JPH01271220A - Polyphenylene sulfide film - Google Patents

Abstract

PURPOSE:To prevent unevenness to be generated on a film at the time of metallizing of the film, by making use of a specific biaxially oriented polyphenylene sulfide film as the metallizing film. CONSTITUTION:A sheet comprised of a resin composition consisting mainly of poly-P-phenylene sulfide is biaxially oriented longitudinally and laterally at a temperature of 95-115 deg.C and heat-treated at a temperature of at least 200 deg.C and not exceeding the melting point. At the time when a temperature rise is performed at a rate of 10 deg.C/min. up to 70 deg.C from 25 deg.C while applying tension of 3kg per section of 1mm<2> in a longitudinal direction, in a film, a biaxially oriented polyphenylene sulfide film whose elongation of a longitudinal direction is 0.4% or less is obtained. When a film is metallized, since a deformation of the film is little, unevenness is hard to occur and a phenomenon succumbing to heat at the time of metallizing is not generated. An obtained metallized film has favorably dimensional accuracy and shows favorable properties as a capacitor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyphenylene sulfide film.

[Prior Art] Previously, in Japanese Patent Application Laid-Open No. 60-255978, it has been disclosed that a biaxially oriented polyphenylene sulfide film is vacuum-deposited with aluminum or the like to form a metallized film, and that the metallized film is used for capacitors, etc. It is disclosed that it can be used for.

[Problems to be Solved by the Invention] However, when the conventional biaxially oriented polyphenylene sulfide film is subjected to metal vapor deposition using a winding vacuum vapor deposition machine, the film tends to wrinkle on the cooling can of the vapor deposition machine. The drawback was that the wrinkles were fixed by the latent heat of the evaporated metal, leaving wrinkles on the metallized film and causing poor flatness (hereinafter sometimes referred to as "heat loss"). If you try to cut this metallized film that has suffered heat loss to make tape for capacitors, etc., the dimensional accuracy will deteriorate, and for example, the width of the margin part (non-evaporated part) will fluctuate, resulting in a defective capacitor. There are negative effects such as number that causes.

An object of the present invention is to eliminate the drawbacks of conventional polyphenylene sulfide films as described above, and to provide a polyphenylene sulfide film that is less susceptible to "heat loss" when metal deposition is performed using a winding type vacuum deposition machine.

[Means for Solving the Problems] In order to achieve the above object, the present invention provides a film that is heated from 25°C to 70°C for 10 minutes while applying a tension of 3 kg per square millimeter of cross-sectional area in the longitudinal direction of the film. This is a biaxially oriented polyphenylene sulfide film which has a longitudinal elongation of 0.4% or less when heated at a rate of °C/min.

In the present invention, polyphenylene sulfide film (
Hereinafter, Pl) S film may be abbreviated as a biaxially oriented film of a resin composition containing poly-p-phenylene sulfide as a main component. The thickness of the film ranges from 0.4 to 25 μin, but from 0.4 to 1
The effect is large in the 0 μm range. Average surface of the film■
The radius Ra is preferably in the range of 0.03 to 0°10 from the viewpoint of workability on the right side and adhesion during hot pressing after winding.

Moreover, it is preferable that the crystallized film has a crystallinity of 25% to 45% as measured by X-ray diffraction. Furthermore, the degree of orientation OF determined for the crystal peak at 20=20-21°C by wide-angle X-ray diffraction is 0.07 to 0 in the End direction and Edge direction.
．． 5, T h r OIJ g '0.6 ~ 1 in h direction
．． Preferably, the film is biaxially oriented in the range of 0 to 1.
．． 7.

Here, the resin composition containing poly-p-phenylene sulfide as a main component (hereinafter sometimes abbreviated as PPS-based composition) refers to a composition containing 70 weight percent or more of poly-p-phenylene sulfide.

i-cuff containing poly-p-phenylonone sulfide 0
Less than 1.% by weight of the composition. The crystallinity, thermal transition temperature, etc. of the composition are lowered, and the characteristics of the film made of the composition, such as heat resistance, dimensional stability, and mechanical properties, are impaired. The remaining less than 30% by weight of the composition is poly p-phenylene 1. It may also contain additives such as polymers other than sulfide, inorganic or organic fillers, lubricants, colorants, and ultraviolet absorbers.

The melt viscosity of the resin composition is preferably in the range of 500 to 12,000 poise (more preferably 700 to 10,000 poise) at a temperature of 300° C. and a shear rate of 2001/sec in terms of film formability. The melt viscosity of the resin composition is equal to the melt viscosity of the finally obtained silane sulfide film.

In the present invention, in poly-p-phenylene sulfide (hereinafter sometimes abbreviated as PPS), 70 mol% or more (preferably 85 mol% or more) of repeating units are represented by the structural formula E@-8→- A polymer consisting of structural units. If the content of such components is less than 70 mol%, the crystallinity of the polymer
The heat transition temperature, etc. becomes low, and the heat resistance, dimensional stability, mechanical properties, etc., which are the characteristics of a film made of a resin composition containing PPS as a main component, are impaired.

The JP position containing a copolymerizable sulfide bond may be included as long as it is less than 30 mol%, preferably less than 1-5 mol% of the repeating positions.

Further, it is preferable to contain inorganic fine particles in the film of the present invention for the purpose of smoothing the surface.

In the present invention, the elongation in the longitudinal direction is 0.4 when the film is heated at a rate of 10°C/min from 25°C to 70°C while applying a tension of 3 kg per square millimeter of cross-sectional area in the long hair direction of the film. % or less. The relevant elongation is 0
□If it exceeds 4%, "heat loss" mentioned in -L will occur during vacuum deposition.
Therefore, the first objective of the present invention cannot be achieved. The magnitude of such elongation is preferably 0.3% or less. Also, under the same conditions, the elongation was 0 when the temperature was raised to 80℃.
It is more preferable if it is 4% or less.

As a method for manufacturing the film of the present invention, Japanese Patent Application Laid-Open No. 55
-111235 etc., the well-known method Tepoly p-
A resin composition containing Fe, 21 non-sulfide as a main component is supplied to an extruder or the like, melted, extruded from a T-die onto a cooling drum, bound with a non-oriented sheet, and the sheet is
Simultaneously or sequentially biaxially stretched longitudinally and transversely at a temperature of ~115°C, and then heat treated at a temperature of 200°C or higher and below the melting point to obtain an intermediate. 1120
Examples include, but are not limited to, a method of heat treatment at 1 second to 10 degrees Celsius. The time for the heat treatment can be appropriately selected depending on the temperature. Generally, it takes a long time at low temperature and short time at high temperature. The heat treatment can be carried out continuously with the production of the intermediate on the film production line11, or it can be carried out once after one winding. In the latter, Furuno,.

It can be carried out continuously while unrolling it, or it can be carried out in a roll form in a hot air oven. Further, the heat treatment can be performed in two or more stages at different temperatures.

Vacuum deposition of the film can be carried out using a continuous winding type deposition machine under well-known conditions.

[Methods for measuring and evaluating properties] (1) Elongation 57o (or 58o) In the present invention, from 25°C to 70°C (or 80°C) while applying a tension of 3 kg per 1 square millimeter of cross-sectional area in the longitudinal direction of the film. To measure the elongation in the longitudinal direction when the temperature is raised at a rate of 10'C/min,
．． A test piece of 100 mm and a width of 10 mm was cut out, a load equivalent to 3 kg per 1 square mm of cross-sectional area of the test piece was attached to the lower end, and the test piece was hung in a hot air oven kept at a temperature of 25°C at intervals of about 1000 mm. The interval Lo between the marked lines placed near both ends of the film was read using two optical position detectors (line sensors), and the temperature of the hot air oven was adjusted to 10℃/
At the moment when the temperature reaches 70℃ (or 80℃) at a rate of 100X (L
-Lo)/Lo (unit: %) to calculate elongation 57o (or 58o).

(2) Degree of "heat loss" during vapor deposition Aluminum was vapor-deposited onto a film sample with a width of 500 mm using a continuous winding single-sided vapor deposition machine manufactured by Nippon Shinku Giken Co., Ltd. At this time, the film tension before and after the cooling can is 3 kg/
mm2, the temperature of the refrigerant circulating inside the cooling can is -30℃, 9
The film was deposited in a stripe shape in which evaporated areas with a width of mm and non-evaporated areas with a width of 1 mm were alternately repeated.

The metallized film after vapor deposition was observed, and the degree of "heat loss" was determined based on the following criteria.

O: Ten or more wrinkles running in the vertical direction of the metallized film are observed, but other parts have good flatness.

Δ: In addition to more than a dozen wrinkles running in the longitudinal direction of the metallized film, undulations are seen throughout the film, but the wrinkles disappear while tension is applied.

×: In addition to more than ten wrinkles running in the longitudinal direction of the metallized film, undulations were observed throughout the film, and the wrinkles remained even when tension was applied.

[Effects of the Invention] By having the above structure, the film of the present invention is less susceptible to "heat loss" during vapor deposition, which was a drawback of conventional biaxially oriented polyphenylene sulfide films, and as a result, When cutting the obtained metallized film to make tape for capacitors, the dimensional accuracy is improved and the defective rate of capacitors is reduced. Further, even when the obtained metallized film is coated for the purpose of manufacturing a so-called lacquer coating type multilayer capacitor, there is also the effect that dimensional deviation from the coating pattern is less likely to occur.

[Function] It is not clear why the biaxially oriented polyphenylene sulfide film of the present invention is less susceptible to "heat loss" during vapor deposition, but if the elongation as described in the present invention is large, the film will experience a cooling can during vapor deposition. When passing over the top, the film stretches and wrinkles due to the tension applied to it, making contact with the cooling can poor.In addition, when metal vapor flies, the latent heat of condensation cannot be released to the can, and the film due to heat deformation occurs, whereas if the elongation referred to in the present invention is small, such a phenomenon is unlikely to occur.

[Example] Example 1 (1) Production of pps-no used in the present invention In an autoclave, 32.6 kg of sodium sulfide (250 mol, containing 40 wt% of water of crystallization), 100 g of sodium hydroxide, and 36° 1 kO of sodium benzoate were placed in an autoclave. (250 mol), and N
-Methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) 79°2 kO was charged and dehydrated at 205°C, then 1.4 dichlorobenzene (hereinafter abbreviated as p-DCB) 3
7°5 kg (255 moles), and NMP20. OJI was added and reacted at 265°C for 4 hours. The reaction product was washed with water and dried to obtain 21 ytkg (yield: 78%) of poly-p-phenylene sulfide containing 100 mol % of p-phenylene sulfide and having a melt viscosity of 3100 voids.

This composition contains zero fine silica powder with an average particle size of 0.7 μm.
1-wt% and 1% calcium stearate O405W were added and heated at 310°C using a 40 mm diameter extruder.
95% cut hole diameter 10 μm using metal fiber
After filtering with a filter, the length is 400 meters and the gap is 1.5 m.
The film was extruded through a 1" die having a linear lip of 25 mm, cast onto a metal drum whose surface was kept at 25 DEG C., and cooled and solidified to obtain an unstretched film with a thickness of about 25 .mu.m.

This film is stretched by a longitudinal stretching device consisting of a group of rolls.
3 at a film temperature of 100°C and a stretching speed of 30,000%/min.
．． Stretched 6 times, then using a tenter at a temperature of 100°C.
It was stretched 3.5 times at a stretching speed of 1000% 7/min, and then heat treated under tension at 270°C for 10 seconds in a subsequent heat treatment chamber in the same tenter to obtain a 2 μm thick intermediate (Intermediate-1).
) was obtained.

The intermediate was wound into a roll, and the roll was heat-treated in an oven at 60°C for 24 hours to obtain the film of the present invention (Film-1). The evaluation results of the film are shown in Table-1. From Table 1, it can be seen that the intermediate material (corresponding to the conventional polyphenylene/sulfide film) has a large heat loss j during vapor deposition, whereas the film of the present invention is less prone to heat loss U.

Example 2 The intermediate 1- obtained in Example 1 was wound up into a roll, the temperature and time of heat treatment were changed appropriately, and the film according to the present invention was subjected to heat treatment 1- in the same manner as in Example 1-. While applying a tension of 3 kg per square millimeter of cross-sectional area in the longitudinal direction of
Five types of films (Film-2 to Film-6) having different elongations in the longitudinal direction when heated from 5°C to 70°C at a rate of 1-0°C/min were obtained. The evaluation results of these films are shown in Table 1.8 From Table 1, it can be seen that when the elongation as defined in the present invention is 0.4% or less, heat loss during vapor deposition is less likely to occur.

Claims (1)

[Claims] (1) When the film is heated at a rate of 10°C/min from 25°C to 70°C while applying a tension of 3 kg per square millimeter of cross-sectional area in the longitudinal direction of the film, the elongation in the longitudinal direction is 0.4. % or less.