JPH0911419A - Laminated body - Google Patents

Abstract

PURPOSE: To give heat resistance and oil resistance to a laminated body by a structure wherein the laminated body is made respectively of a specified sealing layer, an adjacent layer, an intermediate layer and a base material layer from inside in the order named under the condition that the meld index of the sealing layer is larger by a specified value than that of the intermediate layer and the ply separation strength between the sealing layer and the adjacent layer is weaker than that between the adjacent layer and the intermediate layer and is of a specified separation strength value. CONSTITUTION: This laminated body consists from inside of at least four or more layers or a polypropylene sealing layer having the melting point of 160 deg.C or higher as the first layer, an adjacent layer made of a mixture of 20-90wt.% of polypropylene and 80-10wt.% of 4-methylpentene-1 as the second layer, an intermediate layer made of polypropylene having the melting point of 160 deg.C or higher and the melt index of 0.5-30 as the third layer and a base material layer mainly made of polypropylene containing 10-60wt.% of an inorganic filler. The melt index of the sealing layer is 1.1 or more times as high as that of the intermediate layer and the ply separation strength between the sealing layer and the adjacent layer is set to be weaker than that between the adjacent layer and the intermediate layer and the separation strength is set to be 0.2-2.5kg/15mm under the pulling speed of 300mm/min.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the field of packaging, in particular, to a laminate which is preferably used for the production of containers, and a sealing property and an opening property for accommodating and packaging foods, chemicals and the like produced using the same. It relates to an excellent easy-open container.

[0002]

2. Description of the Related Art There is an increasing number of containers in which foods are sealed in plastic containers, subjected to high temperature sterilization treatment, and stored and distributed.
In addition, there are cases where the product is heated by a microwave oven when it is used by the consumer, and when the content contains oil, the temperature of the content may become high. It has an excellent sealing property and an excellent opening property. As a container with excellent sealing and easy opening properties,
Rather than performing the peeling of the seal portion that is generally performed during use, a multi-layer container is used as the container, and the layers of the multi-layer container are used as the opening / peeling surface, and both the sealing property and the easy-open property are achieved. Have been proposed (Japanese Patent Application Laid-Open No. 50-375).
98, Japanese Patent Publication No. 5-63385, Japanese Patent Publication No. 5-
79587). However, in these containers, since the release layer is PE (polyethylene), the high temperature treatment condition is 120 ° C as the upper limit, and when the cooked food containing a large amount of oil is filled, the release layer shows swelling. However, there was a defect that the seal layer was broken due to the softening of the seal layer due to the high temperature. For the purpose of compensating for these drawbacks, a container having a layer structure in which the heat resistance is increased by using a polypropylene resin as the innermost layer as disclosed in Japanese Patent Publication No. 7-2409 is proposed. Although the heat resistance is improved as compared with the above, PE is still used as an intermediate layer in these constitutions in order to enable peeling, and although some improvement in heat resistance is recognized, sterilization at a higher temperature (ex 130 (° C), the intermediate layer is softened and melted, so that the laminate strength between the intermediate layer and the surface layer is rapidly reduced, peeling occurs during sterilization, and the sealing performance is impaired. Also, with respect to the heat resistance of the entire container, since deformation occurs in ordinary polypropylene, it is necessary to use a material having excellent heat resistance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is a laminate suitable for use in the production of an easily openable container having a heat seal layer and an opening and peeling layer separated from each other, the opening and peeling layer (sealing layer). The present invention provides a laminate having heat resistance and oil resistance while ensuring the easy peelability.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a laminate used for producing an easily-openable container has a specific layer structure, It has been found that the above problems can be solved, and the present invention has been completed based on this finding. That is, the present invention
A sealing layer (A) in which the first layer is polypropylene having a melting point of 160 ° C. or higher from the inside, and the second layer is polypropylene 20 to 9
Adjacent layer (B) made of a mixture of 0% by weight and 80% by weight of 4 methylpentene 1 resin, the third layer has a melting point of 160 ° C. or higher, and a melt index (JIS K6758) 1
The intermediate layer (C) made of polypropylene of 30 to 30, the outermost layer having a base material layer (D) mainly composed of polypropylene containing 10 wt% to 60 wt% of inorganic filler, and the melt index of the seal layer (A). Is 1.1 times or more the melt index of the intermediate layer (C), the interlaminar peel strength between (A) and (B) is weaker than the interlaminar peel strength between (B) and (C), and the peel strength is 0. A laminate having a thickness of 2 to 2.5 kg / 15 mm (pulling speed of 300 mm / min) and comprising at least 4 layers, and optionally an intermediate layer.
(B) is obtained by adding 3 to 20 parts by weight of polyethylene or unsaturated carboxylic acid-modified polypropylene to 100 parts by weight of a mixture consisting of 20 to 90% by weight of polypropylene and 80 to 10% by weight of 4-methylpentene 1 resin. It is a laminated body which is a composition, and preferably the thickness of the innermost layer (A) is
It is a laminated body having a thickness of 5 to 100 μm or less.

The seal layer (A) of the present invention has a melting point of 160.
It is made of polypropylene (hereinafter referred to as PP) having a temperature of not less than 0 ° C. By using this PP, a laminate having heat resistance and oil resistance can be obtained. Further, the melt index of PP used in (A) (JIS K6758)
Must be greater than 1.1 times the PP used in (C). The present inventors have found that the delamination from the adjacent layer (B) is controlled by the difference in PP melt index (hereinafter referred to as MI). In other words, sandwiching (B) 2
It was found that the two interlaminar peel strengths were affected by the MI of PP adjacent to (B), and the interlaminar peel strength of the larger MI was smaller. In the case of the present invention, (A) and (B)
It is necessary to peel off between (A) MI and (C) M
When it is 1.1 times or more of I, the interlaminar peel strength between (A) and (B) becomes smaller than that between (B) and (C), which is suitable for easy opening. Further, the thickness of (A) is preferably 5 to 100 μ,
If it is smaller than 5 μ, the sealing may be insufficient, and if it is larger than 100 μ, the open feeling may be impaired. P to use
As P, the melting point is 160 ° C., and MI is arbitrary as long as it is 1.1 times or more of (C). Considering the sealing property with the lid and the moldability, PP is 3 to 2 per 100 parts by weight.
It is also possible to blend 0 weight of polyethylene. In addition to polyethylene, blending of a thermoplastic resin such as unsaturated carboxylic acid-modified polyolefin or ethylene vinyl acetate is also possible within a range that does not impair the heat-resistant peeling property with the intermediate layer.

The intermediate layer (C) of the present invention is intended to maintain the strength, heat resistance and moldability of the laminate. This layer also needs heat resistance, and polypropylene having a melting point of 160 ° C. or higher is used. Further, one of the purposes of the intermediate layer is to adjust the interlaminar peel strength with the adjacent layer (B).
Should be 0.5 to 30. When the MI is 30 or more, it is difficult to adjust the interlaminar peel strength between (A) and (B) and between (B) and (C), and it is difficult to provide a difference in interlaminar peel strength. Further, when these conditions are satisfied, it is possible to blend an arbitrary thermoplastic resin such as polyethylene for the purpose of adjusting moldability and the like. The base layer (D) of the present invention is mainly composed of polypropylene containing 10 to 60% by weight of an inorganic filler. As the inorganic filler having a plate-like, scaly, or the like form, for example, talc, titanium oxide, kaolin, clay, aluminum hydroxide, graphite, yarisite, perlite mica, or a mixture thereof is raised, and a non-scaly inorganic substance. As a filler, calcium carbonate, calcium silicate, magnesium oxide, titanium oxide, magnesium hydroxide, quartz powder, magnesium carbonate,
Gypsum magnesium or the like is used, and when used, any single substance or a mixture is used. Mica, talc and calcium carbonate are preferred. If the filling amount of the inorganic filler is too small, heat resistance and rigidity cannot be improved. Further, if it is too large, it will be difficult to produce a laminate, so that the range of 20% by weight to 60% by weight is suitable, and more preferably the range of 30% by weight to 50% by weight. preferable.

The adjacent layer of (B) of the present invention plays the most important role in the present invention, and this layer is mainly composed of a blend of polypropylene and 4-methylpentene-1 resin. The blending ratio is arbitrary, but 90 to 20% by weight as the amount of polypropylene and 80 to 10% by weight as the 4-methylpentene 1 resin are preferable, but the most preferable compounding ratio is 80 to 40% by weight as the amount of polypropylene. If the amount of polypropylene is 90% by weight or more, unsealing becomes difficult, while if it is 20% or less, the delamination strength becomes weak and delamination may occur. It is also possible to blend polyethylene in order to adjust the delicate delamination strength, but if the blending amount is too large, the target heat resistance may be impaired, and the blending amount is based on 100 parts by weight of polypropylene. Therefore, the upper limit is 20 parts by weight, and if the blending amount is small, the interlaminar peel strength cannot be adjusted. Therefore, the lower limit is preferably 3 parts by weight. Similarly, unsaturated carboxylic acid-modified polypropylene may be blended in order to adjust the delicate delamination strength, but with this blend too, if the blending amount is too large, the peeling strength is increased and the blending amount is small. 20 parts by weight or less 3
It is desirable that the amount is more than weight part.

Further, in addition to the four layers (A) to (D), any resin can be laminated outside the (D) layer or between the (C) layer and the (D) layer. As the resin to be laminated, polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Polypropylene (PP), vinylidene chloride resin (PVD
C), ethylene vinyl alcohol copolymer (EVO
H), polypropylene filled with inorganic material, and the like. Also (D)
The outer layer and between the (B) layer and the (C) layer are not limited to a single layer but may be arbitrarily selected such as a multilayer. In this case, unsaturated carboxylic acid-modified polypropylene is preferable as the adhesive layer (AD). That is, the outside of the (D) layer or the (C) layer and the (D) layer
The layers added between the layers are PP / AD / EVOH / A
D / PP, PP / AD / PVDC / AD / PP, etc. can be arbitrarily selected. Other than that, not only plastic but also metal layers such as aluminum foil and steel foil can be used. In particular, when it is necessary to improve the oxygen gas barrier property of the laminate, an ethylene vinyl alcohol copolymer is used by being laminated on the outside of the (D) layer or between the (C) layer and the (D) layer. The ethylene polymerization ratio is 20
Those having a content of up to 50% by weight are optionally used according to the purpose.
Further, when the ethylene vinyl alcohol copolymer is used between the (C) layer and the (D) layer, considering the moldability, the same type of PP as the (C) layer or another PP is provided after the (C) layer. When it is used through the PP of the kind, the moldability is improved. That is, the layer structure is preferably 8 layers of A / B / C / PP / AD / EVOH / AD / D. The layer structure of the present invention can be obtained by coextrusion, laminating or the like using the above resin.
As the laminating process, any method such as extrusion laminating, coextrusion laminating, dry laminating or thermal laminating can be used.

[0009]

The most important point of the present invention is to blend the adjacent layer (B) of polypropylene with 4 methylpentene 1 resin. The melting point of polypropylene is usually about 150 ° C. for random PP and about 160 ° C. for homo PP. On the other hand, the melting point of 4-methylpentene 1 is about 240 ° C. By blending these, it has a heat resistance of 15 ° C or higher as compared with the conventional intermediate layer mainly composed of polyethylene,
Even if the temperature of the contents becomes high (for example, 140 ° C. or higher) during sterilization, the intermediate layer does not soften or melt. For example, the melting point of HDPE (high-density polyethylene), which has the highest heat resistance, is around 135 ° C. as compared with the case of conventional PE. When the temperature exceeds 120 ° C, the softening progresses rapidly, and the interlayer peel strength between the seal layer and the intermediate layer is 1.
Even if the width was 0 to 1.5 kg / 15 mm, it was 125 ° C.
Peeling strength is 0-0.2kg if you experience the heat of
/ 15mm and it will fall sharply. Therefore, 125 ℃
In the above sterilization at high temperature, if the pressure change during sterilization causes the lid material to swell even a little, the seal layer and the intermediate layer are easily peeled off, and the state as a sealed container cannot be maintained. Becomes On the other hand, according to the present invention, when the intermediate layer is used, the heat resistance of the intermediate layer itself is excellent even at a high temperature treatment of 130 ° C. or higher, so that the above-mentioned form does not occur, and stable high temperature treatment becomes possible. . Furthermore, by using PP having the outer layer filled with an inorganic filler, it becomes possible to improve the heat resistance and rigidity of the entire laminate. In addition, by filling with an inorganic filler, the incineration property is excellent. Further, when a blend of polypropylene and 4-methylpentene-1 resin is laminated, easy peeling property is exhibited. The strength depends on the blend ratio, but for example, the mixing ratio is 50 to 90% by weight in terms of polypropylene weight ratio.
In the range of, the interlayer adhesion strength is 0.5-2.5kg / 15kg
Within the range of easy peel strength. Therefore, the peeling of the seal layer can be easily performed.

The laminate of the present invention is molded and used as a container, and is sealed with a lid material. The lid is opened between the (A) layer and the (B) layer and must be easily opened. I won't.
Therefore, the delamination strength between (A) and (B) is 0.2-2.5kg.
/ 15 mm (pulling speed 300 mm / min), and in order to perform peeling smoothly at this time (C)
It is also necessary to take the delamination strength between (D) into consideration.
When the delamination strength between (B) and (C) is smaller than the delamination strength between (A) and (B), delamination may occur between (B) and (C), and unsealing is not stable. Therefore, to easily open the package, the interlaminar peel strength between (A) and (B) should be (B).
It is necessary to make it smaller than the interlaminar peel strength between (C).
Therefore, the strength can be adjusted by changing the MI of PP used in (A) and (C). That is, the MI of the PP of (A) is set to 1.
The present invention has found that this relationship is established by making the ratio 1 or more. Therefore, the sealing layer of the lid material and the innermost layer (A) must be firmly adhered, and normally, the material of the sealing layer of the lid material is the same or the same as the material of the innermost layer (A). It Furthermore, in order to improve the opening property, the thickness of the innermost layer (A) is preferably in the range of 5 to 100 μm. If the thickness of (A) is 5 μm or less, the sealing property may be impaired, and if it exceeds 100 μ, the unsealing feeling may be impaired.

[0011]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Table 1
Table 3 shows the constituent resins and layer thicknesses of the laminate structures of Examples and Comparative Examples, and Tables 2 and 4 show the laminates of Examples and Comparative Examples before and after heating between (A) and (B). It shows the laminate strength, the laminate strength before and after heating between (B) and (C), the sterilization suitability, the internal pressure resistance, the heat resistance, and the unsealing property of the container formed by using each laminate. These laminates were laminated by a coextrusion method in which they were kneaded and extruded by separate extruders and introduced into a multi-layer die.

The resins used in the examples and comparative examples are as follows. -PP1: polypropylene Melting point 155 ° C MI = 0.
5 · PP2: polypropylene Melting point 164 ° C. MI = 2.
0 • PP3: polypropylene Melting point 162 ° C MI = 1.
5 · PP4: polypropylene, melting point 160 ° C. MI = 3.
0 · PP5: polypropylene, melting point 155 ° C. MI = 2.
5 · PP6: polypropylene Melting point 153 ° C. MI = 1.
0 · PP7: polypropylene, melting point 165 ° C., MI = 3
5.0 ・ PP8: polypropylene Melting point 164 ° C. MI = 2
0.0-PP9: polypropylene Melting point 162 ° C. MI = 4
0.0-AD: carboxylic acid anhydride-modified polypropylene-EVOH: ethylene vinyl alcohol copolymer-MP: 4-methylpentene 1-HDPE: high-density polyethylene-modified PP: carboxylic acid-modified polypropylene-CA: calcium carbonate

The evaluations in the examples and comparative examples were carried out by the following methods. Laminate strength before heating: The laminate strength between (A) and (B) and between (B) and (C) of the laminate is measured. Pulling speed 300 mm / min. (Peeling by 180 degrees) -Lamination strength after heating: The laminate is left under a dry heat condition of 135 degrees for 1 hour and then the laminate strength between (A) and (B) and between (B) and (C) of the laminate. Measure. Pulling speed 300 mm / min. (Peeling by 180 degrees) ・ Suitable sterilization (bag breaking rate): Using the laminates of Examples and Comparative Examples, caliber 65 mmφ, height 25 mm, capacity 70 cc
The round-shaped container was prepared by vacuum forming. 9 water in the container
It was filled with 0% and was sealed by a heat seal method with a lid film having a four-layered structure of PET / aluminum foil / PET / PP and a thickness of 100 μm. After that, sterilization was performed in hot water of 130 ° C. under pressure at n = 10, and after the sterilization was completed, the presence or absence of water leakage was counted by visual inspection. The number of water leaks in the numerator and the number of tests in the denominator. -Internal pressure resistance: After evaluation of sterilization suitability, for those without water leakage after sterilization, compressed air was injected from the lid material side so as not to leak, and the pressure when the sealing was released was measured. -Heat resistance: 90% of vegetable oil was filled in a container used for proper sterilization, and heated at an electronic cash register with an output of 500 W for 2 minutes.
After completion of heating, the appearance of the container was observed, and when the container was deformed, it was evaluated as poor, and when the container was not deformed, it was evaluated as good. -Opening property: A container used for proper sterilization was subjected to the same sterilization treatment, and then an opening test was conducted by a female monitor. The peelability of the release layer was poor at the time of opening, and a whisker-like thing was generated, or a thing which could not be opened smoothly was regarded as a defect. Tensile modulus: measured according to ASTM D882. .

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

INDUSTRIAL APPLICABILITY The laminate of the present invention can stably control the easy-opening property and sealing property after high temperature treatment. In addition, the easy-open container obtained from this laminate has excellent sealing and opening properties, and its practical value is great.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 23/12 LCF B65D 1/00 A

Claims (3)

[Claims] 1. A seal layer (A) in which the first layer is polypropylene having a melting point of 160 ° C. or higher from the inside, and the second layer is 20 to 90% by weight of polypropylene and 4 methylpentene 1 resin 80.
Adjacent layer (B) made of a mixture of 10 to 10% by weight and the third layer have a melting point of 160 ° C. or higher and a melt index of 0.5 to 3
0 middle layer (C) made of polypropylene, outermost layer 1
It has a base material layer (D) mainly composed of polypropylene containing 0% to 60% by weight of an inorganic filler, and the melt index of the seal layer (A) is 1.1 times or more the melt index of the intermediate layer (C). And the interlaminar peel strength between (A) and (B) is weaker than the interlaminar peel strength between (B) and (C), and the peel strength is 0.2 to 2.5 kg / 15 mm (pulling speed 30
0 mm / min) and at least 4 layers or more. 2. Adjacent layer (B) is polypropylene 20-9
2. A composition comprising 3 to 20 parts by weight of polyethylene or an unsaturated carboxylic acid-modified polypropylene added to 100 parts by weight of a mixture consisting of 0% by weight and 80 to 10% by weight of 4-methylpentene 1 resin. Stack of. 3. The laminate according to claim 1, wherein the innermost layer (A) has a thickness of 5 to 100 μm.