JPH11198315A - Poly(4-methyl-1-pentene)-based resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the anti-fogging properties of a laminate without lowering its transparency and gas permeability by a method wherein a 4-methyl-1-pentene- based polymer and a specified propylene-based polymer of ethylene-based polymer including an anti-fogging agent are laminated to each other through an adhesive layer as an intermediate layer. SOLUTION: A poly(4-methyl-1-pentene)-based resin laminate consists of a layer made of a 4-methyl-1-pentene-based polymer, a intermediate layer made of a bonding resin and a layer made of a propylene-based polymer containing an anti-fogging agent or an ethylene-based polymer containing the anti-fogging agent. In this case, the 4-methyl-1-pentene-based polymer represents a copolymer including about 85 wt.% or more of a single 4-methyl-1-pentene polymer or of the constitutional unit derived from 4-methyl-1-pentene. Further, the propylene- based polymer or ethylene-based polymer includes 0.05-5 wt.% of the anti-fogging agent. Thus, the anti-fogging properties of a laminate can be improved without lowering its transparency and gas permeability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a poly-4-methyl-1-pentene resin laminate, and more particularly to a poly-4-methyl-1-pentene resin laminate having excellent antifogging properties.

[0002]

BACKGROUND OF THE INVENTION In recent years, various plastics have been used as packaging materials for commodities, and characteristics required for the packaging materials differ depending on the types of commodities. For example, when used as a packaging material for fresh products, transparency, gas permeability, anti-fog properties, and the like are required. If the packaging material has poor gas permeability, it will be difficult to maintain the freshness of fresh products for a long time,
If the antifogging property is inferior, water vapor generated from perishables during storage or transportation may condense, causing fogging on the inner surface of the packaging material, significantly impairing the appearance quality of perishables, and causing perishables to perish. is there.

The 4-methyl-1-pentene polymer is a material having excellent transparency and gas permeability and is suitable as a packaging material for fresh products, but there is room for improvement in antifogging properties. . As a method for imparting anti-fogging property to the resin, there is a method of adding an anti-fogging agent. It has been difficult to produce a molded article containing sublimation and an antifogging agent. Further, since the 4-methyl-1-pentene polymer has a low surface tension, it was difficult to laminate another resin containing an antifogging agent.

The inventors of the present invention have conducted intensive studies in such a situation, and as a result, the adhesive layer was used as an intermediate layer to form 4-methyl-1-
When a pentene polymer and a specific propylene polymer or ethylene polymer containing an antifogging agent are laminated, a laminate having excellent antifogging properties can be obtained without significantly lowering transparency and gas permeability. This led to the completion of the present invention.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been made in consideration of the above-mentioned problems.
It is intended to provide a 1-pentene resin laminate.

[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 (B) and a layer composed of (III) a propylene polymer (C) containing an antifogging agent or an ethylene polymer (D) containing an antifogging agent. .

In the present invention, the 4-methyl-1-pentene-based polymer (A) comprises 85 units of a 4-methyl-1-pentene homopolymer or a structural unit derived from 4-methyl-1-pentene.
It is preferable that the copolymer contains not less than% by weight.

The adhesive resin (B) comprises (a) 4-methyl
(B) 1-pentene polymer in an amount of 40 to 70 parts by weight;
Butene copolymer 30-60 parts by weight ((a) + (b)
= 100 parts by weight), or (a) 20 to 60 parts by weight of a 4-methyl-1-pentene-based polymer, and (b) 5 to 40 parts by weight of a 1-butene-based polymer. ,
(C) 30 to 60 parts by weight of an ethylene / butene copolymer, and (d) 0 to 30 parts by weight of a propylene / butene-based polymer ((a) + (b) + (c) + (d) = 100 parts by weight) )
Preferably, the adhesive resin composition comprises:

The propylene polymer (C) or the ethylene polymer (D) preferably contains an antifogging agent in a proportion of 0.05 to 5% by weight.

[0010]

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

The 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 (B). ) And (III) a layer made of a propylene polymer (C) containing an antifogging agent or a layer made of an ethylene polymer (D) containing an antifogging agent.

First, each component constituting the poly-4-methyl-1-pentene resin laminate according to the present invention will be described. 4-Methyl-1-pentene polymer (A) The 4-methyl-1-pentene polymer used in the present invention is
It is a homopolymer of -methyl-1-pentene or a copolymer of 4-methyl-1-pentene and an α-olefin other than 4-methyl-1-pentene having 2 to 20 carbon atoms.

Other α-olefins other than 4-methyl-1-pentene having 2 to 20 carbon atoms include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, -Tetradecene, 1-octadecene, 1-hexadecene, 1-dodecene, 1-tetradodecene, 1-eicosene and the like. These other 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, the structural unit derived from 4-methyl-1-pentene is 100 to 8
5 mol%, preferably 98 to 90 mol%, and the structural unit derived from other α-olefin is 0 to
It is desirably present in a proportion of 15 mol%, preferably 2 to 10 mol%. When the content ratio of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from another α-olefin is within the above range, the 4-methyl-1-pentene polymer has a gas permeable property. And excellent in mechanical strength.

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 desirable to be 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.

Adhesive Resin (B) The adhesive resin (B) used in the present invention includes, for example, (a) a 4-methyl-1-pentene polymer, and (b) a 1-butene copolymer. An adhesive resin composition comprising: (a) 4-
Adhesion consisting of methyl-1-pentene polymer, (b) 1-butene polymer, (c) ethylene / butene copolymer, and if necessary (d) propylene / butene polymer And a resin composition.

(A) The 4-methyl-1-pentene polymer is 4
It is a homopolymer of -methyl-1-pentene or a copolymer of 4-methyl-1-pentene and another α-olefin. Α other than 4-methyl-1-pentene having 2 to 20 carbon atoms
-As the olefin, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-
Examples include tetradecene, 1-octadecene, 1-hexadecene, 1-dodecene, 1-tetradodecene, 1-eicosene, and the like. These other α-olefins can be used alone or in combination of two or more. Among these, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexene or 1-eicosene is preferred.

(A) In the 4-methyl-1-pentene polymer, the structural unit derived from 4-methyl-1-pentene is 1
It is preferable that the content of the structural unit derived from 00 to 80 mol% and the other α-olefin is in the range of 0 to 20 mol%. Particularly, from the viewpoint of the adhesiveness of the adhesive resin (B), it is preferably a copolymer, and the structural unit derived from 4-methyl-1-pentene is 99.9 to 80 mol%, and other α-olefins 0.1-20 mol% of the structural unit derived from
Are preferred.

This (a) 4-methyl-1-pentene polymer has an MFR of 0.1 to 200 measured under the conditions of a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238.
g / 10 minutes, preferably in the range of 1.0 to 150 g / 10 minutes.

(B) The 1-butene-based polymer is a homopolymer of 1-butene or a copolymer of 1-butene and another α-olefin, and has a structural unit derived from 1-butene. 60
It is a copolymer containing not less than% by weight. In particular, when the content of the structural unit derived from 1-butene is 80% by weight or more,
(B) The 1-butene polymer has excellent compatibility with (a) the 4-methyl-1-pentene polymer.

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

This (b) 1-butene-based polymer is 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 (b) 1-butene-based polymer is within the above range, the mixing property of (b) 1-butene-based polymer and other components is improved, and the adhesive resin (B) has high adhesive performance. Demonstrate.

(C) The ethylene / butene copolymer is an ethylene / butene random copolymer containing 50 to 90% by weight of a structural unit derived from ethylene. In particular, the content of the structural unit derived from ethylene is 55 to 8
When the content is within the range of 5% by weight, the adhesive resin (B) is excellent in flexibility, and the dispersibility of (c) the ethylene / butene copolymer in the composition becomes high. ) Exhibits excellent adhesion performance.

Here, butene includes 1-butene, isobutene and 2-butene. These can be used alone or in combination of two or more. Among these, 1-butene and isobutene are preferred. (C)
The ethylene / butene copolymer may contain a structural unit derived from an α-olefin other than ethylene and butene, for example, an α-olefin having 3 to 20 carbon atoms other than butene.

This (c) ethylene / butene copolymer is:
According to ASTM D1238, the MFR measured under the conditions of a load of 2.16 kg and a temperature of 190 ° C is 0.1 to 50 g /
It is desirably in the range of 10 minutes, preferably 1.0 to 30 g / 10 minutes. (C) MF of ethylene / butene copolymer
When R is within the above range, the mixing property of (c) the ethylene / butene copolymer and other components is improved, and the adhesive resin (B) exhibits high adhesive performance.

(D) The propylene / butene copolymer is
It is a propylene / butene random copolymer containing 50 to 90% by weight of a structural unit derived from propylene. In particular, when the content ratio of the structural unit derived from propylene is in the range of 60 to 85% by weight, the adhesive resin (B)
Has excellent mechanical strength and high adhesion performance to a layer made of 4-methyl-1-pentene polymer (A), a layer made of propylene polymer (C), and a layer made of ethylene polymer (D) Demonstrate.

Here, butene includes 1-butene, isobutene and 2-butene. These can be used alone or in combination of two or more. Among these, 1-butene and isobutene are preferred. And (d)
The propylene / butene copolymer may contain a constituent unit derived from another olefin, for example, an olefin having 2 to 20 carbon atoms other than propylene and butene.

This (d) propylene / butene copolymer has an MFR of 0.1 to 200 measured under the conditions of a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238.
g / 10 minutes, preferably in the range of 1.0 to 100 g / 10 minutes. When the MFR of the (d) propylene / butene copolymer is within the above range, (d) the propylene / butene copolymer
The miscibility of the butene copolymer with other components is improved, and the adhesive resin (B) exhibits high adhesive performance.

The adhesive resin (B) used in the present invention comprises:
When (a) 4-methyl-1-pentene polymer and (b) 1-butene copolymer are used, (a) 40 to 70 parts by weight of 4-methyl-1-pentene polymer; (B) 1-butene polymer preferably comprises 30 to 60 parts by weight ((a) + (b) = 100 parts by weight), and (a) 4-methyl-1-
45 to 65 parts by weight of a pentene-based polymer and 35 to 55 parts by weight of (b) 1-butene-based polymer ((a) + (b) = 10)
0 parts by weight) from the viewpoint of adhesive strength.

The adhesive resin (B) used in the present invention comprises: (a) a 4-methyl-1-pentene polymer;
When (b) a 1-butene polymer, (c) an ethylene / butene copolymer, and if necessary (d) a propylene / butene polymer, (a) 4-methyl-1- 20 to 60 parts by weight of a pentene-based polymer, 5 to 40 parts by weight of (b) a 1-butene-based polymer, 30 to 60 parts by weight of an ethylene-butene copolymer, and (d) a propylene-butene-based polymer Copolymer 0 to 30 parts by weight ((a) + (b) +
(C) + (d) = 100 parts by weight), and (a) 4-methyl-1-pentene polymer 30 to 50
Parts by weight, (b) 10 to 30 parts by weight of a 1-butene-based polymer, (c) 35 to 50 parts by weight of an ethylene / butene copolymer, and (d) propylene / butene-based copolymer 5 to 20
Parts by weight ((a) + (b) + (c) + (d) = 10
0 parts by weight) is more preferable in terms of adhesive strength.

This adhesive resin (B) is made of ASTM D1
The MFR measured under the conditions of a load of 5.0 kg and a temperature of 190 ° C. according to 238 is desirably in the range of 0.1 to 200 g / 10 min, preferably 1.0 to 100 g / 10 min. When the MFR of the adhesive resin (B) is within the above range,
(I) comprising 4-methyl-1-pentene polymer (A)
High adhesion performance can be exhibited with respect to the layer (III) made of the propylene polymer (C) containing the antifogging agent or the ethylene polymer (D) containing the antifogging agent.

The adhesive resin (B) is the same as (a) 4-methyl
The 1-pentene polymer and (b) the 1-butene polymer are mixed by a conventionally known method and then melt-kneaded, or (a) the 4-methyl-1-pentene polymer, (b) A) 1-butene-based polymer and (c) an ethylene-butene copolymer,
If necessary, it can be produced by mixing (d) a propylene / butene-based copolymer by a conventionally known method, followed by melt-kneading. For example, a predetermined amount of (a) and (b), or (a), (b) and (c), and if necessary, (d) is mixed with a V blender, a ribbon blender, a Henschel mixer, a tumbler blender, or the like. After that, it can be produced by melt-kneading with a single-screw extruder or a double-screw extruder and granulating, or by melt-kneading and kneading with a kneader, a Banbury mixer or the like.

To the adhesive resin (B), various compounding agents usually used in addition to the polyolefin, such as a silane coupling agent, a weather stabilizer, a heat stabilizer, a slip agent, a nucleating agent, and a dye, may be added. Good.

Propylene Polymer (C) As the propylene polymer (C) used in the present invention, the proportion of a propylene homopolymer or a structural unit derived from propylene is 90 mol% or more, preferably 95 mol%. The above propylene / ethylene random copolymer,
Propylene-based random copolymers such as propylene / ethylene / 1-butene random copolymer and propylene / 1-butene random copolymer, and propylene / ethylene block copolymers having a proportion of structural units derived from ethylene of 5 to 30 mol%. Polymers.

This (C) propylene polymer is AST
According to MD1238, load 5.0kg, temperature 260 ℃
MFR measured under the conditions of 0.01 to 100 g / 10
Min, preferably 0.1 to 50 g / 10 min.

Ethylene Polymer (D) The ethylene polymer (D) used in the present invention includes:
Ethylene homopolymer such as high-pressure low-density polyethylene (LLDPE) and high-density polyethylene; 85 mol% or more, preferably 85 to 98 mol% or more of structural units derived from ethylene.
Mole%, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene
Ethylene copolymers such as a vinyl acetate copolymer and an ethylene / acrylic acid copolymer are exemplified.

This ethylene-based polymer (D) is obtained from ASTM
According to D1238, load 2.16kg, temperature 190 ℃
MFR measured under the conditions of 0.1 to 200 g / 10 min,
Preferably, it is in the range of 1.0 to 100 g / 10 minutes.

The propylene polymer (C) and the ethylene polymer (D) are compounded with the following antifoggants. Specific examples antifogging agents antifogging agent, stearic acid monoglyceride, linoleic acid oleic acid monoglyceride, oleic acid monoglyceride, Beherin acid monoglyceride, glycerol fatty acid esters, such as ricinoleic acid monoglyceride; lauric acid sorbitan esters, palmitic acid sorbitan esters And sorbitan fatty acid esters such as sorbitan stearate and sorbitan oleate. Further, polyoxyethylene / glycerin / monostearate, polyoxyethylene / glycerin / monooleate, or the like can also be used. These antifogging agents can be used alone or in combination of two or more.

The propylene-based polymer (C) contains 0.05 to 5% by weight, preferably 0.5 to 2.0% by weight of an antifogging agent.
It is desirable to mix in the ratio of. The ethylene-based polymer (D) is desirably blended with an antifogging agent in a proportion of 0.05 to 5% by weight, preferably 0.5 to 2.0% by weight.

As a method of blending the propylene polymer (C) and the ethylene polymer (D) with the antifogging agent, a conventionally known method can be adopted, and the blending agent and the like are blended with the polyolefin resin. A conventionally known method used at that time, for example, a method of kneading using a mixer such as an extruder or a plast mill can be adopted.

Laminate The 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. (B) an intermediate layer;
(III) a layer comprising a propylene polymer (C) containing an antifogging agent or an ethylene polymer (D) containing an antifogging agent.

The thickness ratio of each layer constituting the poly-4-methyl-1-pentene resin laminate of the present invention is not particularly limited.
Usually, the ratio of the layers (I), (II) and (III) is usually 1
~ 100: 1 ~ 100: 1 ~ 100, preferably 50 ~
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 2.0 mm, preferably about 0.02 to 2.0 mm.
It is about 0.5 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 (B),
A method of co-extrusion with a propylene polymer (C) containing an antifogging agent or an ethylene polymer (D) containing an antifogging agent,
There is a method of manufacturing a laminate by press-molding a sheet, a film, or the like, which has been prepared from each resin by press molding, extrusion molding, or the like in advance. Further, the obtained sheet or film may be uniaxially or biaxially stretched.

Further, a 4-methyl-1-pentene polymer (A), an adhesive resin (B) and a propylene polymer (C) containing an antifogging agent or an ethylene polymer containing an antifogging agent (D) may be co-extruded and blown to obtain a multilayer blown film.

The poly-4-methyl-1-pentene resin laminate of the present invention is excellent in transparency, gas permeability and anti-fogging properties, and is therefore useful for maintaining freshness of fresh products such as vegetables, fruits and flowers. It can be suitably used for packaging materials. Also food,
It can also be used for containers such as chemicals.

When the poly-4-methyl-1-pentene resin laminate according to the present invention is used as a packaging material for perishable products,
The layer (III) is the inner layer (the side that comes into contact with fresh products).

[0049]

The poly-4-methyl-1-pentene resin laminate according to the present invention has excellent antifogging properties. Further, it has excellent transparency and gas permeability.

[0050]

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

The physical properties of the polymer and the film were measured as follows. MFR (Melt Flow Rate) Based on ASTM D1238, 4-methyl-1-pentene polymer is used at 260 ° C under 5 kg load, propylene polymer is used at 230 ° C under 5 kg load, and other resins are used. Was measured at 190 ° C. under a load of 5 kg.

[0052] attach the sample to the apparatus shown in antifogging Figure 1, tilt the device so that the sample surface is inclined angle of 15 °, to observe the state of the water droplets adhering to the lower surface of the sample film after 30 minutes,
The film was evaluated as the antifogging property. The laminate was attached such that the propylene-based polymer layer or the ethylene-based polymer layer faced down.

[Evaluation Criteria] 流: No water droplets are recognized in a flowable state. △: Stream streaks and water droplets are mixed.

[0054]

Example 1 4-methyl-1-pentene polymer (A-1): melting point: 237 ° C., MFR: 25 g / 10 min, density: 0.8
35 g / cm ³ (ASTMD 1505) 4-methyl-1-pentene polymer (trade name: TPX RT18, manufactured by Mitsui Petrochemical Industries, Ltd.).

Adhesive resin (B-1) 4-methyl-1-pentene polymer (1-octadecene content =
6% by weight, MFR = 3.0 g / 10 min) and 60 parts by weight of 1-butene polymer (ethylene content = 5% by weight, MFR
= 2.5 g / 10 min) as a stabilizer and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1 as a stabilizer. -Dimethylethyl]
2,4,8,10-tetrakispiro [5,5] undecane (trade name:
Sumilizer GA80, manufactured by Sumitomo Chemical Co., Ltd.)
10 parts, penta (erythrityl-tetra-β-mercaptonyl) propionate (trade name: Seanox 412)
S, 0.20 parts by weight of Cipro Kasei Co., Ltd.) and 0.02 parts by weight of calcium stearate (manufactured by Sankyoki Gosei Co., Ltd.).
3 parts by weight, mixed at a low speed for 3 minutes with a Henschel mixer, and mixed the mixture with a twin screw extruder for 2 minutes.
An adhesive resin obtained by extrusion at a temperature of 80 ° C.

Propylene Polymer (C-1) Stearic acid monoglyceride was added to polypropylene (trade name: F-600, manufactured by Grand Polymer Co., Ltd.) having an MFR of 10 g / 10 min and a density of 0.91 g / cm ^3. A propylene-based polymer obtained by extruding a mixture of 0.5% by weight at a temperature of 220 ° C. with a twin-screw extruder.

Forming a three-layer film Using a co-extrusion T-die extruder, (A-1) 4-methyl-1-
The pentene polymer is extruded at 280 ° C, the (B-1) adhesive resin is extruded at 260 ° C, and the (C-1) propylene polymer is extruded at 220 ° C. A three-layer film was formed as a layer. The film thickness composition is (A-
1) / (B-1) / (C-1) = 80 μm / 10 μm / 10 μ
m.

[0058]

Example 2 Propylene-based polymer (C-2) Stearic acid monoglyceride was added to polypropylene (trade name: F-600, manufactured by Grand Polymer Co., Ltd.) having an MFR of 10 g / 10 min and a density of 0.91 g / cm ^3. A propylene-based polymer obtained by extruding a mixture of 2.0% by weight at a temperature of 220 ° C. with a twin-screw extruder.

Molding of Three-Layer Film (B-1) Adhesion was carried out in the same manner as in Example 1 except that (C-2) a propylene polymer was used instead of the (C-1) propylene polymer. A three-layer film having a resin layer as an intermediate layer was formed. The film thickness composition is (A-1) / (B-
1) / (C-2) = 80 μm / 10 μm / 10 μm.

[0060]

Example 3 Adhesive resin (B-2) 4-methyl-1-pentene polymer (1-octadecene content =
30% by weight of 6% by weight, MFR = 3.0 g / 10min), an ethylene / butene copolymer (1-butene content = 45% by weight,
50 parts by weight of MFR = 1.0 g / 10 min. And 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g)
/ 10 min) as a stabilizer, 3,9-bis [2- {3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetrakispiro [5,5] undecane (trade name: Sumilizer GA80, 0.10 part of Sumitomo Chemical Co., Ltd.), 0.20 part by weight of penta (erythrityl-tetra-β-mercaptonyl) propionate (trade name: Seanox 412S, manufactured by Cypro Chemical Co., Ltd.), and calcium stearate (Manufactured by Sankyoki Gosei Co., Ltd.) in a ratio of 0.03 parts by weight, mixed by low-speed rotation with a Henschel mixer for 3 minutes, and extruded the mixture at a temperature of 280 ° C. with a twin-screw extruder. Adhesive resin obtained by

Ethylene polymer (D-1) MFR: 2.1 g / 10 min, density: 0.920 g / cm ³
Polyethylene (trade name: Ultex X202L,
An ethylene polymer obtained by extruding a mixture of stearic acid monoglyceride at a ratio of 0.5% by weight into a twin screw extruder at a temperature of 200 ° C. with Mitsui Petrochemical Industry Co., Ltd.).

[0062] using a molding coextrusion T-die extrusion molding machine of the three-layer film, with (A-1) poly-4-methyl-1-pentene 280 ° C., the (B-2) adhesive resin 26
At 0 ° C., the (D-1) ethylene-based polymer was extruded at 200 ° C. to form a three-layer film having a layer composed of (B-2) an adhesive resin as an intermediate layer. The film thickness composition is (A-1) /
(B-2) / (D-1) = 80 μm / 10 μm / 10 μm.

[0063]

Example 4 Ethylene Polymer (D-2) MFR 2.1 g / 10 min, density 0.920 g / cm ³
Polyethylene (trade name: Ultex X202L,
An ethylene polymer obtained by extruding a mixture of sorbitan oleate at a ratio of 0.5% by weight into a twin screw extruder at a temperature of 200 ° C. into Mitsui Petrochemical Industries, Ltd.).

Formation of Three-Layer Film (B-1) The procedure of Example 3 was repeated except that (D-2) an ethylene polymer was used instead of the (D-1) ethylene polymer.
2) A three-layer film having an adhesive resin as an intermediate layer was formed. Film thickness composition is (A-1) / (B-2) / (D-2)
= 80 μm / 10 μm / 10 μm.

[0065]

Comparative Example 1 4-methyl-1-pentene polymer (A-2) having a melting point of 237 ° C. and an MFR of 25 g / 10 min.
A mixture of a pentene-based polymer (trade name: TPX RT18, manufactured by Mitsui Petrochemical Industries, Ltd.) and monoglyceride stearate at a ratio of 2.0% by weight was mixed with a twin-screw extruder.
4-methyl-1-pentene polymer obtained by extrusion at 80 ° C.

[0066] Film using a molding T-die extruder at 280 ℃ (A-2) 4- methyl-1-pentene polymer is extruded and formed a monolayer film. The thickness of the film was 100 μm.

[0067]

Comparative Example 2 Propylene Polymer (C-3) Polypropylene having an MFR of 10 g / 10 min and a density of 0.91 g / cm ³ (trade name: F-600, manufactured by Grand Polymer Co., Ltd.).

Molding of Three-Layer Film (B-1) The procedure of Example 1 was repeated except that (C-3) polypropylene was used in place of (C-1) propylene-based polymer.
1) A three-layer film having an adhesive resin as an intermediate layer was formed. Film thickness composition is (A-1) / (B-1) / (C-3)
= 80 μm / 10 μm / 10 μm.

[0069]

Comparative Example 3 Film Formation Using a T-die extruder, a (A-1) 4-methyl-1-pentene polymer was extruded at 280 ° C. to form a single-layer film. The thickness of the film was 100 μm.

Table 1 shows the results of measuring the antifogging properties of the films obtained in the above Examples and Comparative Examples. As shown in Table 1, the laminate of the present invention has good antifogging properties. On the other hand, a film formed by adding an anti-fogging agent directly to a 4-methyl-1-pentene polymer (Comparative Example 1)
Has poor anti-fog properties. This is considered because the temperature at which the 4-methyl-1-pentene polymer was formed into a film was as high as 280 ° C., and the antifogging agent was sublimated.

[0071]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a perspective view showing an apparatus for evaluating the antifogging property of a film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/20 C08L 23/20 C09J 123/20 C09J 123/20

Claims (5)

[Claims] 1. A propylene containing (I) a layer consisting of a 4-methyl-1-pentene polymer (A), (II) an intermediate layer consisting of an adhesive resin (B), and (III) an antifogging agent. A layer comprising an ethylene-based polymer (C) or an ethylene-based polymer (D) containing an antifogging agent.
-1-pentene resin laminate. 2. The 4-methyl-1-pentene polymer (A) contains 85% by weight or more of a 4-methyl-1-pentene homopolymer or a structural unit derived from 4-methyl-1-pentene. 2. The poly-4-methyl-1 according to claim 1, which is a copolymer.
-Penten resin laminate. 3. The adhesive resin (B) comprises: (a) 40 to 70 parts by weight of a 4-methyl-1-pentene-based polymer;
-Butene copolymer 30-60 parts by weight ((a) +
(B) = 100 parts by weight). 3. The poly-4-methyl-1-pentene-based resin laminate according to claim 1, wherein the composition comprises: 4. The adhesive resin (B) comprises (a) 20 to 60 parts by weight of a 4-methyl-1-pentene polymer, and (b) 1
-Butene-based polymer 5 to 40 parts by weight, (c) ethylene / butene copolymer 30 to 60 parts by weight, and (d) propylene / butene-based polymer 0 to 30 parts by weight ((a) +
4. The composition according to claim 1, wherein the composition comprises (b) + (c) + (d) = 100 parts by weight).
Methyl-1-pentene resin laminate. 5. The propylene-based polymer (C) or the ethylene-based polymer (D) contains an antifogging agent in a proportion of 0.05 to 5% by weight. Poly-4-methyl-1-pentene resin laminate.