JPH1081710A - 4-methyl-1-pentene-based polymer sheet, its production and production of stretch forming product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a 4-methyl-1-pentene-1-based polymer sheet suitably used as a raw sheet for producing a stretch forming product of the 4-methyl-1- pentene-based polymer and to provide a method for producing the 4-methyl-1- pentene-based polymer sheet. SOLUTION: This sheet comprises a 4-methyl-1-pentene-based polymer and has >=0.3 orientation coefficient in the machine direction(MD), 30-50% crystallinity and further <=15 coefficient defined by the formula The coefficient of variation in thickness = (S/t)×100 [S is the standard deviation of the sheet thickness; (t) is the average value of the sheet thickness]. The sheet can be produced by rolling the 4 methyl-1-pentene-based polymer and is suitable as a raw sheet for stretch forming. Thereby, the stretch forming product excellent in thickness uniformity, transparency and mechanical strength can efficiently and economically be produced by suppressing the occurrence of the stretch unevenness and stretch breakage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel 4-methyl-1-
Penten-based polymer sheet, method for producing the same, and 4-
The present invention relates to a method for producing a stretch-formed product of a 4-methyl-1-pentene polymer, which comprises stretching a methyl-1-pentene polymer sheet. More specifically, it is possible to suppress the occurrence of stretching unevenness and stretch breakage, that is, to improve the productivity and economically excellent stretch molding suitable for 4-methyl-1-.
The present invention relates to a pentene polymer sheet, a method for producing the same, and a method for producing a 4-methyl-1-pentene polymer stretch-formed product.

[0002]

2. Description of the Related Art 4-Methyl-1-pentene polymer
G is used for release films, etc., taking advantage of its features such as high melting point, good releasability, and high transparency. However, there is a disadvantage that the elastic modulus and strength at high temperatures are low despite the high melting point.

It is generally known that stretching a resin sheet improves mechanical strength at room temperature and high temperature. However, the 4-methyl-1-pentene polymer sheet has poor stretch moldability, often causes stretching irregularities such as necking, and stretch breakage, and it has been desired to improve a method for producing a stretch molded product.

[0004] For these reasons, studies have been made on the production of stretch-formed products composed of 4-methyl-1-pentene polymers, as disclosed in JP-A-55-11821 and JP-A-58-182. JP-A-191734, JP-A-58-2
17327 and the like. However, Japanese Patent Application Laid-Open
The methods disclosed in JP-A-112181 and JP-A-58-217327 need to be performed under specific molding conditions, and the condition management during molding is complicated. Moreover, it is difficult to obtain a high-stretched product even if both techniques are applied. JP-A-58-19
No. 1734 discloses the method of solid 4-methyl-1-.
There is also a problem that the mixing operation is difficult because a liquid hydrocarbon oil is blended with the pentene polymer, and that a blocking easily occurs in an extruder hopper when a sheet is formed using the blend. Further, the characteristics of the 4-methyl-1-pentene polymer may be impaired by blending the hydrocarbon oil.

[0005]

SUMMARY OF THE INVENTION The present invention relates to 4-methyl-
The purpose of the present invention is to efficiently and economically produce a stretch-formed product of a 1-pentene polymer without causing stretching unevenness or stretch breakage.

[0006]

Means for Solving the Problems The present inventors mainly contain a 4-methyl-1-pentene polymer, and have an orientation coefficient of 0.3 or more in the extrusion direction of a sheet determined by X-rays. When the resin sheet is stretched, the degree of crystallinity determined by a line is 30 to 50%, and the thickness variation coefficient defined by the formula (1) is 15 or less. We found good things and completed the present invention.

[0007]

DETAILED DESCRIPTION OF THE INVENTION [4-Methyl-1-pentene-based polymer sheet] The novel 4-methyl-1-pentene-based polymer sheet of the present invention comprises 4
Containing a methyl-1-pentene polymer, having an orientation coefficient in the sheet extrusion direction of 0.3 or more, more preferably 0.4 or more, as determined by X-rays, and crystallization as determined by X-rays. The degree is 30 to 50%, more preferably 35 to
The thickness variation coefficient is within a range of 45%, and the thickness variation coefficient defined by the equation (1) is 15 or less, more preferably 12 or less. The extrusion direction of a sheet refers to the direction in which the sheet is formed and travels during sheet formation, and
Sometimes called the chine direction (MD direction) or the vertical direction.

The thickness of the 4-methyl-1-pentene polymer sheet is not limited, but is usually 2
0 μm to 1 mm.

The 4-methyl-1-pentene polymer used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and another α-olefin such as ethylene and propylene. And 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like. It is a polymer mainly composed of 4-methyl-1-pentene containing 80% by weight or more. Preferred copolymer components are 1-
Decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane or 1-eicosene. And, of course, a mixture of two or more of these α-olefins can also be used.

The content of the copolymer component of the 4-methyl-1-pentene polymer is preferably less than 20% by weight from the viewpoint of heat resistance and rigidity of the stretched product.

The melt flow rate (MFR) of the 4-methyl-1-pentene polymer is 0 according to ASTM D1238, and the melt flow rate (MFR) measured at a load of 5.0 kg and a temperature of 260 ° C. is 0. .1 to 50
It is preferably in the range of 0 g / 10 minutes. Further 1.
It is particularly preferred that it is in the range of 0 to 200 g / 10 minutes. When the MFR is in this range, stretch moldability and the resulting stretch molded product are excellent in impact resistance and mechanical strength.

The 4-methyl-1-pentene polymer used in the present invention may contain a plasticizer in an amount of not more than 30% by weight, as long as the object of the present invention is not impaired. Examples of the plasticizer include mineral oils such as paraffinic, naphthenic, and aroma-based, oligomers and cooligomers of α-olefins, ester-based plasticizers, various vegetable oils, and animal oils. Such a plasticizer improves the moldability during stretching.

The 4-methyl-1-pentene polymer of the present invention may contain other resins, for example, polyolefins, polyamides, polyesters, and the like in a proportion of 30% by weight or less of the whole.

The 4-methyl-1-pentene polymer of the present invention contains various compounding agents, such as weathering stabilizers, heat stabilizers, slip agents, nucleating agents, pigments and dyes, which are usually used in addition to polyolefins. You may add in the range which does not impair the objective of invention.

The 4-methyl-1-pentene polymer sheet used in the present invention preferably contains 70% by weight or more of the 4-methyl-1-pentene polymer.

[Production method of 4-methyl-1-pentene polymer sheet] Such a 4-methyl-1-pentene polymer sheet is melted by, for example, an ordinary T-die molding machine and extruded from a die. The immediately following sheet can be produced by rolling, for example, using a nip roll, preferably in a state where the sheet is heated to a temperature equal to or higher than the glass transition temperature of the 4-methyl-1-pentene polymer. The rolling ratio at this time is not particularly limited, but the rolling ratio (ΔT = sheet thickness after rolling / sheet thickness before rolling) 0.99 to 0.9.
01, particularly preferably 0.95 to 0.01. Here, once the sheet-like material is obtained, it may be cooled and then supplied to the rolling step again, or the step of obtaining the sheet-like material and the rolling step may be continuous.

[Production Method of Stretch-Molded Product] The above-mentioned 4-methyl-1-pentene polymer sheet is preferably used as a raw sheet in the production of a stretch-molded product described below. When the content is in the above range, the stretchability is particularly excellent, and unevenness in stretch and stretch breakage are less likely to occur.

The produced raw sheet is stretched by biaxial stretching,
Although blow molding or the like is possible, it is preferable to perform molding by uniaxial stretching or vacuum molding, and particularly preferred is uniaxial stretching. Stretching is usually 120 to 200 ° C, preferably 140 ° C
To 180 ° C., more preferably 150 ° C. to 170 ° C. For good stretchability, the sheet is preferably preheated before stretching.
It is usually sufficient to preheat for 5 minutes or more in a temperature range of from 150 to 170 ° C, more preferably from 150 to 170 ° C. The stretching speed is generally 1 mm / sec to 500 mm / sec, more preferably 5 mm / sec to 100 mm / sec. The stretching ratio is usually 2-6 times, preferably 3-5 times. When stretching under such conditions,
A stretch-formed product can be efficiently produced without causing stretch unevenness or stretch breakage. The direction of stretching is
It is particularly preferable to perform in the extrusion direction of the raw sheet,
In this case, the stretch formability is particularly excellent.

In the method for producing a stretch-formed product of the present invention, it is determined whether the raw sheet is once supplied to the stretch-forming apparatus or the above-described operation is continuously performed after the raw sheet is once manufactured. , Any of which is possible.

The shape of the stretched product is not particularly limited, but when it is formed into a film or a sheet, the stretchability is particularly excellent, and the thickness uniformity, transparency and mechanical strength of the stretched product are excellent.

The thickness of the stretched product can be adjusted by changing the thickness of the raw sheet, the stretching ratio, etc., and is usually 2 to 100 μm, preferably 10 to 100 μm.
μm, more preferably 20 μm to 50 μm.

The stretch molded product obtained by the method of the present invention has excellent thickness uniformity and transparency, and is particularly excellent in mechanical strength as compared with an unstretched molded product, and is suitable for a release film or the like that requires strength. It is possible to provide.

[0023]

According to the present invention, a stretch-formed article can be produced without stretching unevenness or breakage by stretching a sheet containing a 4-methyl-1-pentene polymer having specific physical properties. In addition, the produced stretch molded article can provide a molded article having excellent thickness uniformity and transparency, particularly excellent mechanical strength as compared with an unstretched molded article. The stretch molded product mentioned here includes, for example, a film, a sheet and the like.

Hereinafter, the 4-methyl-1-pentene polymer sheet of the present invention and the stretch molding thereof will be described based on examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. It is not limited.

[0025]

EXAMPLES The methods for measuring the physical properties shown in the examples are described below. (1) Thickness variation coefficient The thickness of the raw sheet was measured at 30 points, and the average value and standard deviation were determined.

(2) Orientation Coefficient The relationship between the azimuth and the X-ray intensity is determined by X-ray diffraction of the raw sheet, and the result is used to determine “X-ray diffraction of polymer (top)”.
(Chemistry, Leroy E. Alexander, first edition, 1973)
Of p226.

(3) Crystallinity Using an X-ray diffractometer, a relationship diagram between the diffraction angle and the X-ray intensity was obtained by a transmission method, peaks derived from a crystal part and an amorphous part were separated, and the area ratio was obtained. .

(4) Rigidity (Initial Elastic Modulus) A test piece was cut out from a stretched product (film) and subjected to a tensile test under the following conditions. Test piece shape ASTM Type IV Test speed 200mm / min Test temperature 160 ° C

(5) Evaluation of stretch formability The raw sheet was stretched at a stretching temperature of 160 ° C. and a stretching speed of 10 mm / s.
Under the conditions of ec, the sheet was uniaxially stretched in the extrusion direction of sheet formation to a stretch ratio of 4 times, and stretchability and stretchability of the stretched product were reduced to 1%.
The rigidity at 60 ° C. was evaluated. The stretch formability was visually evaluated in a stretch ratio section where uniform stretching was possible, that is, a stretch ratio section where uniform stretching was possible without causing stretching unevenness, necking and sheet breakage. Table 2 shows the magnification at which uniform stretching started and the magnification at which uniform stretching was no longer possible. Here, the stretching ratio refers to (film length after stretching) / (film length before stretching).

[0030]

Example 1 4-methylpentene-1 and 1-dodecene,
1-tetradecene copolymer (4-methylpentene-1
Content: 95% by weight, MFR: 26g / 10min)
-Methyl-1-pentene polymer sheet (raw sheet)
Was prepared. Specifically, the copolymer was supplied to an extruder, melt-kneaded at a molding temperature of 270 ° C., extruded from a T-die, and then rolled through a nip roll. The rolling ratio here was 0.94. Table 1 shows the properties of the raw sheet. The sheet was uniaxially stretched in a molding extrusion direction (molding direction), and the stretch formability and the rigidity of the stretched product at 160 ° C. were evaluated. Table 2 shows the evaluation results.

[0031]

Example 2 A stretch molded product was prepared in the same manner as in Example 1 except that the amount of the copolymer used in Example 1 was increased from the extruder to increase the thickness of the raw sheet. The stretch moldability and the rigidity of the stretch molded product at 160 ° C. were evaluated. The results are shown in Tables 1 and 2.

[0032]

Comparative Example 1 A stretch-molded product was prepared in the same manner as in Example 1 except that a raw sheet was obtained by cooling using a normal roll without rolling with a nip roll, and stretch-forming properties and stretching were performed. The rigidity of the molded product at 160 ° C. was evaluated. The results are shown in Tables 1 and 2.

[0033]

Comparative Example 2 A stretch molded article was prepared in the same manner as in Comparative Example 1 except that the amount of the copolymer used in Example 1 was increased from the extruder to increase the thickness of the raw sheet. The stretch moldability and the rigidity of the stretch molded product at 160 ° C. were evaluated. The results are shown in Tables 1 and 2.

[0034]

Comparative Example 3 A sheet of the copolymer used in Example 1 was produced by a press molding machine. The prepared sheet was formed into a stretched product in the same manner as in Example 1, and the stretch formability and the rigidity of the stretched product at 160 ° C. were evaluated. The results are shown in Tables 1 and 2.

[0035]

[Table 1]

[0036]

[Table 2]

Continued on the front page (72) Inventor Toshimasa Takada 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd.

Claims (7)

[Claims] 1. A sheet containing a 4-methyl-1-pentene polymer, having an orientation coefficient of 0.3 or more in the extrusion direction of a sheet determined by X-ray, and having a crystallinity of 3 determined by X-ray.
A 4-methyl-1-pentene polymer sheet having a thickness variation coefficient of 0 to 50% and a thickness variation coefficient defined by the formula (1) of 15 or less. ## EQU1 ## Thickness variation coefficient% = (S / t) × 100 (1) (S: standard deviation of sheet thickness, t: average value of sheet thickness) 2. The 4-methyl-1-pentene polymer is
A homopolymer of 4-methyl-1-pentene or a random copolymer of an α-olefin having 2 to 20 carbon atoms and 4-methyl-1-pentene, wherein the content of 4-methyl-1-pentene is 80; The 4-methyl-1-pentene-based polymer sheet according to claim 1, which is not less than% by weight. 3. A 4-methyl-1-pentene polymer,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or their α
A mixture of two or more olefins and 4-methyl-1-
The 4-methyl-1-pentene polymer sheet according to claim 1, which is a random copolymer of pentene. 4. The 4-methyl-1-pentene polymer according to claim 1, wherein the 4-methyl-1-pentene polymer is melted, extruded into a sheet, and then rolled. Sheet manufacturing method. 5. A sheet containing a 4-methyl-1-pentene polymer, having an orientation coefficient of 0.3 or more in an extrusion direction of a sheet determined by X-rays, and having a crystallinity of 3 determined by X-rays.
Production of a stretch-molded article, characterized by stretching a 4-methyl-1-pentene polymer sheet having a thickness variation coefficient defined by the formula (1) of not more than 15 which is 0 to 50%. Method. ## EQU2 ## Thickness variation coefficient% = (S / t) × 100 (1) (S: standard deviation of sheet thickness, t: average value of sheet thickness) 6. The method for producing a stretch-formed product according to claim 5, wherein the stretching is performed in a forming direction of the 4-methyl-1-pentene polymer sheet. 7. The method according to claim 5, wherein the stretching operation is performed by uniaxial stretching.