JPS60176741A - Stretched film - Google Patents

Abstract

PURPOSE:To obtain a stretched film excellent in heat resistance, mechanical strength, electrical properties, chemical resistance, etc., by stretching an unstretched film, which has been prepared from a 3-methylbutyl-1 (co)polymer having a specified melt viscosity, at or over a specified ratio. CONSTITUTION:3-Methylbuten-1 is polymerized or 3-methylbuten-1 and a polyene and/or an olefin of 2-12C are copolymerized to produce a poly-3-methylbutyl-1 having a melt viscosity of 1X10<4> poises or more measured at 330 deg.C and a shearing rate of 0.11/sec. This is formed into a film by a conentional film forming method such as a T-die method or the like, and the obtained unstretched film is stretched at a draw ratio of 2 or more by a conventional stretching manner to obtain the intended stretched film. USE:Magnetic recording base films, heat-resistant and electrical insulating film, various packaging materials, sheets, condenser films, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stretched films. Specifically, the present invention relates to a stretched film of a 3-methylbutene-1 polymer or copolymer suitable for use in electrical and electronic parts.

In recent years, various plastic films with excellent heat resistance, mechanical strength, and electrical properties have been used in many fields including electrical and electronic parts. For example, polyethylene terephthalate film and polyimide film are currently used as typical plastic films for magnetic recording base films and 7-lexiple printed wiring boards. However, these conventional films are not necessarily satisfactory in terms of physical properties.

Namely, polyethylene terephthalate film has insufficient heat resistance, and polyimide film has problems in that it has a large hygroscopic expansion coefficient and is expensive.

On the other hand, poly-3-methylbutene-7, which is a crystalline polyolefin, is known to exhibit a high melting point;
However, they generally have poor flexibility and poor elongation properties, making them difficult to stretch and, as such, difficult to use for the above-mentioned purposes. ff1J Normally, plastic film is stretched at temperatures below the melting point of the plastic, -
Poly-3-methylbutene-7 is stretched at a temperature above the next transition point to achieve plane orientation, and is approximately 0°C to 3/3°C.
It will be stretched at a temperature of about 0°C. However, this polymer has a relatively small elongation at break, which tends to cause uneven stretching, and this is thought to be due to the fact that when high-strength stretching is carried out in row 9, the film breaks, making it difficult to obtain a uniform stretched film. .

The inventors of the present invention have conducted intensive studies to overcome these drawbacks of poly-3-methylbutene-1 and to develop a plastic film with excellent physical properties such as heat resistance, mechanical strength, and electrical properties. The present invention was achieved by discovering that a stretched film having the above-mentioned excellent physical properties can be easily obtained when Bo17 3-methylbutene-1 or a copolymer thereof having a specific melt viscosity is used.

That is, 1 Invention FiJ J, 0°C, shear rate θ, //
A homopolymer of 3-methylbutene-7 or a copolymer of 3-methylbutene-7 and an α-olefin and/or polyene having a carbon number of -/- having a melt viscosity of /x10" poise or more when measured under conditions of The present invention is a stretched film obtained by stretching an unstretched film formed from a combination at a stretching ratio of 2 times or more.

The present invention will be explained in more detail below.

Poly-3-methylbutene-' used in the present invention
It is a homopolymer of VibJ-methylbutene-7 or a copolymer of 3-methylbutene-7 and an α-olefin and/or polyene having a carbon number of λ to /. Examples of α-olefins having 1 to 1 carbon atoms copolymerized with 3-methylbutene-1 include U ethylene, propylene, butene-1, hexene-1%, goo-methylpentene-/, octene-11 styrene, vinylcyclohexane, etc. , and polyenes include butadiene, hexadiene, methylhexadiene, ethylidene norbornene, and the like.

The copolymerization method may be so-called random copolymerization or block copolymerization. Among these, 3-methylbutene-
7, a random copolymer of J-methylbutene/and ethylene, propylene or butene, a block copolymer, and a copolymer of 3-methylbutene/and a small amount of diene. It is preferable that the amount of these copolymerized components in the polymer is less than 0.2 mm, more preferably less than 20 mm.

The melt viscosity must be measured downstream with a conical disc rotary rheometer and must be below / A high melt viscosity is preferable in terms of stretchability and mechanical properties, but if it is too high, extrusion moldability when the original polymer is melted becomes undesirable.

Usually, the melt viscosity is expressed by the above measurement method: /X10'~/
Selected from a range of X10 Maboaz.

Poly-3-methylbutene with such a melt viscosity
Any method may be used to manufacture 7, and there are no particular limitations. For example, the following method may be used.

i.e. hexane, hegetane, cyclohexane.

In an aliphatic, alicyclic or aromatic hydrocarbon such as benzene, in a liquid olefin, or in the absence of a solvent, the aluminum content is 0. / and the presence of a catalyst system consisting of a solid titanium trichloride catalyst complex containing a complexing agent and aluminum diisobutyl monochloride or further as a third component an electron-donating compound such as an ether, ester, amine, amide. Below, 3-methylbutene-7 is independently polymerized at a polymerization degree of 0 to 750°C, or J-methylbutene-1 is copolymerized with an α-olefin and/or polyene having a carbon number of λ~/co. be.

Such solid titanium trichloride catalyst complex is
g da jl, same! r, t-gguSko, samejS-f 00
J, same j41-core 87/, same jj-, ytrits
, JP-A Sho Doug-34I Gua et al.

In addition, 3-methylbutene-1 may be combined with M alone in the presence of the above polymer or a commonly known Ziegler catalyst, or may be combined with J-methylbutene-/trifluoride prime number λ~/co of α-olefin and/or polyene. It is also possible to crosslink a polymer obtained by copolymerizing.

The thus obtained poly-3-methylbutene-/ij, T
The film is formed by a conventional film forming method such as a die method or an inflation method. The formed unstretched film is then uniaxially or biaxially stretched by a conventional stretching method to improve its strength. Stretching temperature Fi is at a temperature higher than the second-order transition point and lower than the melting point,
It is usually about go~310°C. The stretching ratio is more than 10 times.

The stretched film obtained by the present invention has excellent chemical resistance, solvent resistance, transparency, etc. in addition to heat resistance, mechanical strength, and electrical properties, so it can be used as a magnetic recording base film, a flexible printed wiring board base film, and heat resistance. Suitable for use in electrical insulation films, various packaging materials, sheets, capacitor films, and other applications.

Examples will be shown below, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

In addition, the mechanical properties of the stretched films in the examples are as follows: AST
This is a value measured according to M-DAJg.

Production example / iAJ Production of homogeneous titanium trichloride solution Purified toluene /! rOml and fl' tetrachloride 790
Prepare mmol and further di-n-butyl ether? 0
771 mol was added. Titanium tetrachloride and di-n-butyl ether react with some heat and are uniformly dissolved in toluene.

An orange-yellow homogeneous solution was obtained. While stirring the solution and keeping it at 5°C, 47% of diethylaluminum monochloride was added to it. When a solution of rrrLmol dissolved in toluene was gradually added, a dark orange homogeneous solution of titanium trichloride was obtained.

(Bl Precipitation formation of titanium trichloride and production of catalyst (above) When the homogeneous solution of titanium trichloride obtained in the sword process was heated to 95°C, a purple precipitate of titanium trichloride was observed to form during the heating process. After stirring at 95°C for 60 minutes, the precipitate was separated and washed three times with 100 ml of n-hebutane to obtain a finely divided purple titanium trichloride catalyst complex. Elemental analysis revealed that this catalyst complex had the formula TiO] a(A)all, )0.00 da[(
non He )s O:] had a composition of 0.0.

Example: Using the solid titanium trichloride catalyst complex obtained in Production Example 1 in an induction stirring autoclave with a container lid, 3-methylbutene
Polymerization of No. 7 was carried out as follows. Thoroughly vacuum dry
In an autoclave purged with nitrogen, the solid titanium trichloride catalyst complex obtained in Production Example 1 was added to O, Lycium Qll and diisobutylaluminum monochloride were added to 1/6771 m
I prepared ol. Then, liquefied 3-methylbutene-7 was added to 63
09 After charging, 3. It took a while to polymerize. Next, x sml of isobutyl alcohol was charged to stop the polymerization, and excess unreacted monomer was expelled. Next, dP'9-//θθOat was introduced into the normal reactor, and after stirring for 3θ minutes at SO°C, the supernatant was taken out and the catalyst component in the polymer was washed away. After repeating this operation 5 times, it is dried to form a white powder poly-3-methylbutene-/, 2
f6. fI was obtained.

To the obtained poly J-methylbutene-/, 061 parts of Irganoxno 010 was added as an additive, and Irgafos P-KP was added.
A part of Q was made of O0 (Japanese chihari X10" Poise).Using the above pellet, extrude a film with a thickness of 00μ through a T-die at 330°C, pass it through a cold roll, and then uniaxially heat it at 200°C. Stretching was performed. The mechanical properties of the obtained stretched film are shown in Table 7.

In Example/Example/, the polymerization temperature was 30°C and the amount of catalyst was 3.01.
! The amount of diisobutylaluminum monochloride is 101
6 g@mol, and a small amount of butene was introduced every 3 minutes at the same time as the polymerization started, so that the amount of butene was 1 g per mol of the total polymer production. Polymerization was carried out in exactly the same manner as in Example 1, except that the weight ratio was copolymerized and the polymerization time was set to co-hours.

It was /×7 bipoise. Table 1 shows the mechanical properties of the stretched film obtained in the same manner as in Example except that the stretching temperature was set to iso°C.

Example 3 In Example 3, 3 methylbutene was added to vinylcyclohexane 711. Polymerization was carried out in the same manner as in Example 1, except for charging kl.

The mechanical properties of the stretched film are shown in Table 7.

Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1 except that the polymerization temperature was 0° C. and the cocatalyst was triethylaluminum. The resulting resin had a very low viscosity of 101 poise. The film was extruded using a T-die in the same manner as in Example 1, and -axially stretched, but the film broke during stretching for 1 g.

Comparative Example In Example 1, polymerization was carried out in exactly the same manner as in Example 1, except that diethylaluminum chloride was used as the cocatalyst. The resulting resin had a melting point of poise and a low viscosity. The film was extruded using a T-die and uniaxially stretched in the same manner as in Example 1, but high-strength stretching was not possible. /;, 1
Table 7 shows the physical properties of the double-stretched product.

Comparative Example 3 The physical property values of the unstretched film in Example 1 are shown in Table-1.

As is clear from Table 7, the stretched film of poly3 methylbutene-7 according to the present invention has much greater strength than the unstretched film, and has the electrical properties required for electrical and electronic parts. It can be seen that it is very useful as a film for

Claims (1)

[Claims] A homopolymer of 3-methylbutene-l having a melt viscosity measured at
Alternatively, a stretched film obtained by stretching an unstretched film formed from a copolymer with polyene at a stretching ratio of 0.5 times or more.