JPH11129418A - Poly-4-methyl-1-pentene resin laminate and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To adjust a gas permeability from a high range to a low range by laminating a layer made of a 4-methyl-1-pentene polymer, an intermediate layer made of an adhesive resin composition, and a layer made of an olefin polymer. SOLUTION: The poly-4-methyl-1-pentene resin laminate is constituted by laminating a layer made of a 4-methyl-1-pentene polymer, an intermediate layer made of an adhesive resin composition, and a layer made of an olefin polymer. As the adhesive resin composition, a composition of the 4-methyl-1-pentene polymer and a 1-butene polymer or a composition of the 4-methyl-1-pentene polymer, the 1-butene polymer and a propylene polymer is used. Thus, an oxygen permeability can be adjusted from a high range to a low range. For example, it can be used as a freshness holding packaging material of fruit and vegetable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate containing a 4-methyl-1-pentene polymer layer and its use, and more particularly, to a gas containing a 4-methyl-1-pentene polymer layer. The present invention relates to a resin laminate whose transmittance can be easily adjusted and a packaging material made of the laminate.

[0002]

BACKGROUND OF THE INVENTION It has been conventionally known that fruits and vegetables such as vegetables and fruits are wrapped in a packaging material in order to prevent rot and deterioration of the fruits and vegetables and maintain freshness. For example, vegetables such as lettuce, peppers, broccoli, asparagus, spinach, shiitake mushrooms, fruits such as peaches, etc. are wrapped in a packaging material made of polypropylene, low-density polyethylene, polybutadiene, etc. to maintain freshness. ing. However, fresh fruits, such as broccoli and asparagus, which have a high respiratory rate are particularly difficult to maintain freshness, and there has been a demand for the development of a packaging material capable of maintaining freshness for a long period of time.

[0003] In order to maintain the freshness of fruits and vegetables having a large amount of respiration, it is generally said that it is desirable to use a packaging material having excellent gas permeability. As a method of increasing the gas permeability of the packaging material, a method of reducing the thickness of the packaging material can be considered.However, it is difficult to reduce the thickness due to the problem of maintaining an appropriate strength as the packaging material and the problem of manufacturing technology. There is a limit. Further, a method of increasing the gas permeability of the packaging material by kneading the filler into the resin may be considered, but a problem such as generation of a pinhole occurs. Further, JP-A-5-168398, JP-A-5-260892, and JP-A-6-22
No. 686 and Japanese Patent Application Laid-Open No. 7-264975 describe a method for improving gas permeability by making a fine hole in a packaging material, but there is a possibility that bacteria may enter from the hole, which is preferable for hygiene. Absent.

On the other hand, it is said that it is desirable to package fruits and vegetables with a packaging material having low gas permeability in order to maintain the freshness of fruits and vegetables having a small amount of respiration. As described above, it is necessary to use a material having a gas permeability corresponding to the breathing amount of the fruits and vegetables to be packaged as the packaging material for maintaining the freshness of the fruits and vegetables. However, it has been difficult to adjust the gas permeability of the packaging material from a high range to a low range by the conventional technology.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and has as its object to provide a resin laminate in which the gas permeability can be easily adjusted and a packaging material comprising the laminate. And

[0006]

SUMMARY OF THE INVENTION A poly-4-methyl-1-pentene resin laminate according to the present invention comprises: (I) a layer comprising a 4-methyl-1-pentene polymer (A); and (II) an adhesive resin. It is characterized by comprising an intermediate layer composed of the composition (B) and a layer composed of the olefin polymer (C) (III).

As such a poly-4-methyl-1-pentene resin laminate, (1) the adhesive resin composition (B) is a 4-methyl-1-pentene polymer (b-1) (2) the adhesive resin composition (B) is a 4-methyl-1-pentene-based polymer (b-1); and a 1-butene-based polymer (b-2). 40 to 97.5 parts by weight, and 1-butene polymer (b-2) in an amount of 2.5 to 60 parts by weight (provided that (b-1) and (b-2) ) Is 10
0 weight. ) Laminate as composition (3) The olefin polymer (C) is a propylene polymer (c-1), and the adhesive resin composition (B) is
Methyl-1-pentene polymer (b-1) and 1-butene polymer
(b-2) and a 4-methyl-1-pentene polymer (b-
1) in an amount of 40 to 97.5 parts by weight, and 1-butene polymer (b-2) in an amount of 2.5 to 60 parts by weight (provided that (b-1) and (b-1) The total amount with b-2) is 100 weight.)
(4) The adhesive resin composition (B) is composed of a 4-methyl-1-pentene polymer (b-1), a 1-butene polymer (b-2), and a propylene Laminate which is a composition with polymer (b-3) (5) The adhesive resin composition (B) has a 4-methyl-1-pentene polymer (b-1) of 40 to 97.5. 1-butene polymer (b-2) in an amount of 2.5-60 parts by weight (however, the total amount of (b-1) and (b-2)) Is 100
Weight. ), The propylene-based polymer (b-3) and the 4-methyl-1-pentene-based polymer (b-1) and the 1-butene-based polymer (b-
2) A laminate comprising the composition in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total amount of (6) wherein the olefin-based polymer (C) is a propylene-based polymer (c-1) Wherein the adhesive resin composition (B) is 4-
Methyl-1-pentene polymer (b-1) and 1-butene polymer
(b-2) and a propylene-based polymer (b-3), containing a 4-methyl-1-pentene-based polymer (b-1) in an amount of 40 to 97.5 parts by weight, 2.5 to 60 butene polymer (b-2)
It is contained in an amount of part by weight (provided that the total amount of (b-1) and (b-2) is 100 parts by weight). 1 to 10 parts by weight based on 100 parts by weight of the total amount of the pentene polymer (b-1) and the 1-butene polymer (b-2)
(7) The olefin-based polymer (C) is an ethylene-based polymer (c-2), and the adhesive resin composition (B) is 4% by weight. -Methyl-1-pentene polymer (b-1) and 1-butene polymer (b-
2), ethylene-butene copolymer (b-4) and, if necessary, propylene-butene copolymer (b-5), 4-methyl-1-pentene polymer (b-1) In an amount of 20 to 60 parts by weight, a 1-butene-based polymer (b-2) in an amount of 5 to 40 parts by weight, and an ethylene / butene copolymer (b-4) in an amount of 30 to 30 parts by weight.
Propylene / butene copolymer (b-5) in an amount of 0 to 30 parts by weight (provided that (b-
The total amount of 1), (b-2), (b-4), and (b-5) is 100 weight. ) The composition is a laminate.

[0008] Such a poly-4-methyl-1-pentene resin laminate can adjust the gas permeability such as oxygen permeability from a high range to a low range, and is, for example, a packaging material for maintaining freshness of fruits and vegetables. Can be used as

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, poly-4-methyl according to the present invention will be described.
The 1-pentene resin laminate and its use will be specifically described.

The poly-4-methyl-1-pentene-based resin laminate according to the present invention comprises (I) a layer comprising a 4-methyl-1-pentene-based polymer (A), and (II) an adhesive resin composition. It is composed of an intermediate layer composed of (B) and a layer composed of (III) an olefin polymer (C).

First, each resin used in the poly-4-methyl-1-pentene resin laminate according to the present invention will be described. 4-Methyl-1-pentene-based polymer (A) As the 4-methyl-1-pentene-based polymer, a homopolymer of 4-methyl-1-pentene and 4-methyl-1-pentene have the same carbon number as that of 4-methyl-1-pentene. Α other than 2 to 24 4-methyl-1-pentene
-Copolymers with olefins.

Other α-olefins other than 4-methyl-1-pentene having 2 to 24 carbon atoms include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, -Tetradecene, 1-octadecene, 1-hexadecene, 1-dodecene, 1-tetradodecene and the like. These α-olefins can be used alone or in combination of two or more. Among these, 1-hexene is preferred in view of copolymerizability.

In the 4-methyl-1-pentene polymer, units derived from 4-methyl-1-pentene are present in a proportion of 100 to 80 mol%, preferably 98 to 85 mol%, The units derived from olefins are present in a proportion of 0 to 20 mol%, preferably 2 to 15 mol%. When the content of the unit derived from 4-methyl-1-pentene and the unit derived from α-olefin is within the above range, the 4-methyl-1-pentene polymer has gas permeability and mechanical strength. Excellent.

The 4-methyl-1-pentene polymer (A)
Is a melt flow rate (MF) measured under the conditions of a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238.
R) is 0.1 to 200 g / 10 min, preferably 1.0 to 200 g / 10 min.
It is preferably in the range of 150 g / 10 minutes.

The method for producing the 4-methyl-1-pentene polymer is not particularly limited, and it can be produced by a conventionally known method, for example, a method using a Ziegler-Natta catalyst, a method by cationic polymerization, or the like.

The above 4-methyl-1-pentene polymer (A) may be graft-modified with a modifying monomer. From the modified 4-methyl-1-pentene polymer,
It is preferable because a film having excellent adhesiveness and sheet properties can be obtained.

Specific examples of the modified monomer include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, endo-cis-bicyclo [2.2.1 ] Hept-5-ene
Unsaturated carboxylic acids such as -2,3-dicarboxylic acid (Nadic acid ^™ ); and derivatives thereof such as acid halides, acid amides, acid imides, acid anhydrides and esters. Examples of specific compounds of this derivative include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, dimethyl maleate, glycidyl maleate, methyl (meth) acrylate, and methyl (meth) acrylate. ) Acrylic acid alkyl esters and the like. These modified monomers can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof are particularly preferable.

The content (graft amount) of the modified monomer in the modified 4-methyl-1-pentene polymer is usually 0.1.
It is 1 to 20% by weight, preferably 0.5 to 5% by weight.
As a method for modifying a 4-methyl-1-pentene polymer, for example, in a solvent in the presence of a polymerization initiator, 4-methyl
1-pentene polymer and modified monomer in 100-300
C., preferably to a temperature of 125 to 250.degree. C., using an extruder in the presence of a polymerization initiator in the presence of a solvent without using a methyl-1-pentene polymer and a modified monomer at 23.degree.
There is a method of kneading at a temperature of 5 to 250 ° C.

Examples of the polymerization initiator include alkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxy-hexyne-3 and diisopropyl peroxide; Aryl peroxides such as dicumyl peroxide; acyl peroxides such as lauroyl peroxide; aroyl peroxides such as dibenzoyl peroxide; ketone peroxides such as methyl ethyl ketone hydroperoxide and cyclohexanone peroxide; t-butyl Hydroperoxides such as peroxides and cumene hydroperoxide; peroxycarbons; and organic peroxides such as peroxycarboxylates. These can be used alone or in combination of two or more. The amount of the polymerization initiator to be used is usually about 0.01 to 1 part by weight based on 100 parts by weight of the 4-methyl-1-pentene polymer.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and tetradecane; alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclodecane; benzene, toluene , Xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene and other aromatic hydrocarbons; chlorobenzene, bromobenzene,
o-dichlorobenzene, carbon tetrachloride, trichloroethane,
Halogenated hydrocarbons such as trichloroethylene, tetrachloroethane, and tetrachloroethylene; and kerosene, which is a mixture of aliphatic hydrocarbons. These can be used alone or in combination of two or more. The amount of the solvent to be used is generally about 100 to 5,000 parts by weight based on 100 parts by weight of the 4-methyl-1-pentene polymer.

Adhesive resin composition (B) The adhesive resin composition used in the present invention comprises at least 2
And a layer composed of the 4-methyl-1-pentene polymer (A) and an olefin polymer (C) described later.
The resin composition is not particularly limited as long as it is a resin capable of adhering to a layer composed of, but is preferably a resin composition of the following (I) to (III).

(I) 4-methyl-1-pentene polymer (b-
A resin composition comprising 1) and a 1-butene polymer (b-2). The resin composition (I) contains the 4-methyl-1-pentene polymer (b-1) in an amount of 40 to 97.5 parts by weight,
The 1-butene polymer (b-2) is contained in an amount of 2.5 to 60 parts by weight (provided that the total amount of (b-1) and (b-2) is 100 parts by weight. Is preferred.

(II) 4-methyl-1-pentene polymer (b-
1) A resin composition comprising 1-butene-based polymer (b-2) and propylene-based polymer (b-3). This resin composition (II)
Means that the 4-methyl-1-pentene polymer (b-1) is 40 to 9
1-butene polymer (b-2) contained in an amount of 7.5 parts by weight
Is contained in an amount of 2.5 to 60 parts by weight (provided that (b-1)
The total amount with (b-2) is 100 parts by weight. ), The propylene-based polymer (b-3) is preferably contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total of (b-1) and (b-2).

When the adhesive resin composition (B) is the resin composition (I) or (II), the layer composed of the olefin polymer (C) is composed of the propylene polymer (c-1). Is preferred.

(III) 4-methyl-1-pentene polymer (b-
1) a resin composition comprising a 1-butene-based polymer (b-2), an ethylene / butene copolymer (b-4) and, if necessary, a propylene / butene copolymer (b-5) Thing (III).

The resin composition (III) contains the 4-methyl-1-pentene polymer (b-1) in an amount of 20 to 60 parts by weight, and the 1-butene polymer (b-2) Is contained in an amount of 5 to 40 parts by weight, and the ethylene / butene copolymer (b-4) is contained in an amount of 30 to 60 parts by weight.
Propylene-butene copolymer (b
-5) in an amount of 0 to 30 parts by weight (provided that (b-1)
The total amount of (b-2), (b-4) and (b-5) is 100 parts by weight. Is preferred.

The adhesive resin composition (B) is a resin composition (II)
In the case of I), the layer composed of the olefin polymer (C) is preferably composed of the ethylene polymer (c-2).
The 4-methyl-1-pentene polymer (b-1) forming the resin compositions (I) to (III) is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene. 2 to 2 carbon atoms
It is preferably a copolymer with 0 α-olefin. The unit derived from 4-methyl-1-pentene is preferably in the range of 100 to 80 mol%, and the unit derived from another α-olefin is preferably in the range of 0 to 20 mol%.
In particular, from the viewpoint of the adhesiveness of the adhesive resin composition, a copolymer is preferable, and the unit derived from 4-methyl-1-pentene is 99.9 to 80 mol%, and is derived from another α-olefin. The unit to be formed is preferably a copolymer in the range of 0.1 to 20 mol%.

The 1-butene polymer (b-2) forming the resin compositions (I) and (II) is a homopolymer of 1-butene or 1-butene.
A copolymer of butene and an α-olefin other than 1-butene, wherein a structural unit derived from 1-butene is 60% by weight.
It is a copolymer containing the above. In particular, when the structural unit derived from 1-butene is contained in an amount of 80% by weight or more, the (b-2) 1-butene-based polymer becomes compatible with the (b-1) 4-methyl-1-pentene-based polymer. Excellent.

Here, the α-olefin other than 1-butene has 2 to 2 carbon atoms other than butene such as ethylene, propylene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. 20 α-olefins. These α-olefins can be used alone or in combination of two or more. Of these, ethylene and propylene are preferred.

The 1-butene-based polymer (b-2) was obtained from ASTM
According to D1238, load 2.16kg, temperature 190 ℃
MFR measured under the conditions of 0.01 to 100 g / 10
Min, preferably 0.1 to 50 g / 10 min. When the MFR of the 1-butene-based polymer (b-2) is within the above range, the miscibility with the 4-methyl-1-pentene-based polymer (b-1) is improved, and the adhesive resin composition ( B) exhibits high adhesive performance.

The propylene-based polymer (b-3) forming the resin composition (II) has a proportion of a homopolymer of propylene and a constitutional unit derived from propylene of 90 mol% or more, preferably 95 mol% or more. Certain propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, propylene / α-olefin random copolymer such as random copolymer of propylene / α, ratio of structural units derived from ethylene Is a propylene / ethylene block copolymer of 5 to 30 mol%.

This propylene-based polymer (b-3) is AST
Load 2.16 kg, temperature 230 according to MD1238
The MFR measured under the condition of C is 0.01 to 100 g / 10
Min, preferably 0.1 to 50 g / 10 min. When the MFR of the propylene-based polymer (b-3) is within the above range, the miscibility with other resins constituting the resin composition is improved.

Ethylene which forms the resin composition (III)
The butene copolymer (b-4) is a copolymer containing at least 60% by weight, preferably at least 80% by weight, of a structural unit derived from ethylene.

The ethylene / butene copolymer (b-4)
According to ASTM D1238, the MFR measured under the conditions of a load of 2.16 kg and a temperature of 190 ° C. is 0.01 to 100.
g / 10 minutes, preferably 0.1 to 50 g / 10 minutes. When the MFR of the ethylene / butene polymer (b-4) is within the above range, the miscibility with other resins constituting the resin composition is improved, and the adhesive resin composition (B)
Exhibits high adhesion performance.

The propylene / butene copolymer (b-5) forming the resin composition (III) is a copolymer containing 60% by weight or more, preferably 80% by weight or more of a structural unit derived from propylene. is there.

This propylene / butene copolymer (b-5)
Is a 2.16 kg load according to ASTM D1238,
The MFR measured at a temperature of 190 ° C. is 0.01 to 1
It is desirably in the range of 00 g / 10 min, preferably 0.1 to 50 g / 10 min. Propylene-butene polymer (b
When the MFR of -5) is within the above range, the miscibility with other resins constituting the resin composition is improved, and the adhesive resin composition (B) exhibits high adhesive performance.

The resin compositions (I) to (III) can be produced, for example, by melt-kneading the 4-methyl-1-pentene polymer with another resin by a conventionally known method. For example, a predetermined amount of a 4-methyl-1-pentene polymer and another resin are mixed in a V blender, ribbon blender, Henschel mixer, tumbler blender, etc., and then melted in a single screw extruder, a double screw extruder, or the like. It can be manufactured by kneading and granulating, or by melt-kneading with a kneader or a Banbury mixer and pulverizing.

When the intermediate layer is made of the resin composition having the above composition, the surface layer can be firmly bonded. Olefin polymer (C) As the olefin polymer, polyethylene, ethylene.
α-olefin copolymer, ethylene / α-olefin
Ethylene polymers such as non-conjugated polyene copolymers (c-
2); propylene-based polymers (c-1) such as polypropylene, propylene / α-olefin copolymer, block polypropylene and random polypropylene; butene-based polymers such as poly-1-butene and 1-butene copolymer And the like.

As the propylene-based polymer (c-1), in particular, polypropylene, a copolymer of propylene and 30 mol% or less of ethylene, or propylene and 30 mol%
It is preferable to be a copolymer with the following α-olefin having 4 to 12 carbon atoms. This copolymer may be a block copolymer or a random copolymer. The crystallinity measured by the X-ray diffraction method is preferably 30% or more.

The ethylene-based polymer (c-2) is particularly preferably polyethylene or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms of 30 mol% or less. The ethylene-based polymer includes linear low-density polyethylene, high-density polyethylene, and high-pressure low-density polyethylene. The crystallinity measured by the X-ray diffraction method is preferably 30% or more.

Compounding agent The resin forming the poly-4-methyl-1-pentene resin laminate of the present invention may contain an inorganic filler. Specific examples of the inorganic filler include fine powder talc, kaolinite, calcined clay, pyrophyllite, sericite, natural silicic acid or silicate such as wollastonite, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate and the like. Hydroxides such as carbonates, aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc white and magnesium oxide, synthetic silicic acids or silicates such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride Flake filler such as mica; basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotolite, potassium titanate, erestadite, etc. Filler; glass balun, hula Such as balloon-shaped fillers such as ash balloon and the like.

In addition to such inorganic fillers, organic fillers such as high styrenes, lignins, and re-rubbers may be used. As the above-mentioned inorganic filler, fine powder talc is particularly preferred, and one having an average particle size of 0.2 to 3 μm, particularly 0.2 to 2.5 μm is preferably used. In the fine powder talc, the content of particles having a particle size of 5 μm or more is desirably 10% by weight or less, preferably 8% by weight or less. The particle size of the fine powder talc can be measured by a liquid phase sedimentation method.

Among such fine powder talc, talc having an average aspect ratio of 3 or more, particularly 4 or more, is preferable. Used.

The above-mentioned inorganic filler, in particular, fine powder talc may be untreated or may have been previously surface-treated. Specific examples of the surface treatment include a chemical or physical treatment using a treating agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Can be

The resin for forming the poly-4-methyl-1-pentene resin laminate according to the present invention may further comprise a phenolic antioxidant, a sulfuric antioxidant, a phosphorus Antioxidants such as antioxidants; nucleating agents such as aluminum carboxylate, aromatic phosphate, dibenzylidene sorbitol; heat stabilizers, ultraviolet absorbers, lubricants, antiblocking agents, antistatic agents, Flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizers, foaming agents, plasticizers, foam inhibitors, crosslinkers, flow improvers such as peroxides, light stabilizers, weld strength improvers And various compounding agents such as anti-fogging agents.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and stearyl (3,3
Phenols such as -dimethyl-4-hydroxybenzyl) thioglycolate and 4,4'-butylidenebis (2-tert-
Butyl-5-methylphenol) carbonate oligoesters (for example, polymerization degree 2, 3, 4, 5, 6, 7, 8, 9, 1)
0) and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionate. Examples of the phosphorus-based antioxidant include triphenyl phosphite.

The general formula M _x Al _y (OH) _{2x + 3y-2z} (A) _z · aH ₂ O (where M represents Mg, Ca or Zn, A represents an anion other than a hydroxyl group, and x , Y and z are positive numbers,
a is 0 or a positive number. ) Can be added, for example, as a hydrochloric acid absorbent.

Light stabilizers include, for example, 2-hydroxy
4-methoxybenzophenone and the like. Examples of the lubricant include paraffin wax, polyethylene wax, calcium stearate and the like.

These additives can be used in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the resin constituting the poly-4-methyl-1-pentene resin laminate. When the above-mentioned additives and the like are contained in the resin constituting the poly-4-methyl-1-pentene resin laminate, the balance of physical properties, durability, paintability, printability, scratch resistance and moldability are further improved. It results in an improved laminate.

The various compounding agents as described above can be prepared by simultaneously or sequentially mixing the above components, for example, using a Henschel mixer,
It is charged into a V-type blender, tumbler blender, ribbon blender, etc., kneaded, and then melt-kneaded with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc., to obtain poly-4-methyl-1-pentene. It can be blended with the resin forming the base resin laminate.

Among these, it is preferable to use an apparatus having excellent kneading performance such as a multi-screw extruder, a kneader, a Banbury mixer, etc., since each component can be more uniformly dispersed.

Laminate The poly-4-methyl-1-pentene resin laminate according to the present invention comprises a layer composed of a 4-methyl-1-pentene polymer (A) and an adhesive resin composition (B). And a layer made of the olefin polymer (C).

The thickness of each layer constituting the laminate is not particularly limited, and is appropriately set depending on desired oxygen permeability, carbon dioxide permeability, and water vapor permeability. The thickness ratio of each layer constituting the laminate of the present invention is, for example, a layer composed of the 4-methyl-1-pentene polymer (A), an intermediate layer composed of the adhesive resin composition (B), and an olefin weight. The ratio with the layer comprising the coalesced (C) is usually 1 to 100: 1 to 100: 1 to 100, preferably 50 to 100: 1 to 50: 1 to 50.

The thickness of the laminate is not particularly limited, and can be appropriately selected depending on the shape, size, and application of the laminate, and is usually about 0.01 to 3 mm, preferably about 0.02 to 0.5 mm.
mm.

The method for producing the poly-4-methyl-1-pentene resin laminate according to the present invention includes, for example, 4-methyl
1-pentene polymer (A), adhesive resin composition (B), and olefin polymer (C) are co-extruded using a multilayer die such as a T-die casting method or a water-cooled inflation method. Examples include a method of co-extrusion molding by a processing method, and a method of manufacturing a laminate by press-molding a sheet, film, or the like that has been prepared from each resin by press molding, extrusion molding, or the like.

Since the 4-methyl-1-pentene polymer is a resin having a very high gas permeability, it is not available conventionally by laminating with an olefin polymer having a low gas permeability and adjusting the thickness of each layer. It is possible to adjust oxygen permeability, carbon dioxide permeability, water vapor permeability and gas permeability in a wide range. The use of a low-melting-point olefin polymer as a surface layer can impart heat sealing properties.

Packaging Material The packaging material according to the present invention comprises the above-mentioned poly-4-methyl-1-pentene resin laminate, and its shape includes films, sheets, bags, bottles, cans, boxes, tubular containers and the like. is there.
When the thickness of the packaging material is a film, a bag, or the like, the thickness is usually 20 to 100 μm, preferably 30 to 50 μm.
In the case of a bottle, a can, a box, a tubular container, or the like, it is usually 0.2 to 3 mm, and preferably 0.5 to 3 mm.
２2 mm. The thickness of the packaging material can be partially changed in order to adjust the gas permeability.

Further, only a part of the container is made of poly-4-methyl-1-
It may be a film made of a penten-based resin laminate.
The production of the packaging material used in the present invention can be performed according to a conventional method, and is not particularly limited.

In the method for maintaining freshness of fruits and vegetables according to the present invention,
Fruits and vegetables are packaged with the packaging material as described above, and examples of fruits and vegetables that can be kept fresh by the method of the present invention are shown below. Apricot, avocado, fig, strawberry, blackberry,
Blueberry, cranberry, duberry, gooseberry, logan blackberry, raspberry (black), raspberry (red), oyster, chestnut, coconut, cherry, watermelon, none, pineapple (green), pineapple (ripe), banana, papaya, plum, Fruits such as quince, mango, melon (cantaloupe), melon (honeydew), peach, apple; asparagus, green bean, lime bean, okra, turnip, western pumpkin, cauliflower, cabbage, brussels sprouts, cucumber, green peas, kale, sweet potato , Potatoes, sweet corn, popcorn, celery, radish, onion, pepper (shishi), tomato, eggplant, garlic, carrot (with leaves), carrot (root), spinach, Rokkori, mushrooms, rhubarb, lettuce, such as vegetables such as vegetable seeds, and the like.

According to the method of the present invention, the freshness of the cut vegetables can be maintained. As the cut vegetables, carrots (dies, randomly cut, diced, sticks, coin cuts, pinions), potatoes (dies, randomly cut, shredded), Sticks, cabbage (sliced, shredded), radishes (chopped, sticks, pickled), onions (dice, chopped, sliced, sliced), cucumbers (sticks, sliced), celery (sticks), peppers (half,
1/4 cut, round slice, shredded), lettuce (square cut, 1
/ 4 cut, slice), spinach (boiled, raw),
Asparagus (boiled, raw), Broad bean (peeled), Green peas (peeled), Edamame (boiled), Leek onion (for sliced condiments, sliced, shredded), Universal leek (for condiments),
Sunny lettuce (leaves only), parsley (leaves only), eggplant (1
/ 2 cut, 1/4 cut), sweet potato (slice), pumpkin (slice, randomly cut), red carrot (ring), red cabbage (shred), shishito, green beans, lotus, burdock (ring, shredded), etc., and What mixed these two or more types is mentioned.

[0062]

The gas permeability of the poly-4-methyl-1-pentene resin laminate of the present invention can be adjusted from a high range to a low range.

When the packaging material comprising the poly-4-methyl-1-pentene resin laminate according to the present invention is used, freshness of fruits and vegetables can be maintained for a long period of time.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the following examples, physical properties were measured as follows. Oxygen permeability Oxygen permeability is OX-TRAN (manufactured by Modern Control)
Was measured under the conditions of a temperature of 23 ° C. and a humidity of 0%. (3 layers) Oxygen permeation amount V (cc / m ^2.
24 hr · atm), and the oxygen permeation coefficient k (cc · mm / m ² · 24 hr · atm), which is the amount of oxygen permeated per (3 layers) film thickness of 1 mm, was calculated from this.

Note that there is a relationship between V and k, where k = dV / 1000, where d (μm) is the thickness of the film. Measurement of adhesion strength Test speed 300mm / min, peel width 15mm, temperature 23 ° C
The T-peel peel test of the three-layer film was performed under the following conditions.

Freshness Retention Test The freshness of fruits and vegetables was evaluated by visually observing changes in appearance and color at 25 ° C. every day according to the following criteria.

：: Good freshness ：: Somewhat poor ×: Poor The following resin was used as the resin forming the resin laminate or film.

TPX (1): 4-methyl-1-pentene and 1-
Copolymer of tetradecene and 1-dodecene, manufactured by Mitsui Chemicals, Inc., trade name MX021, density = 0.83 g / c
m ³ , MFR = 4 g / 10 min, oxygen permeability coefficient = 1500 c
c · mm / m ² · 24 hr · atm TPX (2): copolymer of 4-methyl-1-pentene and 1-decene, manufactured by Mitsui Chemicals, Inc., trade name DX810, density = 0.83 g / cm ³ , MFR = 4 g / 10 min, oxygen permeability coefficient = 1500 cc · mm / m ² · 24 hr · atm PB: 1-butene polymer, manufactured by Mitsui Chemicals, Inc., trade name
BL3080, density = 0.89 g / cm ³ , MFR =
0.2 g / 10 min, oxygen permeability coefficient = 500 r-PP: propylene polymer, manufactured by Mitsui Chemicals, Inc., trade name: F327, density = 0.91 g / cm ³ , MFR =
7 g / 10 min, oxygen permeability coefficient = 100 PER: propylene / ethylene copolymer, manufactured by Mitsui Chemicals, Inc., trade name S4030, density = 0.89 g / c
m ³ , MFR = 0.2 g / 10 min, oxygen permeability coefficient = 240
cc · mm / m ² · 24 hr · atm TF-A: ethylene polymer, manufactured by Mitsui Chemicals, Inc., trade name A4085, density = 0.88 g / cm ³ , MFR =
3.6 g / 10 min, oxygen permeability coefficient = 510 TF-XR: propylene-based polymer, manufactured by Mitsui Chemicals, Inc.
Product name XR110T, density = 0.89 g / cm ³ , M
FR = 3.2 g / 10 min, oxygen permeability coefficient = 240 cc · m
m / m ² · 24 hr · atm Modified PE (1): Maleic acid-modified polyethylene, manufactured by Mitsui Chemicals, Inc., trade name NE070, density = 0.93 g / c
m ³ , MFR = 1.0 g / 10 min, oxygen permeability coefficient = 250
cc · mm / m ² · 24 hr · atm Modified PE (2): maleic acid-modified polyethylene, manufactured by Mitsui Chemicals, Inc., trade name HE040, density = 0.95 g / c
m ³ , MFR = 2.0 g / 10 min, oxygen permeability coefficient = 200
cc · mm / m ² · 24 hr · atm LLDPE: Linear low-density polyethylene, manufactured by Mitsui Chemicals, Inc., trade name UZ0521L, density = 0.91 g
/ Cm ³ , MFR = 2.0 g / 10 min, oxygen permeability coefficient = 2
00cc ・ mm / m ²・ 24hr ・ atm

[0070]

Example 1 Production of Resin Laminate Using a resin shown in Table 1 as a 4-methyl-1-pentene-based polymer, an adhesive resin composition and an olefin-based polymer, a resin having a thickness of 30 μm was produced by a film molding machine. Three-layer resin laminate (TPX (1) / adhesive resin composition / r-PP = 1
0/10/10 μm). Die temperature is 280
° C and the die clearance was set at 0.5 mm. The extrusion temperature of the 4-methyl-1-pentene polymer was 280 ° C., and the extrusion temperature of the adhesive resin composition was 250.
° C, and the extrusion temperature of the olefin polymer was 220 ° C. With respect to the obtained resin laminate, the amount of oxygen permeation was measured to determine the oxygen permeability coefficient of the laminate. The peel strength of the laminate was measured. Table 1 shows the results.

The adhesive resin composition was prepared by mixing TPX (1) with 90.
Parts by weight, 10 parts by weight of PB, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl as a stabilizer 2,4,8,10-tetrakispiro [5,5] undecane (Sumitomo Chemical Industries, Ltd., trade name: Sumilizer GA80)
0.110 parts by weight of penta (erythrityl-tetra-β
-Mercaptonyl) propionate (Cipro Kasei Co., Ltd.)
0.20 parts by weight of calcium stearate (manufactured by Sannox 412S)
Was mixed in a ratio of 0.03 parts by weight, mixed at a low speed with a Henschel mixer for 3 minutes, and extruded at a temperature of 280 ° C. with a twin-screw extruder to prepare a mixture.

[0072]

Examples 2 to 4 A resin laminate was prepared in the same manner as in Example 1 except that the resins shown in Table 1 were used as the 4-methyl-1-pentene polymer, the adhesive resin composition and the olefin polymer. Was prepared and the amount of oxygen permeation was measured to determine the oxygen permeation coefficient of the laminate. Table 1 shows the results. The adhesive resin composition was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used in the ratios shown in Table 1.

[0073]

Comparative Examples 1 and 2 A resin laminate was prepared in the same manner as in Example 1 except that the resins shown in Table 1 were used as the 4-methyl-1-pentene polymer, the adhesive resin composition and the olefin polymer. Was prepared and the amount of oxygen permeation was measured to determine the oxygen permeation coefficient of the laminate. Table 1 shows the results.

[0074]

[Table 1]

[0075]

Reference Example 1 Copolymer of 4-methyl-1-pentene and 1-tetradecene (4-MP / TD copolymer, 4-methyl-1-pentene / 1-tetradecene content weight ratio = 95/5) ) Was supplied to an extruder, heated and melted at 260 ° C., kneaded, and extruded from a T-die to obtain a film having a thickness of 50 μm. The oxygen permeation amount of this film was measured, and the oxygen permeation coefficient was obtained. Table 2 shows the results.

The obtained film was formed into a bag of about 12 × 12 cm using a side sealing machine. One bag of asparagus was cut into half, put into the bag, sealed, and a freshness holding test was performed. Table 2 shows the evaluation results.

[0077]

Reference Example 2 A resin composition consisting of 90 parts by weight of a 4-MP / TD copolymer and 10 parts by weight of poly-1-butene (M3080, manufactured by Mitsui Petrochemical Industries, Ltd.) was supplied to an extruder. , 260
The mixture was heated and melted at ℃, kneaded, and extruded from a T-die to obtain a film having a thickness of 50 μm. Table 2 shows the results of measuring the oxygen permeability of this film.

The obtained film was formed into a bag in the same manner as in Reference Example 1, cut cabbage was sealed in about half of the bag, and a freshness holding test was carried out. Table 2 shows the evaluation results.

[0079]

Reference Example 3 One asparagus was cut in half in a polyethylene bag (thickness: 30 μm), sealed, and a freshness retention test was carried out. Table 2 shows the evaluation results.

[0080]

REFERENCE EXAMPLE 4 Cut cabbage was put in about half of a polyethylene bag (thickness: 30 μm) and sealed, and a freshness retention test was performed. Table 2 shows the evaluation results.

[0081]

[Table 2]

Claims (10)

[Claims] 1. A layer comprising (I) a 4-methyl-1-pentene polymer (A), (II) an intermediate layer comprising an adhesive resin composition (B), and (III) an olefin polymer. (C) a poly-4-methyl-1-pentene-based resin laminate. 2. The method according to claim 1, wherein the adhesive resin composition (B) is 4-methyl.
1-pentene polymer (b-1) and 1-butene polymer (b-2)
The poly-4-methyl-1-pentene-based resin laminate according to claim 1, which is a composition comprising: 3. The method according to claim 1, wherein the adhesive resin composition (B) is 4-methyl
1-pentene polymer (b-1) is contained in an amount of 40 to 97.5 parts by weight, and 1-butene polymer (b-2) is contained in an amount of 2.5 to 60 parts by weight. (However, the total amount of (b-1) and (b-2) is 100% by weight.) The poly-4-methyl-1-pentene-based resin laminate according to claim 2, which is a composition. 4. The olefin polymer (C) is a propylene polymer (c-1), and the adhesive resin composition (B) is a 4-methyl-1-pentene polymer (b- 1) and 1-butene-based polymer (b-2),
4-methyl-1-pentene-based polymer (b-1) was used in an amount of 40 to 97.5.
1-butene polymer (b-2) in an amount of 2.5 parts by weight.
The composition according to claim 1, which is contained in an amount of up to 60 parts by weight (provided that the total amount of (b-1) and (b-2) is 100 parts by weight).
4. The poly-4-methyl-1-pentene-based resin laminate according to item 1. 5. The method according to claim 1, wherein the adhesive resin composition (B) is 4-methyl
1-pentene polymer (b-1) and 1-butene polymer (b-2)
2. A composition comprising a propylene polymer (b-3) and a propylene polymer (b-3).
4. The poly-4-methyl-1-pentene-based resin laminate according to item 1. 6. The adhesive resin composition (B) according to claim 1, wherein
1-pentene polymer (b-1) is contained in an amount of 40 to 97.5 parts by weight, and 1-butene polymer (b-2) is contained in an amount of 2.5 to 60 parts by weight. (However, the total amount of (b-1) and (b-2) is 100 wt.), And the propylene-based polymer (b-3) is converted to the 4-methyl-1-pentene-based polymer (b- 1 to 100 parts by weight based on 100 parts by weight of the total of 1) and 1-butene polymer (b-2)
The poly-4-methyl-1-pentene-based resin laminate according to claim 5, which is a composition contained in an amount of part by weight. 7. The olefin polymer (C) is a propylene polymer (c-1), and the adhesive resin composition (B) is a 4-methyl-1-pentene polymer (b- 1), a 1-butene-based polymer (b-2) and a propylene-based polymer (b-3), and the 4-methyl-1-pentene-based polymer (b-1) is 40 to 97.5% by weight. 1-butene polymer (b-2) in an amount of 2.5-60 parts by weight (provided that the total amount of (b-1) and (b-2) is 100 weight)) and the propylene-based polymer (b-3)
The composition according to claim 1, which is a composition containing the pentene polymer (b-1) and the 1-butene polymer (b-2) in an amount of 1 to 100 parts by weight based on a total amount of 100 parts by weight. Poly 4-methyl-1-
Penten-based resin laminate. 8. The olefin polymer (C) is an ethylene polymer (c-2), and the adhesive resin composition (B) is a 4-methyl-1-pentene polymer (b- 1) and 1-butene polymer (b-2) and ethylene
A 4-methyl-1-pentene-based polymer (b-1) consisting of a butene copolymer (b-4) and, if necessary, a propylene / butene copolymer (b-5), in an amount of 20 to 60% by weight; 1-butene-based polymer (b-2) in an amount of 5 to 40 parts by weight, and an ethylene / butene copolymer (b-4) in an amount of 30 to 60 parts by weight. Containing a propylene / butene copolymer (b-5) from 0 to 3
0 parts by weight (however, (b-1), (b-2) and (b-
The total amount of 4) and (b-5) is 100 weight. 2. The poly-4-methyl-1-pentene resin laminate according to claim 1, which is a composition. 9. The poly according to claim 1, wherein
A packaging material excellent in oxygen permeability, characterized by comprising a 4-methyl-1-pentene resin laminate. 10. A packaging material for maintaining the freshness of fruits and vegetables, comprising the poly-4-methyl-1-pentene resin laminate according to any one of claims 1 to 8.