JPH0770390A - 4-Methyl-1-pentene polymer composition - Google Patents

Abstract

(57) [Abstract] [Purpose] 4-Methyl-1-, which has excellent heat-sealing properties and impact resistance, and is suitable as a film for packaging fruits and vegetables, various structural materials, and materials such as tableware bodies and lids. Provided is a pentene polymer composition. [Constitution] (A) 4-methyl-1-pentene polymer 20
~ 97.5 parts by weight, and (B) 1-butene polymer 2.5
˜80 parts by weight, and (C) polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer to 1.0 part by weight based on 100 parts by weight of the total of (A) + (B).
A 4-methyl-1-pentene polymer composition obtained by melt-blending 100 to 100 parts by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 4-methyl-1-pentene polymer composition, and particularly to a film such as a film for packaging fruits and vegetables, and various structural materials, which is excellent in heat sealability and impact resistance. The present invention relates to a 4-methyl-1-pentene polymer composition suitable as a material for a tableware body, a lid, and the like.

[0002]

2. Description of the Related Art A 4-methyl-1-pentene polymer is
It has excellent transparency and a high melting point of 220-240 ° C.
In addition, since it has a high heat deflection temperature, it is widely used for applications such as tableware for MWO, syringes of syringes, analysis cells, laboratory instruments such as beakers and flasks, synthetic leather process papers, and the like.
However, the 4-methyl-1-pentene polymer has a low impact resistance, and the film has a drawback that it has poor heat sealability. Generally, as a method of improving the heat-sealing property of an α-olefin polymer, it is well known to blend an ethylene resin such as low density polyethylene or ethylene / propylene copolymer. But 4
Even if an ethylene resin is added to the -methyl-1-pentene polymer, the heat-sealing property is hardly improved, and conversely, there is a problem in that poor dispersion results in reduced impact resistance. In order to improve the heat-sealing property of the 4-methyl-1-pentene polymer film, 4-methyl-pentene-based polymer film is used.
It has been proposed to use a composition in which a specific propylene / α-olefin copolymer is blended with a 1-pentene polymer (JP-A-60-28442).

[0003]

[Problems to be Solved by the Invention]
-Methyl-1-pentene polymer and specific propylene
The film composed of the composition with the α-olefin copolymer did not have sufficient heat seal strength and the impact resistance of the injection molded product was not sufficient. Thus, 4-methyl-1-pentene-based polymer which retains the characteristics of 4-methyl-1-pentene polymer and has improved heat sealability and impact resistance.
There is a strong demand for pentene polymer compositions.

Therefore, an object of the present invention is 4-methyl-1-.
While retaining the excellent heat resistance that the penten-based polymer originally possesses, as well as excellent heat-sealing and impact resistance, it can be used in films such as packaging films for fruits and vegetables, various structural materials, tableware main bodies and lids. 4-methyl- suitable as a material
It is to provide a 1-pentene polymer composition.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have aimed to solve the above-mentioned problems and improve the heat-sealing property and impact resistance while taking advantage of the characteristics of the 4-methyl-1-pentene polymer. Various studies were conducted. As a result, 4-methyl-1
-By blending a 1-butene-based polymer and a polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer into a pentene-based polymer, the heat-sealing property and the impact resistance of the injection molded product are remarkably improved. It was found that the composition was improved and a composition suitable for a film material or various materials was obtained, and the present invention was completed.

That is, the present invention provides (A) 4-methyl-
20-97.5 parts by weight of 1-pentene polymer, (B)
2.5-80 parts by weight of 1-butene-based polymer and (C) polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer are added to the above (A) + (B) in a total of 1
The present invention provides a 4-methyl-1-pentene polymer composition obtained by melt-blending 1 to 100 parts by weight with respect to 00 parts by weight.

The 4-methyl-1-pentene polymer composition of the present invention (hereinafter referred to as "the composition of the present invention") will be described in detail below.

The 4-methyl-1-pentene polymer, which is the component (A) of the composition of the present invention, is a homopolymer of 4-methyl-1-pentene, or 4-methyl-1-pentene and other It is a copolymer of α-olefin. Other α-olefins include, for example, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 1-decene, 1
-Tetradecene, 1-octadecene, etc. having 2 to 20 carbon atoms
.Alpha.-olefin and the like. These α-olefins may be used alone or in combination of two or more in the (A) 4-methyl-1-pentene polymer.
Among these α-olefins, 1-decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane and 1-eicosene are preferable.

The content of 4-methyl-1-pentene in the (A) 4-methyl-1-pentene polymer is such that a composition having a high melting point and sufficient heat resistance can be obtained.
Usually, it is 80% by weight or more, and preferably 85 to 98% by weight. Further, in order to have excellent heat resistance, impact resistance and transparency, it is preferable to use an α-olefin having 2 to 20 carbon atoms and 4
A random copolymer of -methyl-1-pentene is preferable, and particularly α-olefins such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-decene.
Octadecene is preferred.

The melt flow rate (MFR) of this (A) 4-methyl-1-pentene polymer shows appropriate fluidity at the time of molding, and therefore it is easy to mold, and it has excellent heat sealability and impact resistance. In terms of obtaining an excellent composition, AST
According to MD1238 Load: 5.0kg, Temperature: 260 ° C
The melt flow rate (MFR) measured under
It is preferably in the range of 0.1 to 150 g / 10 minutes, and particularly preferably in the range of 1.0 to 100 g / 10 minutes.

The (B) 1-butene polymer used in the composition of the present invention is a homopolymer of 1-butene, or 1-butene.
A copolymer of butene and other α-olefins. As other α-olefins, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-
C2-C20 alpha-olefins, such as decene, 1-tetradecene, 1-octadecene, etc. are mentioned. These α-olefins may be used alone or in combination of two or more in the (B) 1-butene polymer. Further, among these α-olefins, ethylene or propylene is preferable.

1 in this (B) 1-butene polymer
The content of butene is such that the compatibility of the (A) 4-methyl-1-pentene-based polymer and the (B) 1-butene-based polymer is good, so that both components are well dispersed and the heat-sealing property is good. And in terms of obtaining a composition having excellent impact resistance, it is usually 60
It is preferably at least wt%.

This (B) 1-butene polymer has an appropriate melt viscosity and can be uniformly dispersed in the (A) 4-methyl-1-pentene polymer, and has heat sealability. The melt flow rate (MFR) is usually 0.01 to 100 g / 10 in that a composition having excellent impact resistance can be obtained.
It is in the range of minutes, particularly preferably in the range of 0.1 to 50 g / 10 minutes. This MFR is ASTM D12
According to No. 38, it is a value measured under the conditions of load: 2.16 kg and temperature: 190 ° C.

As a specific example of this (B) 1-butene polymer, BURON P200 manufactured by Mitsui Petrochemical Co., Ltd.
0, P4000, P7000, M3110, M308
0, M3450, M2181, or M2481. Of these, M3080 or M2181 is particularly preferable. In addition, it is needless to say that other commercially available products can be used as long as they are 1-butene polymers satisfying the above requirements.

In the composition of the present invention, the content ratio of (A) 4-methyl-1-pentene polymer and (B) 1-butene polymer is (A) 4-methyl-1-pentene polymer. The proportion of (B) 1-butene polymer is 2.5 to 80 parts by weight, preferably (A) 4-methyl-1-pentene polymer 40, relative to 20 to 97.5 parts by weight of polymer. It is a ratio of 5 to 60 parts by weight of (B) 1-butene polymer with respect to ˜95 parts by weight.

A polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer (hereinafter referred to as "SEBS") used as the component (C) of the composition of the present invention.
Is a block copolymer having both a block unit A composed of an ethylene / butylene copolymer and a block unit B derived from one or more styrenes in the molecule.

The content ratio of styrene and the rubber component in this SEBS is such that the performance of SEBS as a rubber is good,
In terms of obtaining a composition having excellent heat sealability and impact resistance, the weight ratio of styrene / rubber component is 10/90 to 60 /.
A ratio of 40 is preferable, and particularly 10/90 to 40
A ratio of / 60 is preferable. In the present invention, the rubber component means the block unit A derived from the ethylene / butylene copolymer in SEBS.

Further, this SEBS is based on ASTM D123.
MFR measured under the conditions of load: 2.16 kg and temperature: 230 ° C. according to 8 is preferably 0.01 to 100 g /
It is preferably in the range of 10 minutes, particularly 0.1 to 50 g / 10 minutes.

Further, this SEBS may be graft-modified with various monomers within a range that does not change its basic properties. Examples of this monomer include maleic anhydride, maleic acid, glycidyl methacrylate and the like.

Specific examples of this (C) SEBS include Kraton G1650 and Kraton G manufactured by Shell Chemical Co., Ltd.
1652, Clayton G1657, Clayton G172
6X and Clayton FG1901X, or Tuftec H1052, H1041, H105 from Asahi Kasei Corporation
1, M1913, M1943 and the like. Of these, Kraton G1657 or Tuftec H1052 is particularly preferable. Further, of course, other commercially available products can be used as long as they are SEBS satisfying the above requirements.

The compounding amount of (C) SEBS in the composition of the present invention is such that the performance of SEBS as a rubber component is sufficiently exhibited, and a composition excellent in heat sealability, impact resistance, heat resistance and transparency is obtained. (A) 4-methyl-
1 to 100 parts by weight based on the total (A) + (B) = 100 parts by weight of 1-pentene polymer and (B) 1-butene polymer, and particularly 2.5 to 60 parts by weight. Is preferable.

Further, the composition of the present invention comprises the above (A) 4-
In addition to the methyl-1-pentene-based polymer, the (B) 1-butene-based polymer, and the (C) polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer,
You may contain various compounding agents in the range which does not impair the objective of this invention. For example, a silane coupling agent, a weather resistance stabilizer, a heat resistance stabilizer, a slip agent, a nucleating agent, various additives such as a pigment and a dye, which are usually added to polyolefin, may be contained.

The composition of the present invention can be produced by using (A) 4-methyl-1-pentene polymer, (B) 1-butene polymer and (C) polystyrene-ethylene / butylene copolymer-polystyrene. The triblock copolymer and, if necessary, various compounding agents are melt-blended. This melt blending can be performed according to various known methods. For example, V-type polystyrene blender, ribbon blender, Henschel mixer,
After mixing with a tumbler blender, melt-kneading with a single-screw extruder or a multi-screw extruder, a kneader, a Banbury mixer, etc., and granulation or pulverization can be performed.

The composition of the present invention has an MFR of 0.1 to 150 g / 10 min from the viewpoint of excellent moldability because it exhibits proper fluidity during molding, and excellent heat sealability and impact resistance. It is preferably 1.0 to 100 g / 100 minutes. This MFR is ASTM D1238
The values are measured under the conditions of load: 5.0 kg and temperature: 260 ° C.

[0025]

EXAMPLES Examples and comparative examples of the present invention will be given below.
The present invention will be described more specifically, but the present invention is not limited to these examples unless it exceeds the gist.

The MFs used in Examples and Comparative Examples
The measurement of R and the evaluation of heat sealability were performed according to the following methods.

(1) Film Forming The composition was fed to an extruder (screw diameter: 65 mm) and melt-kneaded at 280 ° C., and a T-die (set temperature: 280).
C.) and cooled with a cooling roll at 60.degree. C. to form a film having a thickness of 100 .mu.m.

(2) Measurement of MFR According to ASTM D1238, load: 5 kg, temperature: 2
The film was subjected to MFR measurement under the condition of 60 ° C.

(3) Heat-sealability Heat-sealability Two films are laminated and three sides are shown in Table 1 below.
Heat seal under the same conditions, each side is 15c
I made a bag of m. After putting 100 g of water in this bag, the remaining one side was also heat-sealed to seal the water in the bag. It was examined whether or not the bag containing water was laid vertically and naturally dropped from a height of 1.5 m to break the bag.

[0030]

Example 1 4-Methyl-1-pentene
1-hexadecene copolymer (1-hexadecene content:
Powder 70 of 6.0% by weight, MFR = 5.0 g / 10 minutes)
Parts by weight, 1-butene polymer (Mitsui Petrochemical Industry Co., Ltd.)
30 parts by weight of brand name: BURON M3080) and 5 parts by weight of SEBS (brand name: Kraton G1657, manufactured by Shell Chemical Co., Ltd.), and 2- [1- (2
-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] 4,6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) 0.10 parts by weight, tetrakis [methylene -3
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Ciba Geigy Corp.)
Manufactured, trade name: Irganox 1010) 0.10 parts by weight, penta (erythritol-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate. (Sankyo Machine Gosei Co., Ltd., trade name:
Calcium stearate) was mixed in a ratio of 0.03 part by weight, and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was mixed with a twin-screw extruder (screw diameter: 65
mm) and melt-kneaded at 300 ° C. to obtain a composition. A film was prepared from this composition, and MFR and heat sealability were measured or evaluated. The results are shown in Table 2.

Example 2 4-Methyl-1-pentene
1-octadecene copolymer (1-octadecene content:
Powder 80 of 6.0% by weight, MFR = 5.0 g / 10 minutes)
Parts by weight, 1-butene polymer (Mitsui Petrochemical Industry Co., Ltd.)
20 parts by weight of brand name: BURON M2181) and 5 parts by weight of SEBS (brand name: Kraton G1657, manufactured by Shell Chemical Co., Ltd.) and 2- [1- (2
-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] 4,6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) 0.10 parts by weight, tetrakis [methylene -3
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Ciba Geigy Corp.)
Manufactured, trade name: Irganox 1010) 0.10 parts by weight, penta (erythritol-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate. (Sankyo Machine Gosei Co., Ltd., trade name:
Calcium stearate) was mixed in a ratio of 0.03 part by weight, and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 300 ° C. to obtain a composition. A film is prepared from this composition and M
FR and heat sealability were measured or evaluated. The results are shown in Table 2.

Example 3 4-Methyl-1-pentene
1-tetradecene copolymer (1-tetradecene content:
5.0% by weight, MFR = 5.0 g / 10 minutes) powder 80
Parts by weight, 1-butene polymer (Mitsui Petrochemical Industry Co., Ltd.)
20 parts by weight of the product, brand name: BURON M3080) and 10 parts by weight of SEBS (product name: Clayton G1657, manufactured by Shell Chemical Co., Ltd.), and 2- [1-
(2-Hydroxy-3,5-ditert-pentylphenyl) ethyl] 4,6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) 0.10 parts by weight, tetrakis [ Methylene
3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Ciba Geigy Corp.)
Manufactured, trade name: Irganox 1010) 0.10 parts by weight, penta (erythritol-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate. (Sankyo Machine Gosei Co., Ltd., trade name:
Calcium stearate) was mixed in a ratio of 0.03 part by weight, and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 300 ° C. to obtain a composition. A film is prepared from this composition and M
FR and heat sealability were measured or evaluated. The results are shown in Table 2.

Example 4 As a 4-methyl-1-pentene polymer, 6.5% by weight of a mixture containing 50/50 of 1-hexadecene and 1-octadecene was added.
Methyl-1-pentene polymer (MFR: 5.0 g / 1
0 min), the ratio of the 4-methyl-1-pentene polymer and the 1-butene polymer used is 4-methyl-1-
A composition was obtained in the same manner as in Example 1 except that 40 parts by weight of 1-butene polymer and 60 parts by weight of SEBS were used with respect to 60 parts by weight of pentene polymer. A film was prepared from this composition, and MFR and heat sealability were measured or evaluated. The results are shown in Table 2.

Example 5 Example 5 was repeated except that the mixing ratio of each component was changed to 40 parts by weight of 4-methyl-1-pentene polymer, 60 parts by weight of 1-butene polymer, and 60 parts by weight of SEBS. A composition was obtained in the same manner as in 4. A film was prepared from this composition, and MFR and heat sealability were measured or evaluated. The results are shown in Table 2.

Comparative Example 1 4-Methyl-1-pentene
1-hexadecene copolymer (1-hexadecene content:
Powder 70 of 6.0% by weight, MFR = 5.0 g / 10 minutes)
To 30 parts by weight of 1-butene polymer (Mitsui Petrochemical Industry Co., Ltd., brand name: Buron M3080), 2- [1- (2-hydroxy-3,5) as a stabilizer was added.
-Ditert-pentylphenyl) ethyl] 4,6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) 0.10 parts by weight, tetrakis [methylene-3 (3,5- The-tert
-Butyl-4-hydroxyphenyl) propionate]
0.10 parts by weight of methane (manufactured by Ciba-Geigy Co., Ltd., trade name: Irganox 1010), penta (erythritol-tetra-β-mercaptolauryl) propionate (manufactured by Cypro Kasei Co., Ltd., trade name: Seanox 412)
S) 0.10 part by weight and calcium stearate (manufactured by Sankyoki Gosei Co., Ltd., trade name: calcium stearate) in an amount of 0.03 part by weight, and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded with a twin-screw extruder at 300 ° C. to obtain a composition. A film is prepared from this composition by extrusion with a T-die,
FR and heat sealability were measured or evaluated. The results are shown in Table 2.

(Comparative Example 2) 4-methyl-1-pentene
1-tetradecene copolymer (1-tetradecene content:
5.0% by weight, MFR = 5.0 g / 10 minutes) powder 10
0 parts by weight, and 10 parts by weight of SEBS (Shell Chemical Co., Ltd., brand name: Kraton G1657), and 2- [1- (2-hydroxy-3,5-ditert-pentylphenyl) ethyl] 4 as a stabilizer. , 6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) 0.10 parts by weight, tetrakis [methylene-3 (3,5-di-tert-butyl-4-).
Hydroxyphenyl) propionate] methane (manufactured by Ciba Geigy Ltd., trade name: Irganox 1010)
0.10 parts by weight, penta (erythritol-tetra-β
-Mercaptolauryl) propionate (manufactured by Cypro Kasei Co., Ltd., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate (manufactured by Sansha Kisei Co., Ltd., trade name: calcium stearate) 0.03
The ingredients were blended in a ratio of 1 part by weight and mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was mixed with a twin-screw extruder to 3
The composition was obtained by melt kneading at 00 ° C. From this composition T-
A film was prepared by extrusion molding with a die, and MFR and heat sealability were measured or evaluated. The results are shown in Table 2.

[0038] Note) Heat sealability ○ There was no abnormality in the heat seal part in the drop test. × The bag was broken in the heat seal part in the drop test.

[0039]

EFFECT OF THE INVENTION The 4-methyl-1-pentene polymer composition of the present invention retains characteristics such as excellent heat resistance originally possessed by the 4-methyl-1-pentene polymer, and It has excellent heat sealability and impact resistance, and also has good transparency.

Therefore, the composition of the present invention is a material suitable for molding various structural materials by the injection molding method. Further, a film or a laminate molded product having the above characteristics can be obtained by the extrusion molding method. This film or laminate molded product can be suitably used, for example, for packaging fruits and vegetables that require heat sealing properties.

Claims (7)

[Claims] (1) 20 to 97.5 parts by weight of (A) 4-methyl-1-pentene polymer, 2.5 to 80 parts by weight of (B) 1-butene polymer, and (C) polystyrene- 4-Methyl-1-pentene obtained by melt-blending an ethylene / butylene copolymer-polystyrene triblock copolymer with 1 to 100 parts by weight based on 100 parts by weight of the total of (A) + (B). -Based polymer composition. 2. The (A) 4-methyl-1-pentene polymer is a random copolymer of an α-olefin having 2 to 20 carbon atoms and 4-methyl-1-pentene, which is 4-methyl The 4-methyl-1-pentene polymer composition according to claim 1, wherein the content of -1-pentene is 80% by weight or more. 3. The (A) 4-methyl-1-pentene polymer is at least one α-olefin selected from 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. And 4-methyl-
The 4-methyl-1-pentene polymer composition according to claim 1, which is a random copolymer with 1-pentene. 4. The (B) 1-butene polymer is a random copolymer of an α-olefin having 2 to 20 carbon atoms and 1-butene, and the content of 1-butene is 60% by weight or more. The 4-methyl-1-pentene polymer composition according to claim 1, which is 5. The 4-methyl-1-pentene polymer composition according to claim 1, wherein the (B) 1-butene polymer is a random copolymer of ethylene or propylene and 1-butene. . 6. The polystyrene-ethylene / butylene copolymer-polystyrene triblock copolymer (C) is contained in a weight ratio of styrene / rubber component of 10/90 to 60 /.
The 4-methyl-1-pentene polymer composition according to claim 1, which is in the range of 40. 7. A load according to ASTM D1238: 5k
The 4-methyl-1-pentene polymer composition according to claim 1, wherein the melt flow rate measured under the conditions of g and temperature: 260 ° C. is in the range of 1.0 to 150 g / 10 minutes.