JP3085642B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate which is preferably used in the field of packaging, especially for the production of containers, and has a sealing property and an opening property for storing and packaging foods, medicines and the like produced using the laminate. It relates to an excellent easy-open container.

[0002]

2. Description of the Related Art The number of containers in which food is sealed in a plastic container, sterilized at a high temperature, and stored and distributed is increasing.
In addition, there are cases where consumers use a microwave oven to use the contents, and if the contents contain oil, the temperature of the contents may be high, and the needs of consumers include heat resistance in cooking, It has excellent sealing properties and excellent opening properties. As a container with excellent sealing and easy-opening properties,
Rather than opening the seal at the time of use by peeling off the seal part which is generally performed, using a multi-layer container as a container, the layer of the multi-layer container is used as an open-peeling surface, and a container having both sealability and easy-openability (Japanese Patent Laid-Open No. 50-375)
No. 98, JP-B 5-63385, JP-B 5-
79587). However, in these containers, since the release layer is made of PE (polyethylene), the upper limit of the high-temperature treatment condition is 120 ° C. In particular, when a cooked food containing a large amount of oil is filled, the release layer shows swelling. And the sealing with the lid material is broken due to softening of the sealing layer due to high temperature. For the purpose of compensating for these drawbacks, a container having a layer structure with increased heat resistance using a polypropylene resin as the innermost layer as shown in Japanese Patent Publication No. Hei 7-2409 has been proposed. Although the heat resistance is improved as compared with the above, PE is still used as an intermediate layer in order to enable peeling, and although some improvement in heat resistance is recognized, sterilization at a higher temperature (ex. ° C), the intermediate layer is softened and melted, so that the lamination strength between the intermediate layer and the surface layer is rapidly reduced, peeling occurs during sterilization, and the sealing property is impaired. In addition, since ordinary polypropylene is deformed in the heat resistance of the whole container, it is necessary to use a material having excellent heat resistance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate preferably used for producing an easily-openable container having a heat-sealing layer and an opening-peeling layer separately. It is intended to provide a laminate having heat resistance and oil resistance while ensuring easy peelability.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by making a laminate used for manufacturing an easy-open container into a specific layer structure, They have found that the above problems can be solved, and have completed the present invention based on this finding. That is, the present invention
A sealing layer (A) in which the first layer is a polypropylene having a melting point of 160 ° C. or more from the inside, and the second layer is polypropylene 20 to 9
The adjoining layer (B), which is a mixture of 0% by weight and 80 to 10% by weight of 4-methylpentene 1 resin, has a third layer having a melting point of 160 ° C. or more and a melt index (JIS K6758) 1.
And an outermost layer having a base layer mainly composed of polypropylene containing 10% by weight to 60% by weight of an inorganic filler (D), and a melt index of the sealing layer (A). Is 1.1 times or more the melt index of the intermediate layer (C), the interlayer peel strength between (A) and (B) is weaker than the interlayer peel strength between (B) and (C), and the peel strength is 0.1. 2 to 2.5 kg / 15 mm (pulling speed: 300 mm / min), comprising at least four layers and, if necessary, 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. The laminate is a composition, preferably the thickness of the innermost layer (A),
A laminate having a size of 5 to 100 μm or less.

The sealing 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 at least 0 ° C. By using this PP, a laminate having heat resistance and oil resistance can be obtained. Further, the melt index of the PP used in (A) (JIS K6758)
Must be greater than 1.1 times the PP used in (C). The present inventors have found that delamination with the adjacent layer (B) is controlled by the difference in melt index (hereinafter referred to as MI) of PP. In other words, 2 sandwiching (B)
It was found that the delamination strength of one of the two layers was influenced by the MI of the PP adjacent to (B), and the delamination strength of the larger MI was smaller. In the case of the present invention, (A) and (B)
It is necessary to separate the M in (A) from the M in (C).
When it is 1.1 times or more of I, the delamination strength between (A) and (B) is smaller than that between (B) and (C), which is suitable for easy opening. Further, the thickness of (A) is preferably 5 to 100 μm,
If it is less than 5μ, the sealing will be insufficient, and if it is more than 100μ, the feeling of opening may be impaired. P to use
P is arbitrary as long as the melting point is 160 ° C. and the MI is 1.1 times or more of (C). In consideration of the sealing property with the lid and the moldability, PP is 3 to 2 parts per 100 parts by weight.
It is also possible to blend 0 weight polyethylene. In addition to polyethylene, a blend of a thermoplastic resin such as an unsaturated carboxylic acid-modified polyolefin or ethylene vinyl acetate is also possible as long as the heat-peelability with the intermediate layer is not impaired.

The intermediate layer (C) of the present invention aims at maintaining the strength, heat resistance and moldability of the laminate. This layer also requires heat resistance, and polypropylene having a melting point of 160 ° C. or more is used. One of the purposes of the intermediate layer is to adjust the peel strength between the adjacent layer (B) and the MI.
Should be 0.5 to 30. When the MI is 30 or more, it is difficult to adjust the interlayer peel strength between (A) and (B) and between (B) and (C), and it is difficult to provide a difference in interlayer peel strength. When these conditions are satisfied, it is also possible to blend an arbitrary thermoplastic resin such as polyethylene for the purpose of adjusting the moldability and the like. The base material layer (D) of the present invention is mainly composed of polypropylene containing 10 to 60% by weight of an inorganic filler. Examples of the inorganic filler having a plate-like or scale-like form include, for example, talc, titanium oxide, kaolin, clay, aluminum hydroxide, graphite, yalcite, pearlite mica, and mixtures thereof. As fillers, calcium carbonate, calcium silicate, magnesium oxide, titanium oxide, magnesium hydroxide, quartz powder, magnesium carbonate,
Gypsum magnesium and the like are used, and upon use, any single substance or mixture is used. Preferably, mica, talc and calcium carbonate are preferred. If the amount of the inorganic filler is too small, heat resistance and rigidity cannot be improved. If the amount is too large, the production of the laminate becomes difficult. Therefore, the range of 20% by weight to 60% by weight is suitable, and the range of 30% by weight to 50% by weight is more preferable. preferable.

The adjacent layer (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 the amount of polypropylene is preferably 90 to 20% by weight and the amount of 4-methylpentene 1 resin is preferably 80 to 10% by weight, and the most preferable blending ratio is 80 to 40% by weight as the amount of polypropylene. When the amount of polypropylene is 90% by weight or more, opening becomes difficult, and when the amount is 20% or less, delamination strength is weakened and delamination may occur. It is also possible to blend polyethylene to finely control the delamination strength, but if the blend amount is too large, the intended heat resistance may be impaired, and the blend amount is 100 parts by weight of polypropylene. Therefore, it is preferable that the upper limit is 20 parts by weight, and the lower limit is 3 parts by weight because the delamination strength cannot be adjusted if the blend amount is small. Similarly, unsaturated carboxylic acid-modified polypropylene may be blended in order to adjust delicate delamination strength. However, if the blend amount is too large, the peel strength is increased and the blend amount is small. 20 parts by weight or less 3
It is desirable that the amount be at least part by weight.

In addition to the four layers (A) to (D), an arbitrary resin can be laminated outside the layer (D) or between the layers (C) and (D). 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) and inorganic-filled polypropylene. Also (D)
Is not limited to a single layer, and may be arbitrarily selected, such as a multi-layered structure, between the (B) layer and the (C) layer. In this case, the adhesive layer (AD) is preferably an unsaturated carboxylic acid-modified polypropylene. That is, the outside of the layer (D) or the layer (C) and the layer (D)
As a layer to be added between layers, PP / AD / EVOH / A
D / PP, PP / AD / PVDC / AD / PP, etc. can be arbitrarily selected. In addition, other than plastic, 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 outside the (D) layer or between the (C) layer and the (D) layer. The ethylene polymerization ratio is 20
Those having a concentration of ５０50% by weight are optionally used according to the purpose.
When the ethylene vinyl alcohol copolymer is used between the (C) layer and the (D) layer, the same type of PP as the (C) layer or another PP is used next to the (C) layer in consideration of moldability. When used through a type of PP, the moldability is improved. That is, the layer structure is preferably eight layers of A / B / C / PP / AD / EVOH / AD / D. The layer structure of the present invention can be obtained by coextrusion, lamination, or the like using the above-mentioned resin.
As a lamination process, any method such as extrusion lamination, coextrusion lamination, dry lamination, and thermal lamination can be used.

[0009]

The most important point of the present invention lies in the fact that polypropylene as the adjacent layer (B) is blended 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 more compared to the conventional intermediate layer mainly composed of polyethylene,
Even if the temperature of the contents becomes high (for example, 140 ° C. or more) during sterilization, the intermediate layer does not soften and melt. For example, when compared with the case of the conventional PE, the melting point of HDPE (high-density polyethylene) having the highest heat resistance is around 135 ° C. When the temperature exceeds 120 ° C., the softening rapidly progresses, and the delamination strength between the seal layer and the intermediate layer becomes 1.
125 ° C even if it is 0-1.5kg / 15mm wide
The peel strength is 0-0.2kg when you experience the heat of even temporarily
/ 15 mm. For this reason, 125 ° C
In the sterilization at high temperatures described above, if the lid material swells even if the pressure change during sterilization is slight, the sealing layer and the intermediate layer are easily peeled off, and the form as a sealed container cannot be maintained. Becomes On the other hand, according to the present invention, when the intermediate layer is used, the intermediate layer itself has excellent heat resistance even at a high temperature treatment of 130 ° C. or more, so that the above-described form is not obtained, and a stable high temperature treatment is possible. . Furthermore, by using PP in which the outer layer is filled with an inorganic filler, it is possible to improve the heat resistance and rigidity of the entire laminate. Also, by filling with an inorganic filler, it is excellent in easy incineration. Further, when a blend of polypropylene and 4-methylpentene 1 resin is laminated, it easily peels off. Its strength depends on the blending ratio, but for example, the mixing ratio is 50 to 90% by weight in terms of polypropylene weight ratio.
In the range, the interlayer adhesive strength is 0.5 to 2.5 kg / 15 kg.
In 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 sealed with a lid material. The lid is opened between the layers (A) and (B) and must be easily openable. No.
Therefore, the delamination strength between (A) and (B) is 0.2 to 2.5 kg.
/ 15 mm (pulling speed 300 mm / min). In this case, in order to perform peeling smoothly (C)
It is necessary to take into account the delamination strength between (D).
When the delamination strength between (B) and (C) is lower than the delamination strength between (A) and (B), delamination may be performed between (B) and (C), and the opening is not stable. Therefore, in order to easily open, the interlayer peeling strength between (A) and (B) should be (B)
It is necessary to make it smaller than the delamination strength between (C).
Therefore, the intensity can be adjusted by changing the MI of the PP used in (A) and (C). That is, the MI of the PP in (A) is set to be 1.
The present invention has found that this relationship is established by making the ratio more than one. Therefore, the sealing layer of the lid material and the innermost layer (A) must be firmly adhered. Usually, the material of the sealing layer of the lid material is the same or the same as the material of the innermost layer (A). You. In order to further 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 μm, the feeling of opening 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 and Table 3 show the thicknesses of constituent resins and layers of the laminates 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 lamination strength, the lamination strength before and after heating between (B) and (C), the sterilization suitability, internal pressure resistance, heat resistance, and openability of the container prepared using each laminate. These laminates were kneaded and extruded by separate extruders, and were laminated by a co-extrusion method of leading to a multilayer 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 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 evaluation in this example and comparative examples was performed by the following method. Lamination strength before heating: The lamination strength between (A) and (B) and between (B) and (C) of the laminate was measured. Pulling speed 300 mm / min. (180 degree peeling) Lamination strength after heating: The laminate was 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. (180 degree peeling) ・ Sterilization adequacy (bag breakage rate): using the laminates of Examples and Comparative Examples, a diameter of 65 mmφ, a height of 25 mm, and a capacity of 70 cc
Was made by vacuum forming. 9 water in the container
It was filled with 0%, and sealed with a heat seal method using a lid film having a thickness of 100 μm and having a four-layer structure of PET / aluminum foil / PET / PP. Then, sterilization was performed in hot water of 130 ° C. under pressure at n = 10, and after sterilization was completed, the presence or absence of water leakage was counted by visual inspection. The numerator is the number of leaks, and the denominator is the number of tests. -Inner pressure resistance: After the sterilization suitability evaluation, if there was no water leakage after sterilization, the air was injected from the lid material side to prevent the compressed air from leaking, and the pressure when the sealing was released was measured. Heat resistance: A container used for sterilization was filled with 90% vegetable oil, and heated for 2 minutes with an electronic cash register having an output of 500 W.
After the completion of the heating, the appearance of the container was observed. If the container was deformed, it was determined to be defective, and if it was not deformed, it was determined to be good. -Openability: The container used for sterilization was subjected to the same sterilization treatment, and then an opening test was performed using a female monitor. When the peelability of the release layer was poor at the time of opening, a whisker-like product was generated, or when the opening was not performed smoothly, it was regarded as defective. -Tensile modulus: measured according to ASTM D882. .

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

According to the laminate of the present invention, the easy-opening property and the sealing property after the high-temperature treatment can be stably controlled. Further, the easily-openable container obtained from this laminate has excellent sealing properties and openability, and its practical value is great.

────────────────────────────────────────────────── ─── Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B65D 65/00-65/46 B65D 81/34

Claims (3)

(57) [Claims] 1. A sealing layer (A) in which a first layer from the inside is a polypropylene having a melting point of 160 ° C. or higher, and a second layer comprising 20 to 90% by weight of polypropylene and a resin of 4-methylpentene 1
The adjoining layer (B) and the third layer each comprising a mixture of 10 to 10% by weight have a melting point of 160 ° C. or more and a melt index of 0.5 to 3
Intermediate layer (C) made of polypropylene of 0, outermost layer of 1
0 wt% to 60 wt% of the base material layer mainly composed of Poripuropi <br/> Le emissions containing inorganic filler (D) has a sealing layer (A)
Is at least 1.1 times the melt index of the intermediate layer (C), and the delamination strength between (A) and (B) is weaker than the delamination strength between (B) and (C). Is 0.2 to 2.5 kg / 15 mm (pulling speed 3
(00 mm / min), comprising at least four layers. 2. An adjoining layer (B) comprising polypropylene 20 to 9
The composition according to claim 1, wherein 3 to 20 parts by weight of polyethylene or unsaturated carboxylic acid-modified polypropylene is added to 100 parts by weight of a mixture of 0% by weight and 80 to 10% by weight of 4-methylpentene 1 resin. Laminate. 3. The laminate according to claim 1, wherein the thickness of the innermost layer (A) is 5 to 100 μm.