JPH06322043A - Modified alpha-olefin polymer with tertiary carbon atoms at side chains and stretached film obtained therefrom - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a modified α-olefin polymer having excellent impact resistance, heat resistance, or mechanical properties and suitable for use in structural materials and films, and a stretched film obtained therefrom. [Structure] (A) 100 parts by weight of an α-olefin polymer having a tertiary carbon in the side chain, and (B) the following formula (1): Here, R is a hydrogen atom or a methyl group, M is a metal cation, X is an anion, m is an integer of 2 or more, and n is an integer of 2 or more, provided that m ≧ n.
Which is obtained by melting reaction with 0.05 to 10 parts by weight of a metal methacrylate or a metal acrylate represented by
-Olefin-based polymers and stretched films obtained therefrom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified α-olefin polymer having a tertiary carbon in its side chain and a stretched film obtained from the polymer. More specifically, impact resistance,
The present invention relates to a modified α-olefin polymer having excellent heat resistance or mechanical properties and suitable for use in structural materials and films, and a stretched film obtained therefrom.

[0002]

2. Description of the Related Art A 4-methyl-1-pentene polymer is
Since it has a melting point of 220 to 240 ° C and a high heat deflection temperature, and is excellent in transparency and mold release property, MWO tableware,
It is widely used for applications such as release film or synthetic leather process paper. However, 4-methyl-1-pentene-based polymers have low impact resistance and low mechanical strength, and are not often used as structural materials. In addition, the stretchability is low, and biaxial stretching is particularly difficult. Therefore, in order to improve the impact resistance of the 4-methyl-1-pentene polymer, 4-methyl-1-
A blend of a pentene polymer and a specific ethylene-α-olefin copolymer has been proposed (JP-A-59-16).
No. 4349). However, since the blended body of this publication has a rubber component with low heat resistance blended therein, the heat resistance is remarkably lowered as compared with the 4-methyl-1-pentene polymer, and the flexural strength and flexural modulus are also reduced. The mechanical strength such as is also reduced.

Further, modification of polyolefin with acrylic acid or methacrylic acid has been proposed (Japanese Patent Laid-Open No. 63-10606 and Japanese Patent Laid-Open No. 2-14021).
No. 2), a radical initiator such as peroxide is also used in each case. However, α having 3 or more carbon atoms such as 4-methyl-1-pentene polymer
-A polymer of olefin is decomposed by radicals generated from a radical initiator, and the molecular weight thereof is drastically reduced. Therefore, the modified polyolefin obtained has very low mechanical strength. On the other hand, in the case of a cross-linkable polyolefin such as polyethylene, on the contrary, the cross-linking progresses and the mechanical properties of the modified product also deteriorate.

Further, modification of polyolefin with acrylic acid or methacrylic acid has been proposed (Japanese Patent Laid-Open Nos. 58-120608 and 63-831).
No. 11), and modification with metal methacrylate or metal acrylate (metal: metal cation having a valence of 2 or more) has not been proposed yet. Therefore, while maintaining the heat resistance of the 4-methyl-1-pentene-based polymer, the impact resistance and mechanical strength are improved, and 4-methyl-1-, which has good stretchability, is used.
There has been a strong demand for the development of pentene polymers.

[0005]

In view of this situation, 4
Various studies have been carried out for the purpose of improving impact resistance, mechanical strength, and stretchability while maintaining heat resistance equivalent to that of a -methyl-1-pentene polymer, and have arrived at the present invention.

That is, the object of the present invention is modified 4-methyl-, which has excellent impact resistance, heat resistance and mechanical strength and is suitable for various structural materials, films, stretched films and the like.
Another object of the present invention is to provide a modified α-olefin polymer having a tertiary carbon in the side chain such as a 1-pentene polymer. Another object of the present invention is to provide a stretched film from the above modified α-olefin polymer of the present invention. Other objects and advantages of the present invention will be apparent from the following inventions.

[0007]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) 100 parts by weight of an α-olefin polymer having a tertiary carbon in a side chain. (B) The following formula (1)

[0008]

[Chemical 2]

Here, R is a hydrogen atom or a methyl group, M is a metal cation, X is an anion, and m
Is an integer greater than or equal to 2 and n is an integer greater than or equal to 2, with m ≧ n,

A modified α-olefin polymer having a tertiary carbon in the side chain, which is obtained by melting reaction with 0.05 to 10 parts by weight of metal methacrylate or metal acrylate represented by is there.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The side chain used in the present invention is the third
Examples of the α-olefin polymer (A) having a primary carbon include 4-methyl-1-pentene polymer, 3-methyl-1-butene polymer, 4-methyl-1-hexene polymer, 5-methyl-1-hexene polymer and 5
-Methyl-1-heptene polymer can be mentioned. Among these, 4-methyl-1-pentene-based polymer (A) is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and other α-olefins such as ethylene and propylene. , 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like, and a copolymer with an α-olefin having 2 to 20 carbon atoms. Among these, a polymer mainly containing 4-methyl-1-pentene containing 80% by weight or more of 4-methyl-1-pentene is preferable. The preferred copolymerization component is 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene. These α
It is of course also possible to use mixtures of two or more olefins.

4-Methyl-1-pentene polymer (A)
When the content of the copolymerization component of 20% by weight is more than 20% by weight, the heat resistance of the 4-methyl-1-pentene polymer is remarkably lowered, so that the material is less attractive when considering the cost performance as a structural material or a film. Become.

The melt flow rate (MFR) of the 4-methyl-1-pentene polymer (A) is AST.
According to MD 1238, load: 5.0 kg, temperature: 260
The melt flow rate (MFR) measured under the condition of
It is preferably in the range of 0.01 to 400 g / 10 minutes. And it is particularly preferable that it is in the range of 1 to 300 g / 10 minutes.

MF of 4-methyl-1-pentene polymer
When R is less than 0.01, it is difficult to obtain a good molded product because the fluidity is low even if the molding temperature is increased. On the other hand, MFR is 4
If it exceeds 00, the molecular weight becomes too small and the impact resistance and mechanical strength tend to decrease.

The metal methacrylate or metal acrylate (B) used in the present invention is represented by the above formula (1).
Specific examples of these include zinc methacrylate, calcium methacrylate, magnesium methacrylate, barium methacrylate, metal methacrylate such as barium methacrylate and tin methacrylate, or zinc acrylate, calcium acrylate, magnesium acrylate,
Mention may be made of metal acrylates such as barium acrylate, aluminum acrylate and tin acrylate. Other compounds can be used as long as they are metal methacrylic acid or metal acrylate containing a divalent or higher valent metal cation. Among these examples, zinc methacrylate, magnesium methacrylate, zinc acrylate or magnesium acrylate is an α-olefin polymer having a tertiary carbon in the side chain such as 4-methyl-1-pentene polymer. It is preferable because it has a relatively high compatibility with. Further, of course, two or more kinds of these can be used without any problem.

The mixing ratio of such metal methacrylate or metal acrylate (metal: a metal cation having a valence of 2 or more) is 100 parts by weight of an α-olefin polymer having a tertiary carbon in the side chain. A range of 0.05 to 10 parts by weight is preferable, a range of 0.1 to 5.0 parts by weight is more preferable, and a range of 0.2 to 3.0 parts by weight is particularly preferable.

When the amount of the metal methacrylate or the metal acrylate is less than 0.05 part by weight, the effect of sufficiently improving impact resistance cannot be recognized. On the other hand, the compounding amount is 10
When it exceeds the weight part, the MFR becomes low and the molding becomes extremely difficult under normal conditions, and the physical properties become brittle.

Produced by melt-reacting (A) 100 parts by weight of an α-olefin polymer having a tertiary carbon in the side chain and (B) 0.05 to 10 parts by weight of metal methacrylate or metal acrylate. The MFR of the modified α-olefin-based polymer of the present invention is in the range of 0.01 to 400 g / 10 minutes as measured according to ASTM D 1238 under the conditions of load: 5.0 Kg and temperature: 260 ° C. It is preferable that it is in the range of 1.0 to 200 g / 10 minutes.

M of the modified α-olefin polymer of the present invention
If the FR is less than 0.01, the fluidity is too low to obtain a good molded product, while if the MFR exceeds 400, the molecular weight of the polymer is too small and the mechanical strength of the molded product is low. Will be lower.

To obtain the modified α-olefin polymer of the present invention, (A) 4-methyl-1-pentene polymer 10
0 parts by weight and (B) metal methacrylate or metal acrylate 0.05 to 10 parts by weight are melt-reacted. For this purpose, various known methods such as V-type polystyrene blender, ribbon blender, Henschel mixer, tumbler blender, and then melt kneading with a single-screw extruder, multi-screw extruder or kneader, Banbury mixer, etc.,
A method of granulating or crushing can be used.

The modified α-olefin polymer of the present invention is produced at a temperature of 4 times with metal methacrylate or metal acrylate.
It is desirable that the temperature is not lower than the temperature at which the methyl-pent-1-pentene polymer is graft-polymerized. That is, the melt-kneading temperature is preferably in the range of 100 to 360 ° C, particularly preferably in the range of 200 to 340 ° C.

The composition using the modified α-olefin polymer of the present invention is usually added to a polyolefin such as a silane coupling agent, a weather resistance stabilizer, a heat resistance stabilizer, a slip agent, a nucleating agent, a pigment or a dye. Various compounding agents used as described above can be added.

Due to the excellent stretchability of the modified α-olefin polymer of the present invention, the present invention further provides a stretched film comprising the modified α-olefin polymer of the present invention. The stretched film of the present invention can be either a uniaxially stretched film or a biaxially stretched film.

The uniaxially stretched film is obtained by melt-extruding an unstretched film from an extruder at a temperature of 120 to 200 ° C., preferably 140 to 180 ° C., and a ratio of 2.5 to 6 times, preferably 4 to 5 times. It can be obtained by stretching. The uniaxially stretched film thus obtained has a thickness of 150 if necessary.
The heat treatment can be performed at a temperature of 220 ° C. The biaxially stretched film is obtained by simultaneously or successively biaxially stretching an unstretched film. The stretching temperature is the same as the above 120-
200 degreeC, Preferably it is 140-180 degreeC. The draw ratio is 2 to 10 times, preferably 4 to 8 times in terms of surface magnification.
The relaxation heat treatment is performed at a temperature of 70 to 200 ° C., if necessary. The thickness of the unstretched film is preferably 20 μm to 1 mm, and the thickness of the stretched film is preferably 2 to 100 μm.

[0025]

The modified α-olefin polymer of the present invention has excellent impact resistance and mechanical strength while maintaining heat resistance equivalent to that of an unmodified 4-methyl-1-pentene polymer. And has excellent stretchability.

That is, by using the modified α-olefin polymer of the present invention, a molded article excellent in impact resistance, heat resistance and mechanical properties can be obtained by various molding methods such as injection molding and extrusion molding. Is obtained. According to the invention,
It is possible to provide a modified α-olefin-based polymer suitable for various structural materials and applications such as films, and a stretched film obtained therefrom. It can be suitably used as a structural material for automobiles, a release film for a flexible printed circuit board, a process paper for artificial leather, or a sheath material for manufacturing a rubber hose.

The modified α-olefin polymer of the present invention is
Behavior with peculiar melt viscosity, that is, resin temperature is 300 ℃
Since the melt viscosity is drastically reduced when it becomes the above, it can be used as various viscosity modifiers.

[0028]

EXAMPLES The modified α-olefin polymer 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 evaluations shown in the examples are performed under the following conditions and methods. (1) Molding of Specimens Specimens were molded by the injection molding method under the following conditions. Molding conditions Injection molding machine Made by Meiki Seisakusho, M100 Cylinder temperature C1 / C2 / C3 / Nozzle 270/290/300 /
300 ℃ Mold temperature 60 ℃

(2) Preparation of biaxially stretched film Molding of original sheet An original sheet was formed under the following conditions. Molding conditions Extruder Modern Co., Ltd., 65
mmφ Cylinder temperature 280 ° C. Cooling roll temperature 60 ° C. Film thickness 370 μ Preparation of biaxially stretched film A biaxially stretched film was produced by stretching a raw sheet under the following conditions. Stretching condition equipment Toyo Seiki's biaxial stretching equipment Remaining heat temperature 160 ° C Remaining heat time 5 minutes Stretching magnification 5x5 times Stretching speed 4m / min Size of biaxially stretched raw sheet 95mmx95mm
× 370μ

(3) Evaluation of Physical Properties Physical properties were evaluated under the following conditions. MFR The MFR of the pellet was measured according to ASTM D1238 under the conditions of load: 5 kg and temperature: 260 ° C. Izod impact strength Izod impact strength was measured according to ASTM D256. Tensile test ASTM-Mold type IV specimen and ASTM
It measured based on D638. Bending test Bending strength and elastic modulus were measured according to ASTM D790. Heat distortion temperature (HDT) HDT was measured according to JIS 7206. However,
The load was 66 psi.

Example 1 4-Methyl-1-pentene / 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR
= 0.5 g / 10 minutes) 100 parts by weight, zinc methacrylate (manufactured by Asada Chemical Co., Ltd.) 1.0 parts by weight, and as a stabilizer 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: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate) 0.03 parts by weight in a Henschel mixer. And mixed at high speed for 1 minute. The obtained mixture was melt-kneaded at 310 ° C. using a twin-screw extruder and reacted to obtain pellets. Then, the MFR of the pellet was measured. Specimens were molded by an injection molding method using the pellets, and their physical properties were evaluated. The results are shown in Table 1.

Example 2 4-Methyl-1-pentene / 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR
= 0.5 g / 10 min) 100 parts by weight, magnesium methacrylate (manufactured by Asada Chemical Co., Ltd.) 1.0 parts by weight, 3,9-bis [2- {3- (3-tert-butyl- Four
-Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (Sumitomo Chemical Co., Ltd.)
Product name: Sumilizer GA80) 0.10 parts by weight,
Penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cipro Kasei Co., Ltd., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate) 0 0.03 part by weight was mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded and reacted at 310 ° C. using a twin-screw extruder to obtain pellets. Then, the MFR of the pellet was measured. This pellet is used to mold Specimen by injection molding,
The physical properties were evaluated. The results are shown in Table 1.

Example 3 4-Methyl-1-pentene / 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR
= 0.5 g / 10 minutes) 100 parts by weight, calcium methacrylate (manufactured by Asada Chemical Co., Ltd.) 1.0 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.)
Product name: Sumilizer GA80) 0.10 parts by weight,
Penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cipro Kasei Co., Ltd., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate) 0 0.03 part by weight was mixed for 1 minute at high speed using a Henschel mixer. The obtained mixture was melt-kneaded and reacted at 310 ° C. using a twin-screw extruder to obtain pellets. Then, the MFR of the pellet was measured. This pellet is used to mold Specimen by injection molding,
The physical properties were evaluated. The results are shown in Table 1.

[0035]

[Table 1]

Comparative Example 1 4-Methyl-1-pentene / 1-hexadecene copolymer powder (1-hexadecene content: 4.0% by weight, MFR
= 0.5 g / 10 minutes) 100 parts by weight, 3,9 as a stabilizer
-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: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate) 0.03 parts by weight in a Henschel mixer. And mixed at high speed for 1 minute. The obtained mixture was melt-kneaded and reacted at 310 ° C. using a twin-screw extruder to obtain pellets. Then, the MFR of the pellet was measured. Specimens were molded by an injection molding method using the pellets, and their physical properties were evaluated. The results are shown in Table 2.

Comparative Example 2 100 parts by weight of polyethylene (MFR = 1.5 g / 10 minutes), 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) 0.1
0 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name:
0.03 parts by weight of calcium stearate) was mixed at high speed for 1 minute using a Henschel mixer. The obtained mixture was melt-kneaded at 210 ° C. using a twin-screw extruder and reacted to obtain pellets. Then, the MFR of the pellet was measured. Specimens were molded by an injection molding method using the pellets, and their physical properties were evaluated. The results are shown in Table 2.

Comparative Example 3 100 parts by weight of polyethylene (MFR = 1.5 g / 10 minutes), 1.0 part by weight of zinc methacrylate, 3,9 as a stabilizer
-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: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name: calcium stearate) 0.03 parts by weight in a Henschel mixer. And mixed at high speed for 1 minute. The obtained mixture was melt-kneaded at 210 ° C. using a twin-screw extruder and reacted to obtain pellets. Then, the MFR of the pellet was measured. Specimens were molded by an injection molding method using the pellets, and their physical properties were evaluated. The results are shown in Table 2.

[0039]

[Table 2]

Example 4 4-Methyl-1-pentene / 1-octadecene copolymer powder (1-octadecene content: 6.0% by weight, MFR
= 0.5 g / 10 minutes) 0.25 parts by weight of magnesium methacrylate (manufactured by Asada Chemical Co., Ltd.), and 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) 0.1
0 parts by weight, penta (erythrityl-tetra-β-mercaptolauryl) propionate (Cypro Kasei Co., Ltd., trade name: Seanox 412S) 0.10 parts by weight and calcium stearate (Sankoki Gosei Co., Ltd., trade name:
0.03 parts by weight of calcium stearate) was mixed at high speed for 1 minute using a Henschel mixer. This mixture was melt-kneaded at 280 ° C. using a twin-screw extruder to obtain pellets. Then, the MFR of the pellet was measured. A raw sheet having a thickness of 370 μ was formed from the pellets, and a biaxially stretched film was formed using the sheet. The physical properties of the obtained biaxially stretched film were evaluated, and the results are shown in Table 3.

Comparative Example 4 Example 4 except that magnesium methacrylate was not added.
A biaxially stretched film was formed in the same manner as in. The results are shown in Table 3.

[0042]

[Table 3]

[0043]

Claims (7)

[Claims] 1. (A) 100 parts by weight of an α-olefin polymer having a tertiary carbon in the side chain, and (B) the following formula (1): Here, R is a hydrogen atom or a methyl group, M is a metal cation, X is an anion, m is an integer of 2 or more, and n is an integer of 2 or more, provided that m ≧ n.
Which is obtained by melting reaction with 0.05 to 10 parts by weight of a metal methacrylate or a metal acrylate represented by
-Olefin-based polymers. 2. The polymer according to claim 1, wherein the α-olefin polymer having a tertiary carbon in the side chain is a 4-methyl-1-pentene polymer. 3. A 4-methyl-1-pentene polymer,
Α-olefins having 2 to 20 carbon atoms and 4-methyl-
Random copolymer of 1-pentene, 4-methyl-
The content of 1-pentene is 80% by weight or more.
The polymers described. 4. A 4-methyl-1-pentene polymer,
Random copolymer of 4-methyl-1-pentene with an α-olefin selected from 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and a mixture of two or more of these α-olefins. The polymer according to claim 2, which is a polymer. 5. The metal cation is Ca ²⁺ , Zn ²⁺ , Mg.
The polymer according to claim 1, which is ²⁺ , Ba ²⁺ , Al ³⁺ or Sn ⁴⁺ . 6. A stretched film comprising the modified α-olefin polymer having a tertiary carbon in the side chain according to claim 1. 7. The stretched film according to claim 6, which is a biaxially stretched film.