JPH09268243A - 4-Methyl-1-pentene resin composition, and laminate comprising the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition for producing laminates, esp. a resin composition for bonding use excellent in bond strength to another resin layer, and to obtain a laminate using this composition. SOLUTION: This 4-methyl-1-pentene-based polymer composition comprises (A) 20-60 pts.wt. of a 4-methyl-1-pentene-based polymer, (B) 30-60 pts.wt. of an ethylene-butene copolymer, (C) 5-40 pts.wt. of a 1-butene-based polymer and (D) 0-30 pts.wt. of a propylene-butene copolymer. The other objective laminate is obtained by using this composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrially useful resin composition, particularly an adhesive resin composition for producing a laminate, and a laminate comprising the resin composition. More specifically, it retains the excellent heat resistance, transparency, gas permeability, releasability, and liquid drainage of the 4-methyl-1-pentene polymer itself, and also has heat seal strength and impact resistance. Not only excellent in mechanical properties such as, but especially 4-methyl-1
-Excellent adhesion to other resins as well as penten resin,
The present invention relates to a 4-methyl-1-pentene resin composition that is preferably used for producing a laminate, and a laminate such as various bottles, containers, films and sheets formed by using the resin composition.

[0002]

2. Description of the Related Art 4-Methyl-1-pentene polymer is used for microwave oven tableware, FPC release film, artificial leather, which utilizes its properties such as heat resistance, transparency, gas permeability, and release property. It has been developed into various applications such as process paper or baking cartons, medical syringes or medicines and agricultural chemicals, storage containers or measuring instruments for cosmetics or blood, fruit and vegetable storage containers, but when heat seal strength and impact resistance are inferior However, there has been a demand for further improvement in practical physical properties. Further, it has been desired to improve the rigidity of the container, especially the characteristics such as high temperature rigidity.

Therefore, multi-layering of 4-methyl-1-pentene resin and other thermoplastic resins such as polyolefin, polyester, polyamide and the like has been studied. For example, multi-layering has been studied in which the characteristics of the 4-methyl-1-pentene resin and the characteristics of another polyolefin resin excellent in heat sealability and impact resistance, especially the characteristics of an ethylene polymer, are complemented with each other.

However, since the 4-methyl-1-pentene polymer has a low surface tension, the adhesive strength with other resins such as an ethylene polymer is high even though it is the same olefin polymer. It was low, and it was difficult to adhere directly to form multiple layers.

Therefore, various adhesive resins used for the adhesive layer as an intermediate medium have been studied. As a result, several kinds of compositions were found (Japanese Patent Publication No. 2-59768, JP-A-60-145844). 4-Methyl-1-pentene resin composition having a good balance of physical properties, in which the use of which further improvement in performance is required in the fields of use and new fields, which have achieved certain results by these techniques, is left. Four
A laminate using the -methyl-1-pentene composition and an adhesive 4-methyl-1-pentene composition for producing a laminate have been desired.

Further, regarding thermoplastic resins other than polyolefin, multi-layering with 4-methyl-1-pentene resin was also studied (Japanese Patent Laid-Open No. 2-107438), but with this technique, interlayer adhesion is still insufficient. However, further improvement was required.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an adhesive composition for multi-layering, that is, an adhesive resin composition having excellent adhesive strength with other resin layers. .

More specifically, the adhesive strength is good for both 4-methyl-1-pentene resin and resins having excellent heat-sealing property and impact resistance (for example, polyolefin, particularly polyethylene polymer or its composition). To provide a strong adhesive composition.

It is also an object of the present invention to provide an adhesive composition having a strong adhesive strength to any of 4-methyl-1-pentene resin and resins having excellent heat resistance, gas barrier property and transparency (for example, nylon and polyester). Is one of the purposes.

Another object of the present invention is to provide a laminated body or a laminated body molded article which comprises the adhesive resin composition as an adhesive layer.

[0011]

According to the present invention (A) 4
-Methyl-1-pentene polymer 20 to 60 parts by weight, (B) ethylene / butene copolymer 30 to 60 parts by weight, and (C) 1-butene polymer 5 to 40 parts by weight (D) ) Propylene / butene copolymer 0 or more and 30 parts by weight or less ((A) + (B) + (C) + (D) = 100 parts by weight) 4-methyl-1-pentene-based copolymer A coalescing composition is provided. According to the present invention,
Provided are a laminated body and a laminated body molded article each including the resin composition as an adhesive layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The 4-methyl-1-pentene polymer composition of the present invention, and a molded article produced by using the composition, particularly a laminate, will be described in detail below.

The 4-methyl-1-pentene polymer (A) used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and other α-.
It is a copolymer with an olefin, which is a polymer mainly containing 4-methyl-1-pentene containing 80% by weight or more of 4-methyl-1-pentene. Particularly, from the viewpoint of improving the adhesiveness, a copolymer is preferable, and the content of 4-methyl-1-pentene is preferably 99.9% by weight or less.

Other α-olefins used for copolymerization include ethylene, propylene, 1-butene, 1-hexene,
Examples thereof include 1-octene, 1-decene, 1-tetradecene, 1-octadecene, 1-eicosene and the like, and α-olefins having 2 to 20 carbon atoms. When such other α-olefin is contained, the α-olefin may contain one kind alone or a combination of two or more kinds. Preferred copolymerization components of these α-olefins include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-decene.
This is Eikosen.

Such a 4-methyl-1-pentene polymer (A) has a load of 5.D according to ASTM D1238.
The melt flow rate (MFR) measured under the conditions of 0 kg and temperature: 260 ° C. is generally 0.1 or more and 200 g / 1.
It is preferably in the range of 0 minutes or less and 1.0 or more and 150
It is particularly preferable that it is in the range of g / 10 minutes or less.

By selecting such a melt flow rate, the miscibility with other components, for example, (B), (C) and (D) is improved and high adhesive performance can be obtained.

The ethylene / butene copolymer (B) used in the present invention is an ethylene / butene random copolymer having an ethylene content of 50 to 90% by weight as a main component. In particular, when the range of 55 to 85% by weight is selected, the flexibility of the adhesive layer is improved, and the dispersion of the ethylene / butene copolymer in the composition is increased, so that the adhesive performance is improved.

Examples of butene used in the copolymerization include butene-1, isobutene and butene-2. These may contain one kind or a combination of two or more kinds, and further other olefins, for example, having 2 or more carbon atoms 20
It may contain the following olefins. Preferred olefins for copolymerization are butene-1 and isobutene.

Such an ethylene / butene copolymer (B) has a load of 2.16 according to ASTM D1238.
The melt flow rate (MFR) measured under the conditions of kg, temperature: 190 ° C. is generally preferably in the range of 0.1 or more and 50 g / 10 minutes or less, and 1.0 or more and 30 g /
It is particularly preferred that it is in the range of 10 minutes or less. By selecting such a melt flow rate, the miscibility with other components such as (A), (C), and (D) is improved, and high adhesion performance can be obtained.

The 1-butene polymer (C) used in the present invention is a homopolymer of 1-butene or a copolymer of 1-butene and other α-olefin, butene-1.
Is a polymer mainly containing butene-1 containing 60% by weight or more. In particular, the content of butene-1 is preferably 80% by weight or more from the viewpoint of good compatibility with the 4-methyl-1-pentene polymer.

Other α-olefins used for the copolymerization include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. It can be illustrated. When such other α-olefin is contained, the α-olefin may contain one kind alone or a combination of two or more kinds. Ethylene and propylene are preferable copolymerization components for these α-olefins.

Such butene-1 type polymer (C) is A
Load according to STM D1238: 2.16 kg, temperature 1
Melt flow rate (MFR) measured at 90 ° C
However, in general, it is preferably in the range of 0.01 to 100 g / 10 minutes, in particular, 0.1 to 50 g / 10.
It is particularly preferable that it is in the range of minutes or less.

By selecting such a melt flow rate, the miscibility with other components such as (A), (B) and (D) is improved and a high adhesive performance can be obtained.

The propylene / butene copolymer (D) used in the present invention is a propylene / butene random copolymer, which is a polymer mainly containing propylene in an amount of 50 to 90% by weight. Particularly, from the viewpoint that the mechanical strength of the adhesive composition is improved and high adhesive performance can be exhibited for both 4-methyl-1-pentene polymer and ethylene polymer, propylene is 60 or more and 85 wt% or less. Is preferred.

Examples of butene used in the copolymerization include butene-1, isobutene and butene-2. These may contain one kind or a combination of two or more kinds, and further other olefins, for example, having 2 or more carbon atoms 20
It may contain the following olefins. Preferred olefins for copolymerization are butene-1 and isobutene.

Such a propylene / butene copolymer (D) has a load of 5 kg according to ASTM D1238,
The melt flow rate (MFR) measured under the condition of temperature: 260 ° C. is generally preferably in the range of 0.1 to 200 g / 10 minutes, and is preferably in the range of 1.0 to 100 g / min.
It is particularly preferred that it be in the range of 10 minutes. By selecting such a melt flow rate, the miscibility with other components such as (A), (B), and (C) is improved, and high adhesion performance can be obtained.

In the composition of the present invention, (A) 4-methyl-1-pentene polymer, (B) ethylene / butene polymer, (C) 1-butene polymer and (D) propylene / butene. The blending ratio of the system-based polymer exhibits high adhesion performance to both the 4-methyl-1-pentene-based polymer and the olefin-based polymer, particularly the ethylene-based polymer, and can firmly bond both layers. In terms of (A) 20 or more and 60 parts by weight or less, (B) 30 or more and 60 parts by weight or less, (C)
It is 5 or more and 40 parts by weight or less and (D) is 0 or more and 30 parts by weight or less, and (A) + (B) + (C) + (D) = 100 parts by weight. To further improve the adhesive strength, (A) 30 or more and 50 parts by weight or less, (B) 35 or more and 50 parts by weight or less, (C) 10 or more and 30 parts by weight or less, and (D) 5 or more and 20 parts by weight or less. And (A) + (B) + (C) + (D)
= 100 parts by weight is preferable.

The composition obtained according to the invention comprises 4-methyl-
As a 1-pentene-based polymer, high adhesion performance can be obtained for both ethylene-based polymers.
According to D1238 Load: 5.0kg, Temperature: 260 ℃
The melt flow rate (MFR) measured under
It is preferably in the range of 0.1 or more and 200 g / 10 minutes or less, and particularly preferably in the range of 1.0 or more and 100 g / 10 minutes or less.

To obtain the 4-methyl-1-pentene polymer composition of the present invention, (A) 4-methyl-1-pentene polymer, (B) ethylene / butene copolymer, (C). 1
-Butene-based polymer and (D) propylene / butene copolymer are mixed in predetermined amounts by various known methods, for example, a V-type blender, a ribbon blender, a Henschel mixer, a tumbler blender, and then a single-screw extruder or a multi-screw extruder. A method of melt kneading with a shaft extruder, a kneader, a Banbury mixer, a twin screw extruder, or the like and granulating or pulverizing can be used.

In the 4-methyl-1-pentene polymer composition of the present invention, a silane coupling agent, a weather resistance stabilizer, a heat resistance stabilizer, a slip agent, a nucleating agent, a pigment, a dye or the like is usually added to a polyolefin before use. The various compounding agents may be added within a range that does not impair the object of the present invention.

The adhesive composition obtained in the present invention is (E) 4
-Methyl-1-pentene content of 80% by weight or more 4
A sheet made of a methyl-1-pentene polymer,
(F) A laminated body can be produced from a sheet made of a thermoplastic resin other than the (E) layer. The adhesive strength between the layers of the laminate depends on the thickness of each layer, but for example, 4-methyl-1-pentene polymer / adhesive layer (composition) / ethylene polymer = 20/10/20 μm, 0.15 kgf /
It can be 15 mm or more.

Therefore, in the present invention, the (E) poly 4-
Methyl-1-pentene polymer or 4-methyl-1-pentene copolymer layer containing 80% by weight or more of 4-methyl-1-pentene as a main component, (F) other than the (E) layer Layer of the thermoplastic resin, and a layer (adhesive layer) of the adhesive resin composition of the present invention interposed between both layers (E) and (F)
There is provided a laminate or a laminate formed from at least three layers of

This laminate of the invention comprises poly-4-methyl-
1-Although it is a laminate of a pentene resin layer and a thermoplastic resin layer, it is excellent in interlayer adhesion strength, forms a strong laminated structure excellent in mechanical strength, and has heat resistance, transparency,
It also shows excellent performance. Further, when formed into a molded product, it is also excellent in impact resistance, drop strength and the like.

Of course, for example, in the 4-methyl-1-pentene resin / polyolefin resin laminate, the gas permeability is also excellent, and the polyolefin resin layers of the laminate, for example, the ethylene resin layers (F) are Heat sealing can make a durable bag with excellent gas permeability.

As a result, it has become possible to newly use it for applications such as freshness keeping packaging. The oxygen permeability of the laminate depends on the thickness of each layer, and is, for example, 4-methyl-1-
Penten polymer / adhesive layer / ethylene polymer = 20 /
7,000 cc / m for three-layer film of 10/20 μm
^{It is 2} · 24 hr · atm. The heat seal strength of the above three-layer film was 1.4 kgf / 15 mm.

Further, 4-methyl-1-pentene resin /
In a laminate of a 4-methyl-1-pentene-based resin such as a polar group-containing resin and an oxygen-containing resin such as polyester or polyamide, the releasability of the 4-methyl-1-pentene-based resin layer As it is a material that combines gas barrier properties with polyester and polyamide resin layers, heat resistance, high temperature rigidity, and is also excellent in transparency, impact resistance, and drop strength,
For example, it is particularly suitable for applications such as bottles, containers, films, and bags, which require both releasability and gas barrier properties.

4-Methyl-used in the laminate of the present invention
The 1-pentene polymer (E) is a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and other α-olefin, and is 4-methyl. -4-Methyl containing 80% by weight or more of 1-pentene
It is a polymer mainly composed of 1-pentene. In particular, a copolymer is preferable from the viewpoint of improving the adhesiveness, and 4-methyl-1-
The content of pentene is preferably 99.9% by weight or less.

Other α-olefins used for copolymerization include ethylene, propylene, 1-butene, 1-hexene,
Examples thereof include 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like, and α-olefins having 2 to 20 carbon atoms. When such other α-olefin is contained, the α-olefin may contain one kind alone or a combination of two or more kinds. These α
The preferred copolymerization component of olefin is 1-decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane or 1-eicosene.

The 4-methyl-1-pentene-based polymer (E) was prepared according to ASTM D1238 under a load of 5.
The melt flow rate (MFR) measured under the conditions of 0 kg and temperature: 260 ° C. is generally 0.1 or more and 200 g / 1.
It is preferably in the range of 0 minutes or less and 1.0 or more and 150
It is particularly preferable that it is in the range of g / 10 minutes or less. The oxygen permeability coefficient is usually 1700 cc · mm / m ²
・ 24hr ・ atm or more, 2300cc ・ mm / m ²・
It is in the range of 24 hr · atm or less.

When the thermoplastic resin (F) used in the present invention is an olefin polymer resin, the α-olefin used is ethylene, propylene, 1-butene,
Examples thereof include those having 2 to 20 carbon atoms such as 1-hexene and 1-octene. The α-olefin may be used alone or in combination of two or more.

Examples of such α-olefin polymer resins include α-olefins having 2 to 4 carbon atoms and polyolefins containing them as the main component, that is, polyethylene, polypropylene, polybutene-1, etc., ethylene, propylene. , 1-butene as a main component is preferable.

Specific examples of the polyethylene include, for example, high-pressure low density polyethylene (LDPE), ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene-4-methyl-1-pentene copolymer. , Ethylene / 1-hexene copolymer, high density polyethylene (HDPE), ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and the like.

Specific examples of polypropylene include polypropylene (propylene homopolymer), propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer and propylene / 1.
-Propylene random copolymer such as butene random copolymer (propylene content is usually 90 mol% or more, preferably 95 mol% or more), propylene / ethylene block copolymer (ethylene content is usually 5 to 30 mol%)
And the like. Of these, homopolymers and random copolymers are preferable because they have excellent transparency.

Specific examples of the poly-1-butene include, for example, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 1-butene.
Butene / 4-methyl-1-pentene copolymer may be mentioned.

In the laminate of the present invention, the olefin-based polymer or copolymer is a homopolymer of ethylene or a copolymer of ethylene and another α-olefin and has a content of ethylene. It is particularly preferable to use an ethylene copolymer containing 70% by weight or more, and particularly 70 to 90% by weight of ethylene as a main component.

In the case of a copolymer, other α-olefins used are propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1
Examples include α-olefins having 2 to 20 carbon atoms such as octadecene. Such other α-olefins may be used alone or in combination of two or more.

Such an ethylene-based polymer is
According to D1238, the melt flow rate (MFR) measured under the conditions of a load of 2.0 kg and a temperature of 190 ° C. is generally preferably 0.1 or more and 200 g / 10 minutes or less, preferably 1.0 or more and 150 g / It is particularly preferable that the range is 10 minutes or less.

The oxygen permeability coefficient is usually 150 cc.
・ Mm / m ²・ 24hr ・ atm or more, 220cc ・ m
It is in the range of m / m ² · 24 hr · atm or less. Furthermore, the heat-sealing strength depends on the thickness, but for a film having a thickness of 20 μm, for example, 1.2 kgf / 15 m
It is in the range of m or more and 2.0 kgf / 15 mm or less.

In addition to the α-olefin polymer shown above, the thermoplastic resin includes the following polar group-containing resins, among which oxygen-containing resins are preferable.

More specifically, more specifically, polyalkylene terephthalate type polyesters or copolyesters such as polyethylene terephthalate and polybutylene terephthalate (the terephthalate component is contained in an amount of 80% by weight or more of the dicarboxylic acid component, and the alkylene group is a butylene group or ethylene). A group consisting of a group, particularly an ethylene group is preferable.)

Thermoplastic polyesters such as polyalkylene naphthalate polyester or copolyester, and the polyester may contain a small amount of cyclohexanedimethanol or cyclohexanedicarboxylic acid.

Nylon 6, nylon 6,6, nylon 1
2, nylon 4,6, nylon 11, nylon 6,1
0, Nylon 6, 12 and other aliphatic polyamides, Nylon 6 / T, Nylon 6 / I, aromatic polyamides such as metaxylene diamine adipamide, polycarbonate, oxygen-containing thermoplastic resins such as polyphenylene oxide You can

Among these, polyester and polyamide are particularly preferable, and polyester is particularly preferable. The intrinsic viscosity [η] of these oxygen atom-containing polymers is preferably in the range of 0.5 to 3 dl / g.

This [η] is an o-dichlorobenzene solution at 25 ° C. when the oxygen-containing polymer is polyester, at 30 ° C. in the case of polyamide, in a concentrated sulfuric acid solution, and at 20 ° C. in the case of polycarbonate. In a methylene solution, in the case of polyphenylene oxide, the measurement can be performed at 25 ° C. in chlorobenzene.

The above (E) which constitutes the laminate of the present invention,
The thickness ratio of each layer of the (F) layer and the adhesive resin composition layer is not particularly limited and can be appropriately selected depending on the shape, size and application of the laminate, but the thickness ratio is usually Is in the range of about 1 to 100: 1 to 100: 1 to 100.

The thickness of the laminate is not particularly limited and may be appropriately selected depending on its shape, size and use, but normally the total thickness is 0.015 to 13 m.
m.

In particular, when the laminate molded product is a container such as a bottle, the layer thickness ratio is 1 to 20: 1 to 20: 1.
It is preferable that the total thickness is about 20 to 20 and the total thickness is about 0.26 to 7.5 mm.

When the laminate molded product is a film, the thickness ratio of each layer is preferably about 1 to 50: 1 to 50: 1 to 50 and the total thickness is about 0.02 to 0.2 mm. Further, the adhesive strength of the laminate is 0.2 kgf / 15 mm or more, and usually in the range of 0.2 to 5 kgf / 15 mm.

The laminate of the present invention has the above-mentioned three layers as essential constituent layers, but may have a layer structure of four or more layers in which other layers are further laminated.

As the method for producing the laminate of the present invention,
Although not necessarily limited thereto, for example, in the case of manufacturing a laminated film or sheet, the adhesive resin composition of the present invention, the (E) poly-4-methyl-1-pentene polymer or copolymer Examples thereof include a combination method, a method in which the thermoplastic resin (F) is coextrusion molded, a method in which resin sheets, films, and the like prepared in advance by press molding, extrusion molding, and the like are laminated by press molding. In the case of manufacturing a container such as a laminated bottle, a molding method such as multilayer blow molding or press molding can be used.

The 4-methyl-1-pentene polymer composition of the present invention comprises a 4-methyl-1-pentene polymer and another thermoplastic resin, especially an olefin polymer, and especially an ethylene polymer. Adhesive performance to both is high, 4-
It can be used for an adhesive layer of a methyl-1-pentene polymer and another thermoplastic resin, particularly an olefin polymer.

Thus, the 4-methyl-1-pentene polymer / adhesive layer / olefin polymer obtained by using the composition obtained in the present invention (especially ethylene polymer was used as olefin) The laminate (multilayer structure) can be used for various packaging materials because the olefin polymer layers, particularly the ethylene polymer layers, can be heat-sealed to each other and a strong bag can be obtained with high adhesive strength. For example, since 4-methyl-1-pentene-based polymer has high gas permeability and heat resistance, it is used for various kinds of bags for storing fruits and vegetables, lids for storing fruits and vegetables, and sterilization process required for instantaneous heat resistance. It can be used for bags and other items. Furthermore, 4-methyl-1-
The pentene-based polymer composition can be suitably used for pesticides, cosmetics bottles, etc. by taking advantage of the good drainage property.

The 2-layer film or sheet of 4-methyl-1-pentene polymer / the present composition can also be used as a lid material which can be heat-sealed to a container made of an ethylene polymer.

Further, 4-methyl-1-pentene resin /
In a laminate of a 4-methyl-1-pentene-based resin such as a polar group-containing resin and an oxygen-containing resin such as polyester or polyamide, the releasability of the 4-methyl-1-pentene-based resin layer As it is a material that combines gas barrier properties with polyester and polyamide resin layers, heat resistance, high temperature rigidity, and is also excellent in transparency, impact resistance, and drop strength,
For example, it is particularly suitable for applications such as bottles, containers, films, and bags, which require both releasability and gas barrier properties.

[0065]

EXAMPLES The compositions of the present invention will be described below with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The compositions shown in the examples were prepared under the following conditions. The measurement methods and conditions for the physical properties shown in the examples are also shown below. (1) Preparation of composition After dry blending each predetermined amount of a 4-methyl-1-pentene polymer, an ethylene / butene copolymer, a 1-butene polymer and a propylene copolymer with a Henschel mixer, 65 mm Was prepared by melt-kneading with an extruder (set temperature: 280 ° C.). (2) Preparation of 3-layer sheet Each sheet of 4-methyl-1-pentene polymer, ethylene polymer and composition was molded by a press molding machine. Then, a 4-methyl-1-pentene-based polymer sheet / composition sheet / ethylene-based polymer sheet were laminated in this order and subjected to a press molding machine to produce a three-layer sheet. The molding conditions for each sheet are shown below. 4-Methyl-1-pentene polymer and composition sheet molding conditions Raw material 4-Methyl-1-pentene and 1-octadecene copolymer 4-Methyl-1-pentene content 94 wt% (hereinafter referred to as PMP-1 Abbreviated) Press temperature 280 ° C. Preheating time 10 minutes Pressure 50 kg / cm ² Pressurization time 4 minutes 4-methyl-1-pentene polymer sheet thickness 1 mm Composition sheet thickness 0.3 mm Ethylene polymer sheet molding conditions Raw material Ethylene homopolymer (LDPE) Ethylene content 100 wt% (hereinafter abbreviated as PE-1) Press temperature 200 ° C. Preheating time 5 minutes Pressure 50 kg / cm ² Pressing time 4 minutes Sheet thickness 1 mm 3 layer sheet molding conditions Press Temperature (4-methyl-1-pentene polymer side) 280 ° C Pressing temperature (ethylene polymer side) 250 ° C Preheating time 8 minutes Pressure 50 kg / cm ² Pressing time 3 minutes Sheet thickness 1.8 mm (thickness of each layer 0.8 / 0.2 / 0.8 mm) (3) Molding of three-layer blow bottle 3 using the following raw materials Layer thickness of 1.5 mm (PMP-1 / composition / ethylene polymer =
A three-layer blow bottle of 1.0 (outer) /0.1/0.4 mm (inner) was molded. The die temperature was set to 250 ° C., and the die clearance was set to 0.5 mm. The extrusion temperature of each raw material is as follows. Raw material Extrusion temperature PMP-1 250 ° C. Composition (adhesive layer) 230 ° C. Ethylene homopolymer (HDPE) 210 ° C. (Ethylene content 100 wt%, abbreviated as PE-2 below) (4) Three-layer film molding Next raw material Using a 3-layer film forming machine with a thickness of 5
0 μ (PMP-1 / composition / ethylene polymer = 20 /
A three-layer film of 10/20 μm) was formed. The die temperature was set to 280 ° C. and the die clearance was set to 0.5 mm. The extrusion temperature of each raw material is as follows. Raw material Extrusion temperature PMP-1 280 ° C. Composition (adhesive layer) 250 ° C. Ethylene-4-methyl-1-pentene copolymer 250 ° C. (Ethylene content 10 wt%, hereinafter abbreviated as PE-3) or Ethylene 4-methyl -1-Pentene copolymer 250 ° C. (ethylene content 5 wt%, abbreviated as PE-4 below) or polyethylene terephthalate 290 ° C. (density 1.41, intrinsic viscosity 1.4 dl / g, abbreviated as PET hereinafter) (1 ) Evaluation of physical properties Measurement of MFR 4-methyl-1-pentene-based polymer, ethylene / butene copolymer, 1-butene-based polymer and propylene / butene copolymer were used in a predetermined amount using a twin-screw extruder. The MFR of the composition prepared by kneading was measured according to ASTM D1238 under the conditions of load: 5 kg and temperature: 260 ° C. Measurement of Adhesive Strength A T-peel peel test of a three-layer sheet, a three-layer blow bottle and a three-layer film was performed under the following conditions to measure the peel strength. Test method T-peel test speed 300 mm / min Peeling width 15 mm Temperature 23 ° C. Measurement of heat seal strength The polyethylene polymer layers of the three-layer film were pressed with a heat seal bar (temperature 120 ° C.) for 2 seconds to perform heat sealing. The heat seal strength was measured under the same conditions as the adhesive strength. Measurement of oxygen permeability The oxygen permeability of the three-layer film is JIS K-7126 B.
It measured using MOCONOXTRAN 10/50 according to the method.

(Example 1) 4-methyl-1-pentene polymer (1-octadecene content = 6% by weight, MFR =
3.0 g / 10 min) 30 parts by weight, ethylene / butene copolymer (1-butene content = 45% by weight, MFR = 1.0)
g / 10 minutes) 50 parts by weight and 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g / 10 minutes)
20 parts by weight, 3,9-bis [2- {3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,
5] Undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., trade name: Synox 412S)
0.20 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate)
It was compounded in a ratio of 03 parts by weight and dry-blended using a Henschel mixer. The resulting mixture was melt-kneaded with a twin-screw extruder set at 280 ° C. to obtain a composition for adhesion (TL
1) was prepared. The MFR of this composition was measured, and the results were shown in Table 1. It is shown in FIG. Next, this composition, PMP-1 (M
FR = 20 g / 10 min) and PE-1 (MFR = 0.
35 g / 10 min) of each sheet was prepared by the pressing method. Subsequently, a sheet of the composition is placed between the sheets of PMP-1 and PE-1 and pressed by the method PMP-1 / adhesive layer / P
A three-layer sheet of E-1 was molded. This thickness composition is 0.8
It was /0.2/0.8 mm. The adhesive strength of the obtained three-layer sheet was measured, and the results are shown in Table. It is shown in FIG.

(Example 2) 4-methyl-1-pentene polymer (1-octadecene content = 6% by weight, MFR =
3.0 g / 10 minutes) 40 parts by weight, ethylene / butene copolymer (1-butene content = 15% by weight, MFR = 3.5)
g / 10 minutes) 40 parts by weight and 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g / 10 minutes)
20 parts by weight, 3,9-bis- [2- {3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,
5] Undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., trade name: Synox 412S)
0.20 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate)
It was compounded in a ratio of 03 parts by weight and dry-blended using a Henschel mixer. The resulting mixture was melt-kneaded with a twin-screw extruder set at 280 ° C. to obtain a composition for adhesion (TL
2) was prepared. The MFR of this composition was measured, and the results were shown in Table 1. It is shown in FIG. Next, this composition, PMP-1 (M
FR = 20 g / 10 min) and PE-1 (MFR = 0.
Each sheet of 35) was prepared by the pressing method. Subsequently,
A sheet of the composition is placed between the sheets of PMP-1 and PE-1 and pressed 3 times PMP-1 / adhesive layer / PE-1.
A layer sheet was formed. This thickness composition is 0.8 / 0.2 /
0.8 mm. The adhesive strength of the obtained three-layer sheet was measured, and the results are shown in Table 2.

(Example 3) 4-methyl-1-pentene polymer (1-octadecene content = 6% by weight, MFR =
3.0 g / 10 minutes) 40 parts by weight, ethylene / butene copolymer (1-butene content = 15% by weight, MFR = 3.5)
g / 10 minutes) 40 parts by weight and 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g / 10 minutes)
10 parts by weight and propylene / butene copolymer (1-butene content = 20% by weight, MFR = 5.0 g / 10 minutes)
10 parts by weight, 3,9-bis- [2- {3- as a stabilizer
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,
5] Undecane (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA80) 0.10 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., trade name: Synox 412S)
0.20 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate)
It was compounded in a ratio of 03 parts by weight and dry-blended using a Henschel mixer. The resulting mixture was melt-kneaded with a twin-screw extruder set at 280 ° C. to obtain a composition for adhesion (TL
3) was prepared. The MFR of this composition was measured, and the results are shown in Table 1. Next, this composition, PMP-1 (MF
R = 20 g / 10 min) and PE-1 (MFR = 0.3
Each sheet of 5) was prepared by the pressing method. Subsequently, a sheet of the composition was placed between the sheets of PMP-1 and PE-1, and a three-layer sheet of PMP-1 / adhesive layer / PE-1 was formed by a pressing method. This thickness composition is 0.8 / 0.2 /
0.8 mm. The adhesive strength of the obtained three-layer sheet was measured, and the results are shown in Table 2.

(Example 4) Using the adhesive composition (TL2) prepared in Example 2, PMP-1 / adhesive composition / P
A three-layer blow bottle of E-2 (MFR = 0.40 g / 10 min) was molded. Thickness composition is 1.0 / 0.1 / 0.4m
m. The adhesive strength of this three-layer blow bottle was measured, and the results are shown in Table 3.

Example 5 Using the adhesive composition (TL3) prepared in Example 3, PMP-1 / adhesive composition / P
A three-layer blow bottle of E-2 (MFR = 0.40 g / 10 min) was molded. Thickness composition is 1.0 / 0.1 / 0.4m
m. The adhesive strength of this three-layer blow bottle was measured, and the results are shown in Table 3.

Example 6 Using the adhesive composition (TL3) prepared in Example 3, PMP-1 / adhesive composition / P
A three-layer film of E-3 (MFR = 2.0 g / 10 min) was molded. The thickness constitution was 20/10/20 μm.
The adhesive strength, heat seal strength, and oxygen permeability of this three-layer film were measured, and the results are shown in Table 4.

Example 7 Using the adhesive composition (TL3) prepared in Example 3, PMP-1 / adhesive composition / P
A three-layer film of E-4 (MFR = 2.0 g / 10 min) was molded. The thickness constitution was 20/10/20 μm.
The adhesive strength, heat seal strength, and oxygen permeability of this three-layer film were measured, and the results are shown in Table 4.

Example 8 Using the adhesive composition (TL3) prepared in Example 3, PMP-1 / adhesive resin composition / PET (polyethylene terephthalate: density 1.4)
1. A three-layer film having an intrinsic viscosity of 1.4 dl / g) was formed. The thickness constitution was 20/10/20 μm. This 3
The adhesive strength, heat seal strength and oxygen permeability of the layer film were measured, and the results are shown in Table 4.

Comparative Example 1 4-Methyl-1-pentene polymer (1-octadecene content = 6% by weight, MFR =
3.0 g / 10 min) 50 parts by weight and ethylene / butene copolymer (1-butene content = 45% by weight, MFR = 1.0)
g / 10 minutes) 50 parts by weight of the adhesive composition (TL
The adhesive strength of the three-layer sheet was measured in the same manner as in Example 1 except that 4) was prepared. Table 2 shows the results.

Comparative Example 2 Instead of 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g / 10 min), propylene / butene copolymer (1-butene content =
The adhesive strength of the three-layer blow bottle was measured in the same manner as in Example 2 except that the adhesive composition (TL5) was prepared using 20% by weight and MFR = 5.0 g / 10 minutes. The results are shown in the table. 3 is shown.

Comparative Example 3 Instead of 1-butene polymer (ethylene content = 5% by weight, MFR = 2.5 g / 10 min), propylene / butene copolymer (1-butene content =
20% by weight, MFR = 5.0 g / 10 min) was used to measure the adhesive strength, heat seal strength and oxygen permeability of the three-layer film in the same manner as in Example 6 except that the adhesive composition (TL5) was prepared. The results are shown in Table 4.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

Industrial Applicability The 4-methyl-1-pentene polymer composition of the present invention has heat resistance, transparency, gas permeability, releasability,
Not only excellent mechanical properties such as liquid-drainability, heat-sealing strength and impact resistance, but also excellent adhesion not only to 4-methyl-1-pentene resin but also to other resins Production resin composition, especially 4-methyl-1
-Suitable as a resin composition for adhesion in a laminate structure of a pentene resin and another olefin polymer resin or a polymer resin containing a polar group, and a laminate formed by using the resin composition of the present invention The molded body and its laminated product have strong interlaminar adhesion strength and excellent mechanical properties such as strength, and also have excellent heat resistance, transparency, gas permeability, releasability, liquid drainage, and heat sealing. Characteristics such as sex,
It is exhibited corresponding to the aspect of the laminated body.

Claims (10)

[Claims] 1. (A) 4-methyl-1-pentene-based polymer 20 to 60 parts by weight and (B) ethylene-butene copolymer 30 to 60 parts by weight and (C) 1-butene-based polymer. 5 to 40 parts by weight and (D) propylene / butene copolymer 0 to 30 parts by weight ((A) + (B) +
(C) + (D) = 100 parts by weight), a 4-methyl-1-pentene polymer composition. 2. The (A) 4-methyl-1-pentene polymer is a 4-methyl-1-pentene homopolymer or an α-olefin having 2 to 20 carbon atoms and 4-methyl-1-pentene. 2. The polymer composition according to claim 1, wherein the content of 4-methyl-1-pentene is 80% by weight or more. 3. The (B) ethylene / butene copolymer is 1
-The polymer composition according to claim 1, which is a random copolymer having a butene content of 10 to 50% by weight. 4. The (C) 1-butene-based polymer is a 1-butene homopolymer or a random copolymer of an α-olefin having 2 to 20 carbon atoms and 1-butene. Content is 60 weight% or more, The polymer composition of Claim 1 characterized by the above-mentioned. 5. A (D) propylene / butene-based polymer 1
-The polymer composition according to claim 1, which is a random copolymer having a butene content of 10 or more and 50% by weight or less. 6. A layer of (E) 4-methyl-1-pentene polymer having a content of 4-methyl-1-pentene of 80% by weight or more, (F) other than the polymer of the (E) layer. A thermoplastic resin layer, and 4-methyl-1 according to any one of claims 1 to 5.
-A laminated molded body comprising an adhesive layer of a pentene resin composition. 7. The laminated molded article according to claim 6, wherein the thermoplastic resin of the (F) layer is an olefin polymer resin. 8. The laminated molded product according to claim 6, wherein the thermoplastic resin of the (F) layer is a polar group-containing polymer. 9. The laminated molded body according to claim 6, wherein the molded body is a container. 10. The laminated molded product according to claim 6, wherein the molded product is a film or a sheet.