JP3320526B2 - 4-methyl-1-pentene polymer composition - Google Patents

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 suitable for use as release paper or synthetic paper for coverlay films and medical compresses. More specifically, the lamination moldability of various substrates is improved, and a lamination molded article having an appropriate mold release weight and excellent heat resistance is provided.
The present invention relates to a 1-pentene polymer composition.

[0002]

2. Description of the Related Art A 4-methyl-1-pentene polymer is
Because of its extremely low surface tension, excellent releasability and high heat resistance, it is used for process paper for producing artificial leather. However, since the release paper of a 4-methyl-1-pentene polymer is too light for a coverlay film or a release paper for a medical compress, the release paper is peeled off during a punching process or transportation. Often occurs. So far, release paper has been developed for this application in which the surface of a PE film or the like has been treated with a silicone release agent. It is not preferable because the adhesive performance is lowered.

On the other hand, it is known that a 4-methyl-1-pentene polymer has a high temperature dependency of a melt viscosity, and has a low melt viscosity and a low melt tension at a high temperature for lamination molding. For this reason, the 4-methyl-1-pentene-based polymer shows a phenomenon that neck-in and tremors are larger than those of polyethylene and polypropylene. On the other hand, to increase the melt viscosity, 4-methyl-1-
If the MFR of the pentene polymer is reduced, drawdown or surging occurs during lamination molding, and it is very difficult to obtain a molded product having a uniform film thickness. Therefore, as a method for improving these, 4-methyl-1 having a high MFR is used.
Using a pentene polymer to blow heated air to both ends of the web or to lower the resin temperature, the effect is not always at a satisfactory level. Accordingly, there has been a strong demand for a material that has an appropriate peeling property, has excellent heat resistance, has a small neck-in and ear sway during lamination molding, and does not generate drawdown or surging.

[0004]

In view of this situation, 4
As a result of conducting various studies with the aim of imparting an appropriate release property and improving lamination moldability while maintaining the heat resistance of the -methyl-1-pentene polymer as much as possible, the 4-methyl-1-pentene polymer was obtained. Polymer and specific modification 4
-Methyl-1-pentene polymer and high-pressure low-density polyethylene blended at a specific ratio in 4-methyl-1
-It has been determined that the pentene polymer composition satisfies the above characteristics, and the present invention has been completed.

[0005] That is, an object of the present invention is to provide an appropriate mold release weight, high heat resistance and excellent lamination moldability, that is, neck-in and ear sway are greatly improved, and drawdown surging is also achieved. 4-methyl- not generated
An object of the present invention is to provide a 1-pentene polymer composition.

[0006]

According to the present invention, there is provided, according to the present invention, (A) 70 to 97 parts by weight of a 4-methyl-1-pentene polymer, (B) an unsaturated carboxylic acid or its unsaturated carboxylic acid. 0.1 to 10 parts by weight of a modified 4-methyl-1-pentene polymer graft-modified with a derivative in the range of 0.01 to 10% by weight and (C) 20 to 3 parts by weight of a high-pressure low-density polyethylene Parts of the 4-methyl-1-pentene polymer composition, wherein the total amount of the components (A), (B) and (C) is 100 parts by weight. Achieved.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The 4-methyl-1-pentene polymer (A) used in the present invention is 4-methyl-pentene polymer.
A homopolymer of 1-pentene, or 4-methyl-1-pentene and another α-olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene And a copolymer with an α-olefin having 2 to 20 carbon atoms such as 1-octadecene. Such copolymers include 4-methyl-1-
4-methyl-1- containing pentene in an amount of 80% by weight or more
Pentene-based copolymers are preferred. Preferred copolymerization components are, for example, 1-decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane or 1-eicosene.

4-methyl-1-pentene polymer (A)
When the content of the copolymer component exceeds 20% by weight, the melting point of the 4-methyl-1-pentene polymer is lowered, and the heat resistance is remarkably lowered.

The melt flow rate (MFR) of such a 4-methyl-1-pentene polymer (A) is AST
Load according to MD 1238: 5.0 kg, temperature: 260
It is desirable that the value measured under the condition of ° C. be in the range of 1 to 400 g / 10 minutes, and it is particularly preferable that the value be in the range of 10 to 300 g / 10 minutes.

4-methyl-1-pentene polymer (A)
When the MFR is less than 1, the extensibility of the composition is reduced during lamination molding at a high speed, and it becomes difficult to produce lamination paper or the like having a uniform thickness. On the other hand, MFR
Exceeds 400, the molecular weight of the resin is too small,
At the time of lamination molding, the sway of the ears becomes large and the productivity is reduced, and the practical value is reduced for the laminated paper in which the crack of the coating film and the peel strength between the resin and the paper are remarkably reduced.

A 4-methyl-1-pentene polymer [hereinafter referred to as a 4-methyl-1-pentene polymer] serving as a base of the graft-modified 4-methyl-1-pentene polymer (B) used in the present invention. (D)] is the aforementioned 4-methyl-
It may be either a homopolymer of 1-pentene or a copolymer of 4-methyl-1-pentene and another α-olefin.

4-methyl-1-pentene polymer (D)
Examples of the unsaturated carboxylic acid or a derivative thereof grafted to an unsaturated carboxylic acid such as maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid, acrylic acid, and methacrylic acid Or derivatives thereof, for example, acid anhydrides, imides, amides, esters and the like. Specific examples include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Among these, unsaturated dicarboxylic acids or anhydrides thereof are preferred, and maleic acid, nadic acid or anhydrides thereof are particularly preferred.

In order to produce a modified product by graft-copolymerizing a graft monomer selected from the unsaturated carboxylic acid or a derivative thereof with the above-mentioned 4-methyl-1-pentene polymer (D), a conventional known method is used. Various methods can be employed. For example, there is a method of melting the 4-methyl-1-pentene polymer (D) or a method of dissolving it in a solvent and adding a graft monomer to carry out graft copolymerization.

The above-mentioned monomer is efficiently graft-copolymerized with the 4-methyl-1-pentene polymer (D) of the present invention to produce a graft-modified 4-methyl-1-pentene polymer (B). The reaction is preferably carried out in the presence of a radical initiator. The grafting reaction is usually 60 to 35
It is performed at a temperature of 0 ° C. The usage ratio of the radical initiator is
It is usually in the range of 0.001 to 2 parts by weight based on 100 parts by weight of the 3-methyl-1-pentene polymer (D). Examples of the radical initiator include organic peroxides, organic peresters, and other azo compounds. Among these radical initiators, dicumyl peroxide, di-t
tert-butyl peroxide, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexyne-3,
Organic peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The graft-modified 4-methyl-1-pentene polymer (B) of the present invention has a graft monomer of 0.01.
It is a 4-methyl-1-pentene polymer modified in the range of 10 to 10% by weight, preferably 1 to 5% by weight. In general, the intrinsic viscosity at 135 ° C. in a decalin solvent is 0.5 to 1
It is a polymer of 0 dl / g, preferably 0.6 to 5 dl / g. If the graft amount is too low, the composition cannot be given an appropriate release weight. On the other hand, if an attempt is made to increase the graft amount, the molecular weight of the graft-modified 4-methyl-1-pentene polymer (B) becomes extremely small, so that the lamination moldability of the composition deteriorates and the productivity decreases.

In the composition of the present invention, 4-methyl-1-graft modified with an unsaturated carboxylic acid or a derivative thereof is used.
The compounding amount of the pentene polymer (B) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total amount of the components (A), (B) and (C). Parts by weight, particularly preferably in the range from 1 to 5 parts by weight.

When the amount of the graft-modified 4-methyl-1-pentene polymer (B) is less than 0.1 part by weight,
The composition cannot be given a proper release weight.
On the other hand, if the compounding amount exceeds 10 parts by weight, the peel strength is too high, and it is not suitable for use as release paper.

The high-pressure low-density polyethylene (C) used in the present invention preferably has the following density, melting point or M
Has FR. Density 0.910-0.930 g / cm ³
, A melting point of 100 to 110 ° C. measured by the DSC method, and a load of 2.16 K according to ASTM D1238.
g, temperature: MFR measured at 190 ° C. is 0.1 to 0.1.
It is in the range of 100 g / 10 min, particularly preferably in the range of 1 to 50 g / 10 min.

The high pressure method low density polyethylene has an MFR of 10
If it exceeds 0 g / 10 minutes, the melt tension of the 4-methyl-1-pentene polymer composition will decrease, and the neck-in will increase, which tends to make it difficult to achieve the intended purpose.

Specific examples of such high-pressure low-density polyethylene include Mirason 10P, Mirason 10L, Mirason 11P, Mirason 14P, Mirason 16P and Mirason 252 manufactured by Mitsui Petrochemical Industries, Ltd. . And among these, Mirason 10P and Mirason 11P are particularly preferable.

The compounding amount of the high-pressure low-density polyethylene (C) is in the range of 3 to 20 parts by weight per 100 parts by weight of the total of the components (A), (B) and (C), and is 5 to 1 parts by weight.
A range of 5 parts by weight is particularly preferred.

When the amount of the high-pressure-process low-density polyethylene (C) is less than 3 parts by weight, the lamination moldability of the composition is poor, and neck-in and tremors are large. On the other hand, if the amount exceeds 20 parts by weight, the heat resistance is greatly reduced.

The composition of the present invention comprises (A) 4-methyl-1
70 to 97 parts by weight of a pentene-based polymer, and (B) an unsaturated carboxylic acid or a derivative thereof having a graft amount of 0.01.
Dry blending or melt blending of 0.1 to 10 parts by weight of a modified 4-methyl-1 pentene polymer modified in the range of 10 to 10% by weight and (C) 20 to 3 parts by weight of a high-pressure low-density polyethylene. Is obtained by If melt blended, the MF of the melt blended composition
R is a load of 5.0K according to ASTM D1238.
g, MFR measured at 260 ° C. is 1 to 40.
0 g / 10 min, preferably 10 to 30 g
It is particularly preferred that it is in the range of 0 g / 10 minutes.

When the MFR of the 4-methyl-1-pentene polymer composition is less than 1, the spreadability of the composition during lamination molding becomes low, and it is difficult to produce laminating paper having a uniform film thickness. . On the other hand, when the MFR exceeds 400,
Since the molecular weight of the resin is too small, the sway of the ears becomes large and the productivity decreases, and at the same time, the cracking of the coating film and the peel strength between the resin and the paper significantly decrease, and the practical value of the laminating paper tends to decrease. Becomes

To obtain the 4-methyl-1-pentene-based composition of the present invention, (A) 70 to 97 parts by weight of a 4-methyl-1-pentene-based polymer, (B) an unsaturated carboxylic acid or a derivative thereof 0.1 to 10 parts by weight of a modified 4-methyl-1 pentene polymer graft-modified in a range of from 0.01 to 10% by weight and (C) 20 to 3 parts by weight of a high-pressure low-density polyethylene. Various known methods, such as dry blending with a V-type blender, ribbon blender, Henschel mixer, tumbler blender, or after dry blending, melt-kneading with a single-screw extruder or a double-screw extruder or a kneader, a Banbury mixer, or the like,
It is preferable to use a method of granulating or pulverizing.

The 4-methyl-1-pentene composition of the present invention is usually used by adding to a polyolefin such as a silane coupling agent, a weather stabilizer, a heat stabilizer, a slip agent, a nucleating agent, a pigment and a dye. Various compounding agents may be added as long as the object of the present invention is not impaired.

[0027]

EXAMPLES The composition of the present invention will be described below with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.

The evaluation shown in the examples was performed under the following conditions and methods. (1) Lamination moldability Laminated paper was molded under the following conditions. The coating width of the obtained laminated paper was measured at 20 points every 1 m, and the following items were calculated. Laminating paper molding conditions Cylinder temperature C1 / C2 / C3 / C4 / die: 300/350/320/320/320 ° C Die width 500mm Base material Kraft paper Molding speed 50m / min, 100m / min Moldability evaluation items Neck-in ( 500-average of coat width) / 2 (mm) Ear shaking σn-1 (mm) of 20 coat width measured values

(2) MFR The MFR of the pellet was measured under the conditions of a load of 5 kg and a temperature of 260 ° C. in accordance with ASTM D1238. (3) Contact Angle In order to evaluate the wettability, the contact angle of the square plate to water was determined using a CA-S micro II type manufactured by Kyowa Interface Science Co., Ltd.
Measured in ° C. (4) Vicat softening point Specimens molded by injection molding at a cylinder temperature of 300 ° C were measured according to JIS 7206.

<Production of maleic anhydride graft-modified 4-methyl-1-pentene polymer> A homopolymer of 4-methyl-1-pentene ([η] = 1.7 dl / g, MFR =
100 g / 10 min) to 100 parts by weight in a toluene solvent,
A graft reaction of maleic anhydride was performed at 145 ° C. in the presence of a dicumyl peroxide catalyst. The polymer was precipitated by adding a large amount of acetone to the obtained reaction product and collected by filtration. The precipitate was repeatedly washed with acetone to obtain a maleic anhydride-grafted poly-4-methyl-
1-pentene (hereinafter abbreviated as M-PMP) was obtained. The graft ratio of maleic anhydride units in this modified polymer was 4.0% by weight, and the intrinsic viscosity in decalin at 135 ° C. was 0.95 dl / g.

Example 1 4-methyl-1-pentene
1-tetradecene copolymer (1-tetradecene content:
5.0% by weight, MFR = 5g / 10min) 90 parts by weight, M
-2 parts by weight of PMP, Mirason 11P (manufactured by Mitsui Petrochemical Industry Co., Ltd., MFR = 7.2 g / 10 min, density = 0.917)
g / cm ³ ), 10 parts by weight, and 0.1% by weight of tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Ciba Geigy K.K., Irganox 1010) as a stabilizer. Parts and 0.03 parts by weight of calcium stearate (manufactured by Sankyoki Gosei Co., Ltd., trade name: calcium stearate) are dry-blended using a Henschel mixer, and then melt-kneaded at 280 ° C. using an extruder to prepare a composition. did. The MFR of this composition was measured. Next, lamination molding was performed using this composition, and the moldability was evaluated. Further, the contact angle of the obtained paper was measured. Table 1 shows the evaluation results. The Vicat softening point was measured using a specimen molded by an injection molding method.

Example 2 4-Methyl-1-pentene
90 parts by weight of 1-decene copolymer (1-decene content: 2.2% by weight, MFR = 180 g / 10 min), M-PM
P2 parts by weight, Mirason 11P (MFR = 7.2 g / 10
Min, density = 0.917 g / cm ³ ), 10 parts by weight, tetrakis [methylene-3 (3,5-di-tert) as a stabilizer
-Butyl-4-hydroxyphenyl) propionate]
Methane (Ciba Geigy Co., Ltd., Irganox 101
0) 0.1 parts by weight and calcium stearate (Sanyo Kiki Gosei Co., Ltd., trade name: calcium stearate)
After dry blending 0.03 parts by weight with a Henschel mixer, the mixture was melt-kneaded at 280 ° C. using an extruder,
A composition was prepared. The MFR of this composition was measured. Next, lamination molding was performed using this composition, and the moldability was evaluated. Further, the contact angle of the obtained paper was measured. Table 1 shows the evaluation results. The Vicat softening point was measured using a specimen molded by an injection molding method.

Example 3 4-Methyl-1-pentene
1-octadecene copolymer (1-octadecene content:
5.0% by weight, MFR = 5g / 10min) 90 parts by weight, M
-5 parts by weight of PMP, Mirason 11P (manufactured by Mitsui Petrochemical Industries, Ltd., MFR = 7.2 g / 10 min, density = 0.917)
g / cm ³ ) 10 parts by weight, and 0.1 parts by weight of tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Irganox 1010, Ciba Geigy KK) as a stabilizer. And 0.03 parts by weight of calcium stearate (trade name: Calcium Stearate Co., Ltd.) was dry-blended with a Henschel mixer, and then melt-kneaded at 280 ° C. using an extruder to prepare a composition. . The MFR of this composition was measured. Next, lamination molding was performed using this composition, and the moldability was evaluated. Also,
The contact angle of the obtained paper was measured. Table 1 shows the evaluation results. The Vicat softening point was measured using a specimen molded by an injection molding method.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that M-PMP was not used, and the lamination moldability and physical properties were evaluated. Table 1 shows the evaluation results.

[Comparative Example 2] A composition was prepared in the same manner as in Example 1 except that Mirason 11P was not used, and the lami moldability and physical properties were evaluated. Table 1 shows the evaluation results.

[0036]

[Table 1]

[0037]

Industrial Applicability The 4-methyl-1-pentene composition of the present invention has an appropriate release weight and high heat resistance, is excellent in lamination moldability, and has greatly improved neck-in and tremors. Drawdown surging does not occur.

By subjecting the composition of the present invention to lamination molding to various substrates, a lamination molded article having an appropriate release weight and high heat resistance can be obtained. For example, a coverlay film, a medical poultice material It can be suitably used for applications such as release paper and synthetic paper.

Claims (5)

(57) [Claims] 1. Graft modification of (A) 70 to 97 parts by weight of a 4-methyl-1-pentene polymer and (B) an unsaturated carboxylic acid or a derivative thereof in a graft amount of 0.01 to 10% by weight. (A), comprising a dry blend or a melt blend of 0.1 to 10 parts by weight of the modified 4-methyl-1-pentene polymer obtained and (C) 20 to 3 parts by weight of a high-pressure low-density polyethylene. A 4-methyl-1-pentene polymer composition, wherein the total of the components (B) and (C) is 100% by weight. 2. The 4-methyl-1-pentene polymer is
Α-olefin having 2 to 20 carbon atoms and 4-methyl-1
The polymer composition according to claim 1, which is a random copolymer of -pentene, and has a content of 4-methyl-1-pentene of 80% by weight or more. 3. A 4-methyl-1-pentene polymer,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene and 4-methyl-1
The polymer composition according to claim 1, which is a random copolymer of pentene. 4. The polymer composition according to claim 1, wherein the modifying agent for the modified 4-methyl-1-pentene polymer is maleic acid, nadic acid or an anhydride thereof. 5. A high-pressure low-density polyethylene having a density in the range of 0.910 to 0.930 g / cm ³ ,
The melting point measured by the method is in the range of 100 to 110 ° C., the MFR measured under the conditions of load: 2.16 Kg and temperature: 190 ° C. according to ASTM D1238 is 1.0 to 100.
2. The polymer composition according to claim 1, which is in the range of g / 10 minutes.