JPH01263045A - Laminated and laminated vessel - Google Patents

Abstract

PURPOSE:To obtain a laminate having excellent heat resistance, strength, rigidity, solution resistance, easy baking, and easy peeling covering material adaptability by providing a resin composition layer containing specific amounts of nonflaky inorganic filler and thermoplastic resin between the resin composition layer containing the specific amounts of nonflaky inorganic filler and thermoplastic resin and a thermoplastic resin layer. CONSTITUTION:A laminate has a resin composition layer B containing nonflaky inorganic filler and thermoplastic resin mixed at 20-80wt.% to the total weight of the nonflaky inorganic filler and the thermoplastic resin between the resin composition layer A containing nonflaky inorganic filler and thermoplastic resin mixed at 20-80wt.% to the total sum weight of the nonflaky inorganic filler and the thermoplastic resin and a thermoplastic resin layer C. The layer A forms a main part which contributes to the improvements in heat resistance and rigidity. The layer C is formed on the inner face of a vessel, and preferably uses resin having excellent heat resistance and oil resistance under the conditions of inhibiting to reduce the adhesive to the layer B. The layer B performs a function of a binder with the layers A and C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminate and a laminate container. More specifically, the yi layer has excellent strength, rigidity, heat resistance, easy incineration, punching properties, and peelability from a lid material when made into a container,
and a packaging container made of a laminate thereof.

[Problems to be Solved by the Prior Art and the InventionJ In recent years, retort food has been heated in a microwave oven or in boiling water in the packaging container containing it. It is often done.

Since such packaging containers are heated while containing food, they need to be made of resin with excellent heat resistance, elution resistance, and oil resistance. Also.

The resin used to form the packaging container is required to have excellent mechanical strength and rigidity, and is also required to be easily incinerated from the standpoint of pollution and incinerator maintenance. Ru.

These containers are manufactured, for example, by vacuum forming, pressure forming, etc., of a sheet made of a resin composition containing an inorganic filler.In order to meet the above requirements, inorganic filler It has been proposed to produce a packaging container from a multilayer sheet having a resin composition layer containing a large amount of inorganic filler and a layer containing substantially no inorganic filler.

For example, Japanese Patent Application Laid-open No. 51-26478 and Japanese Patent Publication No. 60-26028 disclose a highly filled filler layer containing a large amount of filler, a layer laminated on both sides of this highly filled filler layer, and a filler layer containing a large amount of filler. A container is disclosed which is made of a three-layer sheet consisting of a filler layer with no additives or a low filler layer containing a small amount of filler.

Also, JP-A No. 52-11i3283, same! 17-
In Publication No. 15963 and Publication No. 59-165654,
Additive-free or
A sheet provided with a layer containing an inorganic filler in an amount of less than % is disclosed.

However, in the multilayer sheet, the high filler layer is thick and the low filler layer is thin, so an easily incinerated multilayer sheet can be obtained. Interface J with filler layer
J? The adhesion strength is very weak. As a result, containers made from this multilayer sheet are susceptible to impact, and upon impact, the interface between the highly filled filler layer and the lightly filled filler layer may peel off, or even breakage may occur. Furthermore, when sealing the opening of a container made of the multilayer sheet with a lid, the low filler layer, which is the inner layer of the container, may be torn or the bag may be torn. In addition, as mentioned above, since the interfacial adhesion is weak, when punching out the MJ & shaped product of the multilayer sheet with a die, it is not possible to punch out a beautiful punched state, resulting in so-called whiskers.
In some cases, the punching may not even be completed completely.

The present invention has been made based on the above circumstances.

That is, the object of the present invention is to provide an easily peelable lid that has excellent heat resistance, rigidity, elution resistance, and easy incineration property, and also has excellent punching properties and can be easily peeled off and opened. It also has excellent material compatibility)! i conformation, and its I
An object of the present invention is to provide a packaging container made of n-coated materials.

[Means for solving the problem The invention according to claim 1 for achieving the above object is 1M
2 for the total weight of flaky inorganic filler and thermoplastic resin
A scale-like inorganic filler blended in a proportion of 0 to 80% by weight,
and a resin composition layer (A) containing a thermoplastic resin;
Between the thermoplastic resin layer (G), 20 to 8 Off based on the total weight of the non-scaly S machine filler and the thermoplastic resin! The invention according to claim 2 is a laminate characterized by having a resin composition layer (B) containing a non-scaly inorganic filler and a thermoplastic resin blended at a ratio of i%, The laminate according to claim 1 is a laminate sheet formed by a co-extrusion method, and the invention according to claim 3 is a laminate comprising the laminate according to claim 1, wherein the laminate comprises a thermoplastic resin layer. (G) is a clear layer container characterized by forming the inner surface of the container.

The laminate and the laminate container according to the present invention will be described in detail below.

-What should be noted about the present invention is that inorganic fillers with different shapes are used properly, the resin composition layer (A) contains a specific proportion of the scale-like inorganic filler, and the resin composition layer (B)
contained a specific amount of non-scaly inorganic filler.

It is a laminate of at least three layers.

The resin composition layer (A) of the above-ground 11" 11 layer has the required performance of disposability (having properties more similar to paper) when it is made into a 2-layer container according to the present invention (laminate, laminate sheet), ), this layer constitutes the main part contributing to improvement of heat resistance and improvement of X properties.

■ Thermoplastic resin Examples of the thermoplastic resin include polyolefin resins, polyvinyl chloride and its copolymer resins, polystyrene and its copolymer resins, thermoplastic polyester resins, polyamide resins, etc. In particular, polyolefin resins type resins are preferred.

Examples of the polyolefin serving as the base polymer of the polyolefin resin include high-density polyethylene,
Examples include polyethylene such as medium- and low-density polyethylene and linear low-density polyethylene, polyethylene such as isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene, polybutene, poly-4-methylpentene-1, and mixtures thereof. Ruru.

In addition, as the polyolefin, olefins and vinyl monomers such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl chloride copolymers, propylene-vinyl chloride copolymers, etc. Copolymers of and the like can also be used.

Furthermore, a modified polyolefin can also be used as the polyolefin.

Examples of the modified polyolefin include those obtained by chemically modifying a polyolefin with an unsaturated carboxylic acid (including its anhydride) or a derivative thereof.

In order to produce this chemically modified modified polyolefin, it is sufficient to react a polyolefin such as polypropylene with an unsaturated carboxylic acid or a derivative thereof using a radical generator.

In the present invention, polyethylene and/or polypropylene are particularly preferred among the various polyolefins.

In the present invention, when polyethylene and/or polypropylene is used among the various polyolefins, the high density polyethylene has a melt index (MI) of 0.05 to 10 g/10 min, preferably 0.1 to 5 g/10 min. minute, density 0.945-0.965
g/Cm3, and as medium and low density polyethylene, MIz>(0,1~20 g/Cm3).
10 minutes, preferably 0.2-10 g 710 minutes, density 0.910-0.940 g7 cm 17
) The MI of polypropylene is 0.2 to 0.910 minutes, preferably 0.2 to leg/1.
At 0 minutes, the density is 0.980-0.910 g/cm
3 (7) also has notes. In addition, when using a mixture of polyethylene and polypropylene, the mixing ratio is 5 to 7.
0:95-30. Preferably the ratio is 10-65:90-35, in any case, 5g of these
When a resin having an MI of 710 minutes or less is used, thermoformability is good.

The thermoplastic resin may contain one or more of various elastomers and various additives, if necessary, as long as it does not impair the effects of the present invention.

Examples of the elastomer include ethylene-α-olefin copolymer, EPR, EPDM, and SBR.

The additives include, for example, a colorant, an antioxidant, a plasticizer, a heat stabilizer, a surface heat FJ agent, a dispersant, and an ultraviolet absorber. Examples include tF antistatic agents and weathering agents.

■ Scale-like S filler The scale-like inorganic filler has a plate-like, flake-like, etc. form, and includes, for example, talc, titanium oxide, kaolin, clay, etc.
Examples include aluminum hydroxide, graphite, sericite, pallite, vermiculite, mica, and mixtures thereof. The selection of this specific inorganic filler, in which talc and mica are particularly preferred, has the characteristic that a highly rigid laminate can be obtained.

When using talc as the excitation scale-like inorganic filler, there is no particular restriction on the talc, and the average particle size is usually 0.5.
~1100u, preferably an average particle size of 1~5
It is 0 pm hydrated magnesium silicate. Also, according to its composition, 5i0250~60%, MgO25~
Particularly preferred is talc having a composition of 40% and other components and a loss on ignition of 1% or less.

However, talc is not limited to those having the above-mentioned average particle size or composition, and it is possible to use various kinds of talc.1 For example, highly refined talc or acid-treated talc can be used. It is also possible to use talc from which impurities have been removed.

Note that this talc does not require any additional means such as surface treatment, but in order to improve the mechanical properties of a sheet obtained from a resin composition containing this talc, the talc surface is made lipophilic. The lipophilic treatment preferably includes a surfactant having a lipophilic group, a polymerizable monomer that reacts with heating to form a lipophilic group,
Examples include blending of oligomers and silane coupling agents.

■Blending ratio The blending ratio of the scale-like inorganic filler and the thermoplastic resin in the resin composition layer (A) is such that the scale-like inorganic filler is 20 to 20% of the total weight of the scale-like inorganic filler and the thermoplastic resin. 80
% by weight, preferably 25 to 70 jl (% by weight).

When the amount of the scaly inorganic filler is less than the above range,
Decreases in easy incineration, p@ properties, heat resistance, etc. may occur, and if the above range is exceeded, moldability may deteriorate.

■84 Thickness of the composition layer (^) The thickness of the resin composition layer (A) differs depending on the use of the carcass of the present invention, so it is best to determine it appropriately depending on the use. , has a thickness constituting the main part of the transplanted carcass of the present invention.

However, speaking in relative terms, the thickness of this resin composition layer (A) is 40 to 90% of the total thickness of the transplanted carcass.
0%, preferably 50-80%.

This resin composition layer (B) serves as a binder between the resin composition layer (A) and the thermoplastic resin layer (G).

■Thermoplastic resin Thermoplastic S used to form this resin composition layer (B)
The thermoplastic resin similar to that described in the resin composition layer (A) can be used for the resin composition layer (A). The thermoplastic resin used may be the same type of thermoplastic resin as in the thermoplastic resin layer (A), or may be a different thermoplastic resin.

Preferred are polyolefins, more preferred are polyethylene and/or polypropylene.

Particularly preferred is to use the same type of thermoplastic resin as that used in the resin composition layer (A) to form the resin composition layer (B).

■Non-scaly inorganic filler Non-scaly inorganic filler is an inorganic filler having a non-scaly form, such as amorphous, granular, acicular, etc.1 For example, calcium carbonate, calcium silicate, magnesium oxide. , titanium oxide, magnesium hydroxide, quartz powder,
Examples include magnesium carbonate and magnesium digypsum.

Calcium carbonate can be mentioned as a preferred non-scaly inorganic filler.

When calcium carbonate is used as the inorganic filler, there are no particular restrictions on the shape of the calcium carbonate, and it usually has an average particle size of 0.1 to 50 pm, particularly 0.2 to 30 Bm. It is preferable to have one.

■Blending ratio The blending ratio of the non-scaly inorganic filler and thermoplastic resin in the resin composition layer (B) is such that the ratio of the scale-like inorganic filler to the total weight of the non-scaly inorganic filler and thermoplastic resin is 20~
80% by weight, preferably 25-70% by weight.

If the amount of the non-scaly inorganic filler is less than the above range, the adhesion with the resin composition layer (nose) will decrease, and if it exceeds the above range, the adhesion with the thermoplastic resin layer CC) described below will decrease. As the properties deteriorate, the moldability also decreases. Therefore, from the viewpoint of heat resistance, rigidity, incineration property, etc., it is desirable to use a blending ratio close to that of the resin composition layer (A).

■Thickness of resin composition layer (B) Resin! The thickness of the laminated layer B) differs depending on the use of the laminate of the present invention, so it cannot be determined generally, but it is usually from 10 to 200 JLm, preferably from 20 to 200 JLm.
It is 100 lm.

Thermoplastic Resin Layer (C) For the thermoplastic resin layer (C), the same thermoplastic resin as explained in the resin composition layer (A) can be used. The thermoplastic resin used may be the same type of thermoplastic resin as in the thermoplastic resin layer (A), or may be a different thermoplastic resin.

For example, polyethylene and/or polypropylene.

However, the thermoplastic resin (C) is used to form the laminated container described later, and a resin with excellent heat resistance and oil resistance is used on the condition that the adhesiveness with the resin composition layer (B) is not reduced. It is preferable to use

This thermoplastic resin layer (C) is preferably formed from only a thermoplastic resin, but the inorganic fillers exemplified in the explanation of the resin composition layer (A) and the resin composition layer (B) are The inorganic filler may be blended at a ratio of 10!1% or less to the total weight of the inorganic filler and thermoplastic resin, and if it is within this ratio, the effects of the present invention will be impaired. Never.

The thickness of the thermoplastic resin layer (G) is usually 10 to 300 g
m, preferably 20 to 200 gm.

In the laminate of the present invention, the resin composition layer (B) is used as a binder layer (intermediate layer) between the resin composition layer (A) and the thermoplastic resin layer (C). have

In the laminate of the present invention, for example, as shown in Figure t51, resin composition layers (B) are provided on both outer surfaces of the resin composition layer (A).
), and the thermoplastic resin layer (C) is laminated on both outer surfaces of the resin composition layer (B), as shown in FIG. 2, a resin composition layer. Examples include a three-layer laminate having a structure in which a resin composition layer (B) is laminated on (A), and the thermoplastic resin layer CG) is laminated on the resin composition layer (B).

Moreover, in addition to the three-layer laminated structure shown in FIG.

A gas barrier layer is laminated on the surface of the resin composition layer (A) opposite to that on which the resin composition layer (B) is laminated.
For layered structures and even gas barrier layers.

5 layers of laminated resin composition layers (A), resin composition layers (A)
) layer and (C) layer may be stacked to form six layers.

As a gas barrier layer, there are no particular restrictions as long as the resin has at least low oxygen permeability and can be molded.
Examples include polyvinyl chloride, polyvinylidene chloride, halogen-containing polyethylene (eg, polychloropolyfluoroethylene, etc.), ethylene-vinyl alcohol copolymer, polyamide, polyester, and the like.

The laminate of the present invention can be produced by a coextrusion sheet forming method using a T-die method, an inflator method, etc., a multilayer blow method, a multilayer injection molding method: an extrusion lamination method.

Dry lamination method, wet lamination method.

It can be molded by a laminating method such as a hot melt laminating method or a solvent-free laminating method.

In addition, in the present invention, by coextrusion molding method, wood)
It is particularly preferred to obtain a laminate sheet consisting of a laminate of AIJI.

Laminated Container The laminated container of the present invention is not particularly limited and can also be obtained by blow molding or injection molding, but the laminated sheet is manufactured by aging molding methods such as vacuum forming and pressure forming.

There is no particular restriction on the form of the laminated container as long as it has the form of a container, for example.

It can take various forms such as a cup shape, a tray shape, a box shape, and a bag shape.

14 having a tray-shaped, cup-shaped, and box-shaped opening;
In the case of a layered container, it is preferable to store the contents such as one food item and then seal the opening by providing a lid material, and it also has a form such as two bags! ! The i-layer volume is sealed by heat-sealing the opening.

In any form of the stretch-layer container, a laminated container having the thermoplastic resin layer (C) as an inner layer is preferable.

[Example] (Example 1) As the thermoplastic resin, HDPE (high-density polyethylene, trade name: Idemitsu polyethylene 520MB, MI=
0.4; density 0.9641/cs+3) is 60% by weight.

PP (polypropylene, trade name: Idemitsu Polypro E-to)
oc; M I =0.5; density 0.911/cm3
) of 40% by weight was used.

Three extruders with screw diameters of 50 mmφ, 50 mmφ, and 65 mmφ, respectively.

tjS using feed block and flat die
As shown in Figure 1, the resin composition layer (A), the resin composition layer (
A laminated sheet of five layers of three types was molded, consisting of B) and a thermoplastic resin layer (C).

The resin composition layer (A) is composed of 50% by weight of the thermoplastic resin, a scaly inorganic filler, and 50% by weight of a slag having an average on diameter of 12 pm, and has a thickness of 8 % by weight. It is layer 0.

The resin composition layer (B) contains 50% by weight of the thermoplastic resin, a non-scaly inorganic filler, and an average particle size of 2p.
It consists of 50% by weight of calcium carbonate, and the thickness of one layer is 50 μm.

The thermoplastic resin layer (C) is made only of the thermoplastic resin and has a thickness of 50 JLm.

The obtained laminated sheet was evaluated as follows.

From the laminated sheet with peel strength! A strip sample with a width of 5 mm was obtained. The interface between the resin composition layer (A) and the resin composition layer (B) of one layer of this sample, and the resin composition layer (B)
) and the thermoplastic resin layer CC) are each 50 mm apart.
The strength was measured at a peeling speed of 300 mm/min.

Aging type machine R1) M 63/1 manufactured by Erich Co., Ltd. (West Germany)
Immediately after thermoforming into a container, the laminated sheet was punched out using Model 0, and a hole with a diameter of 74 mm was made in the laminated sheet. Evaluation was made based on the phenomenon in which one surface layer was peeled off along the punched holes in the laminated sheet (referred to as delamination) and the presence or absence of stringiness in the surface layer.

In addition, evaluation was made as O if there was no delamination or stringiness, 0 if there were 2 or less delaminations/100 delaminations, and × if 3 or more delaminations/100 delaminations were present.

Easy-peelable lid material suitability 7 Has easy-peelability for a layer made of thermoplastic resin l,
The peel strength with the layer consisting of thermoplastic resin 1 is 1.5 kg/
A 15 mm wide laminate film with a biaxially stretched nylon film having a sealant layer was used as the lid material.

After heat-sealing the lid material and the obtained laminated sheet, the lid material and the obtained A-layer sheet are artificially separated,
The surface condition of the obtained sewn layer sheet was observed.

Note that this surface condition is designated as O if it is in good condition.

The presence of delamination on the surface layer was evaluated as Δ, the surface layer was evaluated as V, and the case where the surface layer was broken was evaluated as ×.

The results are shown in Table 1.

tensile modulus Compliant with JIS K6301.

(Example 2) The same procedure as in Example 1 was carried out except that the resin composition layer (B) was composed of 40% by weight of a thermoplastic resin and 60% by weight of calcium carbonate.

The results are shown in Table 1.

(Example 3) The resin composition layer CB) was made of 60% by weight of a thermoplastic resin,
The same procedure as in Example 1 was carried out except that 40% by weight of calcium carbonate was used to form the u1.

The results are shown in Table 1.

(Example 4) The resin composition layer CB) was made of 70% by weight of a thermoplastic resin,
The same procedure as in Example 1 was carried out except that 30% by weight of calcium carbonate was used.

The results are shown in Table 1.

(Example 5) The resin M1 composition layer A) was composed of 80% by weight of thermoplastic resin and 20% by weight of calcium carbonate, and the resin M1 composition layer (A) was composed of 40% by weight of thermoplastic resin. The same procedure as in Example 1 was carried out except that the sample was composed of 60% calcium carbonate and 60% calcium carbonate.

The results are shown in Table 1.

(Comparative Example 1) The same procedure as in Example 1 was carried out except that the resin composition layer (El) was composed of 90% by weight of a thermoplastic resin and 10% by weight of calcium carbonate.

The results are shown in Table 1.

(Comparative Example 2) Resin ff1I & material layer (B) and resin composition layer (^).

The same procedure as in Example 1 was carried out except that 50% by weight of thermoplastic resin and 50% by weight of calcium carbonate were used.

The results are shown in Table 1.

(Comparative Example 3) The resin composition layer (B) and the resin composition layer (A) were
The same procedure as in Example 1 was carried out except that the thermoplastic resin was composed of a thermoplastic resin having a weight of 0,000 yen and 30% by weight of talc.

The results are shown in Table 1.

(Comparative Example 4) The resin composition layer (B) was made of 40% by weight of a thermoplastic resin,
The resin composition layer (A
) was composed of 50% by weight of thermoplastic resin and 50% by weight of talc, but was carried out in the same manner as in Example 1 above.

The results are shown in table m1.

(Comparative Example 5) The resin composition layer (B) and the resin composition layer (A) were
With 0% by weight of thermoplastic resin and 50% by weight of talc, a
The same procedure as in Example 1 was carried out except for the following.

The results are shown in Table 1.

(Comparative Example 6) The resin composition layer (B) was made of 60% by weight of a thermoplastic resin,
The same procedure as in Example 1 was conducted except that the resin composition layer (A) was composed of 50% by weight of a thermoplastic resin and 50% by weight of talc.

The results are shown in Table 1.

(Comparative Example 7) Resin composition R(A) was mixed with 50% by weight of thermoplastic resin,
The procedure of Example 1 was repeated except that the resin composition layer (A) was composed of 50% by weight of talc and 50% by weight of thermoplastic resin and 50% by weight of calcium carbonate.

The results are shown in Table 1.

[Effect of the invention] Therefore, according to the invention as set forth in claim 1, for example, a layer containing a thermoplastic resin and a large amount of inorganic filler and a thermoplastic resin layer containing no inorganic filler can be used. Heat resistance, rigidity, and oil resistance.

A laminate is provided that has excellent properties such as II resistance, punchability, and compatibility with easily peelable lid materials while maintaining excellent properties such as elution resistance and easy incineration.

Heat resistance and rigidity according to the invention according to claim 2.

It has excellent oil resistance, elution resistance, and easy incineration properties, and
It is possible to obtain a laminated sheet that has excellent punchability, easy peelability, and compatibility with lid materials.

According to the invention according to claim 3, heat resistance, rigidity 2 oil resistance,
It is possible to obtain an end-layer container made of a laminate that has excellent elution resistance and easy incineration properties, as well as excellent impact resistance, punching properties, and compatibility with easily peelable lid materials.

The 211-layer body and the laminated container of the present invention, for example, have excellent punching properties, so they can be easily obtained into any shape, and the laminated container of the present invention can be heat-sealed with the 1M material. Even if used as a container, the lid material can be easily peeled off and opened.

In this way, the laminate and m-layer container of the present invention can be suitably used for microwave oven containers, retort food containers, and the like.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing an example of the laminate of the present invention. FIG. 2 is an explanatory diagram showing an example of a laminate according to the present invention. (A)...Resin composition layer (A), CB)...Red resin composition layer (B), (C)...φ resin composition layer (
B). Procedural amendment dated June 28, 1989

Claims (3)

[Claims] (1) A resin composition layer containing a thermoplastic resin and a scale-like inorganic filler blended in an amount of 20 to 80% by weight based on the total weight of the scale-like inorganic filler and thermoplastic resin (
A non-scaly inorganic filler blended between A) and the thermoplastic resin layer (C) at a ratio of 20 to 80% by weight based on the total weight of the non-scaly inorganic filler and the thermoplastic resin. , and a resin composition layer containing a thermoplastic resin (B
) A laminate characterized by having: (2) The laminate according to claim 1, which is a laminate sheet formed by a coextrusion method. (3) A laminate container comprising the laminate according to claim 1, wherein the resin composition layer (A) forms the inner surface of the container.