MFR (ASTM D 1238, 230 ° C., load 2.16 kg) = 4.0 g
/ 10 minutes 2) Propylene / ethylene random copolymer [hereinafter, R
Abbreviated as PP] Propylene / ethylene [molar ratio] = 96/4 Density (JIS K 7112 D method) = 0.910 g / cm ³ MFR (ASTM D 1238, 230 ° C., load 2.16 kg) = 6.0 g
/ 10 min Polyethylene 1) Ethylene / 1-butene copolymer [hereinafter abbreviated as LL-1] 1-butene content = 6.5 mol% Density (JIS K 7112 D method, at 23 ± 0.1 ° C. temperature) = 0 .905
g / cm ³ MFR (ASTM D 1238, 190 ° C, load 2.16kg) = 2.0g
/ 10 minutes 2) Ethylene / 1-butene copolymer [hereinafter abbreviated as LL-2] 1-butene content = 4.0 mol% Density (JIS K 7112 D method, at 23 ± 0.1 ° C. temperature) = 0. 920
g / cm ³ MFR (ASTM D 1238, 190 ° C, load 2.16kg) = 2.0g
/ 10 min 3) Ethylene / 1-butene copolymer [hereinafter abbreviated as LL-3] 1-butene content = 2.0 mol% Density (JIS K 7112 D method, at 23 ± 0.1 ° C. temperature) = 0. 940
g / cm ³ MFR (ASTM D 1238, 190 ° C, load 2.16kg) = 2.0g
/ 10 minutes elastomer 1) ethylene / 1-butene copolymer rubber [hereinafter, EL-1
Abbreviated] 1-butene content = 11 mol% Density (JIS K 7112 D method, at 23 ± 0.1 ° C temperature) = 0.885
g / cm ³ MFR (ASTM D 1238, 190 ° C, load 2.16kg) = 0.5g
/ 10 minutes 2) Ethylene / propylene copolymer rubber [hereinafter, EL-
Abbreviated as 2] Propylene content = 20 mol% Density (JIS K 7112 D method, at 23 ± 0.1 ° C temperature) = 0.865
g / cm ³ MFR (ASTM D 1238, 230 ° C, load 2.16 kg) = 5.4 g
/ 10 minutes High-density polyethylene 1) Ethylene homopolymer [hereinafter abbreviated as HD] Density (JIS K 7112 D method, 23 ± 0.1 ° C temperature) = 0.965
g / cm ³ MFR (ASTM D 1238, 190 ° C, load 2.16 kg) = 15 g /
10 minutes Mw / Mn: 2.8

[0087]

Example 1 First, 90 parts by weight of EL-1 and HD 1
0 parts by weight was mixed in advance with a Henschel mixer for 1 minute.

Then, the obtained mixture was heated to a resin temperature of 200.
A pelletized composition was obtained while kneading with a uniaxial extruder at ℃. Then, using this composition as a material for forming an intermediate layer,
Using HPP as the outer layer forming material and RPP as the inner layer forming material, the outer layer having a thickness of 30 μm and the thickness of 140 μm
A laminated film was prepared by a water-cooled co-extrusion inflation method so as to form an intermediate layer and a 30 μm thick inner layer.

From the laminated film thus obtained, a four-sided sealed container containing 500 ml of water was formed and retorted at 121 ° C. for 20 minutes, and then the transparency, heat resistance, flexibility and impact resistance of the laminated film were measured. Was evaluated according to the following method. (A) Transparency Transparency was evaluated by haze (%) determined according to ASTM D 1003-61. (B) Heat resistance The heat resistance was evaluated by the deformation start temperature [Td (° C)] described above. (C) Flexibility The flexibility was evaluated by Young's modulus (kg / cm ² ) obtained by conducting a plastic tensile test of JIS K7113.

(D) Impact resistance (impact strength) The impact strength is the pass rate when the above-mentioned four-sided sealed container is cooled to 5 ° C. for each 10 samples and repeatedly dropped 10 times from a height of 1.2 m. It was used as an index and evaluated in the following three stages. Pass: No damage, liquid leakage, etc., when dropping 1 sample 10 times. <Three-step evaluation> A: 8 or more samples out of 10 samples B: 5 to 7 samples out of 10 samples C: 4 samples or less out of 10 samples The results are shown in Table 1.

[0091]

Example 2 In Example 1, the outer layer having a thickness of 30 μm, the intermediate layer having a thickness of 140 μm, and the thickness of 140 μm were formed in the same manner as in Example 1 except that RPP was used instead of HPP as the material for forming the outer layer. A laminated film having an inner layer of 30 μm was prepared, and the transparency, heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1.

[0093]

[Example 3] The same as Example 1, except that RPP was used as the material for forming the outer layer instead of HPP, and LL-3 was used as the material for forming the inner layer in place of RPP. 30 μm thick outer layer and 140 μm thick
A laminated film comprising an intermediate layer of m and an inner layer having a thickness of 30 μm was prepared, and the above-mentioned transparency, heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1.

[0095]

Example 4 In Example 1, RPP was used in place of HPP as the material for forming the outer layer, and the following pelletized composition of EL-1 and HD in Example 1 was used as the material for forming the intermediate layer. A thickness of 30 μm was obtained in the same manner as in Example 1 except that the pellet composition of EL-2 and HD was used.
To prepare a laminated film comprising an outer layer, a 140 μm-thick intermediate layer, and a 30 μm-thick inner layer.
The heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1. EL-2 and H above
The pellet composition with D is 90 parts by weight of EL-2,
10 parts by weight of HD were mixed and prepared in the same manner as in Example 1.

[0097]

Example 5 In Example 1, RPP was used instead of HPP as the material for forming the outer layer, and the following pellet-like composition of EL-1 and HD of Example 1 was used as the material for forming the intermediate layer. The same procedure as in Example 1 except that the pellet-shaped composition of EL-1, LL-2, and HD was used, an outer layer having a thickness of 30 μm, an intermediate layer having a thickness of 140 μm, and an inner layer having a thickness of 30 μm. Was prepared and the transparency, heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1. EL-1 and L above
The pellet composition of L-2 and HD is EL-1 70
Parts by weight, 25 parts by weight of LL-2, and 5 parts by weight of HD were mixed and prepared in the same manner as in Example 1.

[0099]

Example 6 In Example 1, RPP was used in place of HPP as the material for forming the outer layer, and EL-1 and HD of Example 1 were used as the material for forming the intermediate layer in place of the pelletized composition shown below. 30 μm in the same manner as in Example 1 except that the pelletized composition of EL-1 and RPP of
m outer layer, 140 μm thick intermediate layer, 30 μm thick
Was prepared, and the above-mentioned transparency, heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1. EL-1 and R above
A pellet composition with PP was prepared by mixing 90 parts by weight of EL-1 and 10 parts by weight of RPP in the same manner as in Example 1.

[0101]

Example 7 In Example 1, RPP was used instead of HPP as the material for forming the outer layer, and the following pellet-like composition of EL-1 and HD of Example 1 was used as the material for forming the intermediate layer. 30 μm in thickness in the same manner as in Example 1 except that the pellet composition of LL-1 and HD was used.
To prepare a laminated film comprising an outer layer, a 140 μm-thick intermediate layer, and a 30 μm-thick inner layer.
The heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1. LL-1 and H above
The pellet composition with D is 90 parts by weight of LL-1,
10 parts by weight of HD were mixed and prepared in the same manner as in Example 1.

[0103]

Example 8 In Example 1, RPP was used instead of HPP as the outer layer forming material, and the following pellet-shaped composition of EL-1 and HD of Example 1 was used as the intermediate layer forming material. 20 μm thick in the same manner as in Example 1 except that the pellet composition of EL-1 and HD was used.
Of the outer layer, a middle layer having a thickness of 160 μm, and an inner layer having a thickness of 20 μm.
The heat resistance, flexibility and impact resistance were evaluated.

The results are shown in Table 1. EL-1 and H above
The pellet composition with D is 85 parts by weight of EL-1,
15 parts by weight of HD were mixed and prepared in the same manner as in Example 1.

[0105]

Comparative Example 1 A 200 μm-thick monolayer film made of RPP was prepared by a water-cooled inflation method. Hereinafter, the transparency, heat resistance, flexibility and impact resistance of the single layer film were evaluated in the same manner as in Example 1.

The results are shown in Table 1.

[0107]

Comparative Example 2 A 200 μm thick single layer film made of LL-2 was prepared by a water-cooled inflation method. Hereinafter, the transparency, heat resistance, flexibility and impact resistance of the single layer film were evaluated in the same manner as in Example 1.

The results are shown in Table 1.

[0109]

Comparative Example 3 A 200 μm-thick single layer film made of LL-3 was prepared by a water-cooled inflation method. Hereinafter, the transparency, heat resistance, flexibility and impact resistance of the single layer film were evaluated in the same manner as in Example 1.

The results are shown in Table 1.

[0111]

[Table 1]

Claims (6)

[Claims] 1. A resin laminate comprising an outer layer [I], an intermediate layer portion [II] containing one or more intermediate layers, and an inner layer [III], wherein the outer layer [I] is a propylene homopolymer. (A), or 5
Propylene / α-composed of 0 mol% or more of propylene and ethylene or α-olefin having 4 to 8 carbon atoms
At least one intermediate layer [II] which is formed of the olefin random copolymer (b) and constitutes the intermediate layer part [II].
-1] is formed of a composition containing one kind of material selected from elastomer (c), polyethylene (d) and polypropylene (e), or a composition containing two or more kinds of materials, and the inner layer [III ] Is formed by a propylene / α-olefin random copolymer (f) consisting of 50 mol% or more of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms, or polyethylene (g),
Moreover, the resin laminate has (i) a haze of 3 after the retort sterilization treatment.
0% or less, and (ii) a deformation start temperature [Td (° C)] is a temperature exceeding 121 ° C, a resin laminate. 2. The resin laminate according to claim 1, which has a Young's modulus of 3,500 kg / cm ² or less. 3. At least one of the outer layer [I], the intermediate layer [II-1] and the inner layer [III] has a density of 0.
5-30 high density polyethylene (h) having a molecular weight distribution (Mw / Mn) of 4.0 or less at 950 g / cm ³ or more
The resin laminate according to claim 1, wherein the resin laminate is formed of a polyolefin composition containing wt%. 4. The thickness of the intermediate layer portion [II] is 40% or more and less than 75% of the total thickness of the resin laminate, and the intermediate layer [II-1] has a density of 0.950 g / in cm ³ or more, and characterized in that it is formed by a molecular weight distribution (Mw / Mn) of the polyolefin composition comprising 4.0 or less is high density polyethylene (h) in an amount of less than 5 wt% to 15 wt% The resin laminate according to claim 1. 5. The intermediate layer [II] has a thickness within a range of 75 to 90% of the total thickness of the resin laminate, and the intermediate layer [II-1] has a density of 0.950 g. / Cm ³ or more and a molecular weight distribution (Mw / Mn) of 4.0 or less, the high density polyethylene (h) is formed from a polyolefin composition containing 15 to 30% by weight. The resin laminate described. 6. A container comprising the resin laminate according to any one of claims 1 to 5 as a constituent material.