JPS60228545A - Preparation of polymer resin film - Google Patents

Abstract

PURPOSE:To obtain, at a low cost, a polymer resin film having excellent adhesiveness, aging stability, smoothness, slipperiness, etc., suitable for use as a magnetic tape, etc., by treating a polymer resin sheet with low-temperature plasma and stretching it. CONSTITUTION:An unstretched or stretched polymer resin sheet such as polypropylene or polyethylene terephthalate sheet is treated with low-temperature plasma in an atmosphere of a gas such as an inorganic gas (e.g. argon or helium) or a vapor of an organic compound (e.g. methyl alcohol or acetylene), preferably under a pressure of 1X10<-2>-50Torr. The treated sheet is stretched at least once, and preferably is heat-treated after stretching to obtain an objective polymer resin film.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polymers used in information recording media such as porcelain tapes and silver halide photographic films, electrical components such as capacitors, graphic art supplies, and packaging materials. The present invention relates to a method for producing a resin film, particularly a method for producing a polymer resin film with improved surface characteristics.

[Prior Art] Polymer resin films are thin and strong, so they are used in a wide range of applications, including electrical and electronic component applications, information recording applications, packaging applications, and printing applications. However, polymer resin films have many problems with surface properties, particularly properties such as adhesion, smoothness, or slipperiness, and there is a strong need for improvement.

For this reason, for example, corona discharge treatment or low-temperature plasma treatment has been studied to improve adhesion.

However, the corona discharge treatment has the disadvantage that the improvement effect is insufficient and the effect generally decreases over time, and a better improvement method is currently being sought. Japanese Patent Application Publication No. 5
No. 2-135100 and JP-A No. 53-5271 disclose that corona discharge is performed before the film is stretched to form a matte film. Although it is possible to roughen the surface and make it matte by this method, the effect of improving surface properties such as adhesion, which is generally regarded, is not observed at all.

Furthermore, US Pat. No. 4.072.769 discloses a method of treating a polyethylene terephthalate film with low-temperature plasma in the presence of No gas or NO2 gas to facilitate adhesion. Low-temperature plasma treatment has a higher initial reforming effect than corona discharge treatment, but like corona discharge treatment, there are problems such as the effect decreasing orally and high treatment costs, so it has not been put into practical use. Not yet.

Furthermore, the surface of the polymer resin film is originally smooth and does not slip easily, making it extremely difficult to handle. For this reason, conventionally, inorganic particles have been added to the polymer resin to form protrusions on the surface of the polymer resin film to impart slipperiness and facilitate handling. However, in recent years, smoother surfaces have been sought for in various applications, including information application fields such as porcelain tapes. On the other hand, there has been a need for a technology to form a surface with contradictory properties such as smoothness and smoothness.Therefore, methods of adding finer inorganic particles are being considered, but When added to the water, the particles agglomerate secondary and become coarse, making it difficult to form fine protrusions. For this reason, a polymer resin film with a smooth and slippery surface as expected has not yet been produced.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve the above-mentioned defects in the surface properties of polymer resins, and to solve the problem that the improved surface properties deteriorate orally. The present invention provides a method for producing a polymer resin film having unprecedentedly excellent surface properties.

Means for Solving Problem E] The present invention is characterized in that an unstretched or stretched polymer resin sheet (hereinafter referred to as "sheet") is treated with low-temperature plasma, and then stretched at least once or more. This is a method for producing a polymer resin film (hereinafter referred to as film).

The polymer resin referred to in the present invention refers to melt extrusion method, solution casting method,
It is a polymeric resin that can be formed into a sheet by a calendering method or the like, and then made into a thin film by stretching. Such polymer resins include olefin resins such as polyethylene or polypropylene, polystyrene and its copolymer resins, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene or tetrafluoroethylene-hexafluoropropylene copolymers. Fluororesin such as resin, polyester resin such as polycarbonate, cellulose acetate resin, polyethylene terephthalate, polyamide resin such as nylon 11, polyimide resin, polysulfone resin such as polyphenylene oxide, polyphenylene sulfide, polyether sulfone, urethane resin, etc. Typical examples thereof include copolymers of these monomers, copolymers of these monomers with other monomers, and mixed resins thereof. Of course, stabilizers, lubricants, inorganic particles, dyes, pigments, ultraviolet absorbers, plasticizers, etc. may be added to these resins.

By the way, the basic properties normally required of films are mechanical properties, and they are required to be flexible and strong. For this reason, it is desirable for the polymer resin to be a crystalline polymer, but as the crystalline polymer is crystallized from an amorphous state through molding and stretching, its surface properties such as adhesiveness and slipperiness significantly deteriorate. There are drawbacks that make it worse.

However, according to the film manufacturing method of the present invention, it is possible to obtain a film that has significantly superior surface properties compared to films obtained by conventional film manufacturing methods, without impairing the basic properties required of the film. It will become. For this reason, it is more preferable that the polymer resin of the present invention is a crystalline polymer resin.

For this reason, among polymer resins, crystalline olefin resins, polyamide resins, and polyester resins, which have excellent film-forming properties and excellent toughness, transparency, and flexibility required for films, are particularly preferred. Such resins include olefin resins such as polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-1723 copolymer, and nylon-6,
Nylon-66, Nylon-610, Nylon-11,
Typical examples include crystalline aliphatic polyamide resins such as nylon-12 and nylon-6/66 copolymers, and polyester resins made of aromatic dicarboxylic acid and fullkylene glycol, such as polyethylene terephthalate. can be mentioned.

In particular, the film produced by the method of the present invention using a polyester resin containing aromatic dicarboxylic acid as the main acid component and Al4:lene glycol as the main glycol component has good adhesion and shows no slight deterioration. It is the most preferred resin for the present invention because it does not allow the formation of a film with an extremely excellent surface and is easy to slip.

Specific examples of such polyester resins include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarbonhenyl ketone dicarboxylic acid, anthracene dicarboxylic acid, α. β-bis(2-chlorophenoxy)ethane-4,4
′-Dicarboxylic acid and other aromatic dicarboxylic acids as the acid component, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol,
Examples include polyester resins containing alkylene glycols such as hexamethylene glycol and hexylene glycol as a glycol component. Among these, polyethylene terephthalate resin consisting of terephthalic acid and ethylene glycol is particularly desirable.

In the present invention, the sheet refers to an unstretched sheet formed from a polymer resin by melt extrusion, solution casting, or calendaring, or a wide, long, and thick sheet that has been further stretched. say something In addition, the term "film" refers to a thin molded product obtained by subjecting the sheet to low-temperature plasma treatment, stretching at least once, and, in some cases, heat treatment for heat setting. For this reason, films are wider and longer than sheets, and are thinner and thinner. In addition, crystalline polymer resins generally undergo oriented crystallization and have a high degree of crystallinity, and when formed into a film, they have stronger mechanical properties.

Low-temperature plasma treatment is a process in which a sheet is exposed to a so-called glow discharge, a discharge that starts and continues by applying a high voltage to a gas atmosphere under low pressure, and generates electrons, ions, excited atoms, excited molecules, and radicals during the glow discharge. , which treats the sheet with active particles such as ultraviolet light.

The gas pressure in the present invention is preferably IX10'Torr to 50Torr, and the gas pressure is IXlo
If it is less than -2 Torr, the sheet surface may be colored and the surface layer may deteriorate due to stretching, and the adhesive performance tends to decrease. Moreover, when the pressure exceeds 50 Torr, the processing effect is not so noticeable. Especially 5X10-'To
When the gas pressure is higher than rr and 5 TOrr, the processing effect is significant and this is a more preferable gas pressure range.

The frequency of the high voltage applied to discharge, start, and sustain the discharge is not specified, and may be direct current or low frequency. high frequency,
Microwave etc. can be used, but especially 50 Kl-
Films produced by treatment using high frequencies of 1 z to 500 KHz have a significant improvement effect on surface properties, which is a more preferable frequency.

There are no particular limitations on the low-temperature plasma processing equipment, especially the electrode shape, electrode arrangement, etc., but since it processes wide and long items like sheets and made of polymer resin, Showa 52-1 47593
More preferred are devices with asymmetric electrodes, such as those disclosed in US Pat.

In addition, from an industrial production standpoint, sheets are continuously introduced from the atmosphere into a low-pressure low-temperature plasma processing equipment, subjected to low-temperature plasma treatment, and then brought out into the atmosphere. It is more desirable to manufacture a film by continuously molding the resin, performing low-temperature plasma treatment, and stretching.

In order to obtain better electrode conversion characteristics, porcelain tape strictly requires surface smoothness, but as the film surface becomes smoother, slippage becomes worse.

However, surprisingly, when polyethylene terephthalate is formed into a film using the method of the present invention, extremely good slipperiness can be obtained even without the addition of inorganic fine particles. However, if the film is not manufactured continuously as described above, that is, if the sheet is not manufactured continuously, -r! If the sheet is rolled up and subjected to low-temperature plasma, or if the sheet is wound up once after low-temperature plasma and stretched, the sheet will not slip, and the sheets will rub against each other, damaging the sheet surface and losing its surface smoothness. For this reason, in order to obtain a film having smooth and smooth surface characteristics, it is most desirable to manufacture the film continuously, as described above.

The gas used in the low-temperature plasma treatment in the present invention may be an inorganic gas, an organic compound vapor, or a mixture thereof depending on the required performance of the film. When an inorganic gas is used, a treatment generally called plasma surface treatment is performed to chemically or physically modify the surface of the sheet. Further, when organic compound vapor or a mixture of the vapor and an inorganic gas is used, a treatment generally called plasma polymerization is performed, and a polymer made of the organic compound is formed on the sheet surface.

When treated with an inorganic gas, the surface of the film generally has improved adhesion, and depending on the type of gas and treatment conditions, slipperiness may develop.

The inorganic gas used in the present invention is not limited to a specific gas, for example, N2. He, Ne.

Ar, Kr, Xe, N2.02.03. air.

N20. N20. NO, N2O4, N2O3゜Go, C
O2, NH3, SO2, CI 2. Examples include Freon gas such as CF4, or a mixed gas thereof, and may be selected as appropriate depending on the required performance of the film. Among them, He, Ar, and GO.

CO2, N20. Air or a mixed gas containing these is a more preferable gas because it can stably exhibit various surface properties.

In addition, if a gas containing a large amount of 02.03 or these is used, the adhesion may decrease due to the heat treatment when forming the sheet into a film, or the effect of improving some surface properties may be reduced, such as the lack of slipperiness. If such characteristics are desired, it is desirable that the mixing rate of 02 or 03 in the gas is 50 mol% or less, more preferably 30 mol% or less.

When an organic compound vapor or a mixture of the vapor and an inorganic gas is used, a film having easy slipping properties can be obtained.

The organic compound vapor used in the present invention is not particularly limited, as long as it has an appropriate vapor pressure at the operating ambient temperature and can express the surface properties required by the film, such as methyl alcohol. , ethyl alcohol, xylene.

General organic solvents such as toluene, ethylene, acetylene,
Vinyl chloride, styrene, allyl alcohol.

Unsaturated monomers such as acrylic acid (methacrylic acid) and acrylic esters (methacrylic esters), vinylsilane, trimethylmethoxysilane, trimethylchlorosilane, hexamethylsilazane, γ-(2-aminoethyl)
Examples include silane compounds such as aminopropyltrimethoxysilane, fluorine compounds such as tetrafluoroethylene, hexafluoropropylene, and monochlorotrifluoroethylene, but the organic compounds used in the present invention are not limited to these. do not have.

The gas used in the low-temperature plasma treatment of the present invention may be appropriately selected depending on the surface properties required for the film.
When organic compound vapor or a mixed gas of organic compound vapor and inorganic gas is used, the surface often becomes opaque due to stretching after low-temperature plasma treatment, or the adhesiveness deteriorates, which is generally required for the film surface. It is more preferable to use an inorganic gas in order to develop surface properties.

Next, the method for producing the polymer resin film of the present invention will be explained in detail.

First, the desired polymer resin is molded into a sheet using a method appropriate for the resin. For example, polyethylene terephthalate is melt-extruded at 270°C to 300°C and cast on a cooling drum at 80°C or lower to form a non-stretched sheet.

Next, the sheet is subjected to low-temperature plasma treatment either as it is or after being further stretched. The stretching method before the plasma treatment is not particularly limited, and any stretching method may be used as long as it can best impart the required surface properties to the film.

Whether to subject the formed sheet to low-temperature plasma treatment as it is or to subject it to low-temperature plasma treatment after stretching can be selected based on the performance required of the film and the manufacturing process. It is more preferable to do so. Furthermore, according to our experiments, it is more preferable to perform low-temperature plasma treatment on crystalline polymer resins when the degree of crystallinity is low because the surface modification effect is significant. For example, polyethylene terephthalate resin has a crystallinity of 50
% or less, more preferably 45% or less, is desirably subjected to low-temperature plasma treatment.

The surface of the sheet to be subjected to the low-temperature plasma treatment is not particularly limited, and may be appropriately selected depending on the intended use of the film. Further, both sides of the sheet may be treated, or furthermore, only the edges of the sheet may be left untreated.

The sheet treated with low-temperature plasma in this manner is then stretched at least once to form a film. The stretching method and conditions are not particularly limited, and any stretching method suitable for the sheet may be used. For example, in the case of polyethylene terephthalate resin, the sequential biaxial stretching method involves first stretching 2 to 4 times in the machine direction at 75°C to 110°C, and then stretching 3 to 6 times in the transverse direction at 90°C to 125°C. A polyethylene terephthalate film with excellent mechanical strength is obtained. Furthermore, a film with even better mechanical strength can be made by stretching 1.2 to 2.0 times in the longitudinal direction and 1.1 to 1.5 times in the transverse direction at 120°C to 165°C after two-wheel stretching. . Note that if the film has been stretched in the vertical direction before the low-temperature plasma treatment, it may be stretched only in the horizontal direction.

Further, in the case of the simultaneous two-wheel stretching method, the stretching may be carried out at 75° C. to 110° C., with a magnification of 1.5 to 4.0 times in each axis and an area magnification of 6 to 25 times.

Generally, heat treatment of a polymer resin film after stretching improves the thermal stability of various properties of the film. Also in the manufacturing method of the present invention, it is a more preferable method to perform heat treatment. The heat treatment method and conditions are not particularly limited, and any method suitable for the film may be used. For example, a polyethylene terephthalate film can be heat-treated at 180°C to 235°C to obtain an excellent film with low heat shrinkage.

[Operations and Effects of the Invention] The film produced by the production method of the present invention has significantly improved adhesion, and can also be given slipperiness depending on the low-temperature plasma treatment conditions.

Conventionally, methods of improving adhesion by subjecting films to corona discharge treatment or low-temperature plasma treatment have been known, but each method has the drawback that the effectiveness decreases over time. On the other hand, a film made by subjecting the sheet to low-temperature plasma treatment and then stretching it as in the present invention has the advantage of significantly improved adhesion and little change over time. Normally, films that have been subjected to corona discharge treatment or low-temperature plasma treatment at the film stage lose their modifying effect at once when exposed to temperatures higher than 8 temperatures for glass rolling, but the film made by the method of the present invention has no glass properties during the heat treatment process. It can be said that it is an extremely surprising phenomenon that the adhesion improvement effect can be achieved even after being subjected to heat treatment at a temperature much higher than the transition temperature.

Another major feature of the manufacturing method of the present invention is that
Smoothness can be imparted to the film by selecting the conditions for low-temperature plasma treatment. According to the manufacturing method of the present invention,
Excellent slipperiness can be imparted to the polymer resin without adding particles that would create surface irregularities, resulting in a smooth surface.
In addition, a film with pickling properties can be produced. According to experiments conducted by the present inventors, even when the film is subjected to low-temperature plasma treatment at the film stage, the slipperiness is improved, although the reason is unknown. However, this level is significantly worse when particles are added to the polymer resin. On the other hand, in the film of the present invention, even if particles are not added to the polymer resin, slipperiness equivalent to or higher than that obtained when particles are added is exhibited.

By the way, various additives are generally mixed into polymer resins for the purpose of improving the film's performance such as weather resistance, gas barrier properties, and water vapor permeation prevention properties, but in many cases, these additives do not affect the surface of the film. Bleed-out causes various problems, and in some cases, these additives cannot be used.

On the other hand, according to the film manufacturing method of the present invention, the bleed-out of these additives to the film surface is extremely reduced. Further, elution and precipitation of the low molecular weight substance (A ligoma) in the film can be suppressed. These points are also one of the advantages of the present invention.

Furthermore, from a commercial production standpoint, in the manufacturing method of the present invention, the sheet, which is narrow in width and has a slow film transfer rate, is subjected to low-temperature plasma treatment, and the treatment area is expanded by subsequent stretching. Compared to low-temperature plasma treatment at the film stage, the cost of low-temperature plasma treatment per unit surface area is reduced by the amount of area enlargement due to stretching, which has the advantage of reducing production costs.

[Property Measuring Method/Evaluation Standard M] The measuring method and evaluation criteria for the surface characteristics of the film produced by the production method of the present invention are as follows.

(1) Adhesiveness (1)-A Aluminum evaporation power Bell jar type high vacuum evaporation equipment (EB manufactured by Japan Vacuum Technology Co., Ltd.)
Aα was evaporated to a thickness of approximately 100r+m using a vacuum of approximately 1 x 110-51 RIllH using a vacuum cleaner (H = 6 type), and a commercially available cellophane adhesive tape manufactured by Nichiban Co., Ltd. was pasted on the Aα deposition surface and peeled off at 90°. Evaluation was made based on the remaining α adhesion area.

The evaluation criteria are as follows.

A1 remaining adhesion area (%) Vapor deposition index 100% 5 90% or more 100% not W44 75% or more but less than 90% 3 50% or more but less than 75% 2 Less than 50% 1 If the index is 3 or more, it is sufficient for practical adhesive strength.

(1)-B Adhesive force of @-type coating film A commercially available cellophane adhesive tape manufactured by Nichiban Co., Ltd. was pasted on the coated side of the sample coated with the following magnetic paint, and the magnetic coating was applied at a 90° angle.
Evaluation was made based on the remaining adhesion area of the magnetic coating after peeling. The evaluation was based on the same 5-level index as the aluminum vapor deposition power above.

[It-based paint] Ferromagnetic alloy powder (Fe-GO) 300 parts by weight Zinc powder (average particle size 2μ) 25 Cellulose acetate butyrate 30 Polyisocyanate compound 18
0 (Dismodur L-75) Epoxy resin 25II Silicone oil 4 Lecithin 5 Toluene (solvent) 200 Methyl ethyl ketone (solvent) 200 Ethyl acetate (
Solvent) 100 〃 (1)-C Printing Ink Adhesive Strength Add cellophane printing ink ['CG-S T' white, manufactured by Toyo Ink Co., Ltd.] to the film using a metering bar, in a solid content of approximately 3 to 9. /T112, dried with hot air at 60° C. for 1 minute, and subjected to a cellophane adhesive tape peel test in the same manner as the aluminum vapor deposition test above, and evaluated using a 5-level index.

(2) Change in adhesiveness over time After the film was left in an atmosphere at 50° C. and 83% RH for three months, the adhesiveness test described above was conducted.

(3) Slip property The coefficient of static friction (μS) was measured using a slip tester in accordance with ASTM-D-18948-63.

(4) Surface roughness Ra (μm): Indicates the value measured by a stylus type surface roughness meter (cutoff 0.
25mm, measured value 4IllIll teno value. Tatashi, J.I.
s-B-0601).

[Example] Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 Dimethyl terephthalate and ethyl glycol were transesterified and polycondensed by a conventional method, and a polyethylene terephthalate resin containing part of the catalyst precipitated in the course of the reaction as fine particles (internal particles 10.3% by weight) was made into 28% polyethylene terephthalate resin.
The sheet was melt-extruded at 5°C, cast on a cooling drum at 60°C to obtain a non-stretched sheet, and then treated with Ar gas low-temperature plasma.

The process involves feeding a rod-shaped electrode and sheet to which a high voltage is applied.
Using an internal electrode type low-temperature plasma device with an electrode pair serving as a ground electrode, the Ar gas pressure was set at 0.4 Torr.
, high frequency power supply frequency 110K) Il, - next side output voltage 5
One side of the sheet was treated under the conditions of KV and sheet speed of 15 m/10.

Next, the treated sheet was subjected to a conventional sequential two-wheel stretching method.
First, a temperature of 90°C was applied between a pair of rolls with a difference in circumferential speed.
After stretching 3.3 times in the vertical (longitudinal) direction with The film was heat-treated at 218° C. for 5 seconds while being relaxed to obtain a biaxially oriented polyethylene terephthalate film having a thickness of 15 μm.

The adhesiveness of this film and its change over time were evaluated, and the results are shown in Table 1. These results show that the film obtained according to the present invention has excellent adhesive properties (Aff vapor deposition strength, magnetic paint adhesive strength, printing ink adhesive strength) and stability over time.

Examples 2 to 7 In Example 1, N2. C
O2, Co, N20. The sheet was subjected to low-temperature plasma treatment using NHs and air to obtain a biaxially oriented polyethylene terephthalate film. The film manufacturing conditions were all the same except for changing the type of gas.

Table 1 shows the evaluation results of the adhesion properties of these films and their changes over time. As shown in Table 1, all the films obtained according to the present invention had excellent adhesive properties and stability over time.

Comparative Examples 1 to 7 In Example 1, a polyethylene terephthalate film having a thickness of 15 μm was formed using a conventional method without performing low-temperature plasma treatment at the sheet stage.

Next, the film was exposed to various gases (
Ar, N2. CO2, Co, N20゜Nlls
, air) was used for low-temperature plasma treatment.

The difference between Examples (to 1 and 7) and Comparative Examples (1 to 7) is that in the Examples, the sheet was subjected to low-temperature plasma treatment, whereas in Comparative Examples 1 to 7, the film was subjected to low-temperature plasma treatment. The conditions for each step are all the same.

Table 1 shows the evaluation results of the adhesion of the film thus obtained and its change over time. As shown in Table 1, although these films have excellent initial adhesion, their performance deteriorates significantly over time.

Comparative Example 8 A sheet formed in the same manner as in Example 1 was heated to 50W・II/
Corona discharge with energy of T112, then Example 1
A biaxially stretched polyester film having a thickness of 15 μm was obtained by the sequential two-wheel stretching method in the same manner as above.

Table 1 shows the evaluation results of the adhesiveness of this film. As is clear from the results, the method of this comparative example did not show any improvement in adhesive strength.

Comparative Example 9 A film with a thickness of 15μ was formed using the conventional method in the same manner as Comparative Example 1.
m polyethylene terephthalate film at 50W-1
Corona discharge treatment was performed with an energy of 11/m'.

Table 1 shows the evaluation results of the adhesiveness of the treated film. As is clear from these results, although a slight improvement in adhesive strength was observed, it was still insufficient, and the effect completely disappeared after a few days.

Table 1 Example 8 Dimethyl terephthalate and ethylene glycol were transesterified and polycondensed by a conventional method to produce a polyethylene terephthalate resin containing neither internal particles nor external particles.

The resin was melt-extruded at 285°C and cast onto a cooling drum at 60°C to form a non-stretched sheet, and one side of the sheet was treated with low-temperature Ar gas plasma. The same equipment as in the example was used except for the gas pressure and the primary output voltage, and low-temperature plasma treatment was carried out under the same conditions. In this example, the gas pressure is 0. Low-temperature plasma treatment was performed at ITorr and a negative side output voltage of 7 KV.

The low-temperature plasma-treated sheet was then sequentially stretched on two wheels in the same manner as in Example 1 to obtain a two-wheel stretched polyester film of 15 μm. The film was manufactured through all steps including low-temperature plasma treatment continuously. .

The film thus obtained had very good winding properties. The slipperiness and surface roughness of this film were measured and the results are shown in Table 2.

As shown in Table 2, this film has a smooth surface and excellent slipperiness.

Examples 9 to 14 In Example 8, various gases (GO, A
r-CO2 mixed gas, Ar-Go mixed gas, Ar-N
2 mixed gas, Ar-N,? Low-temperature plasma treatment was performed using O mixed gas, Ar-air mixed gas). Table 2 shows the measurement results of the slipperiness and surface roughness of these films.

As shown in Table 2, this film has a smooth surface and excellent slipperiness.

Comparative Example 10 In Example 8, a polyethylene terephthalate film having a thickness of 15 μm was formed using the conventional method without performing the low-temperature plasma treatment at the sheet stage. Since this film had poor slipperiness and could not be rolled up, a small amount of sample was collected and treated in the low temperature plasma processing apparatus used in Example 8 under the same conditions.

As shown in the measurement results in Table 2, the film obtained in this comparative example had improved slip properties, but it was insufficient compared to the film obtained in the present invention, and there were problems in slip properties from a practical point of view. be.

Example 15 Low-temperature plasma treatment was carried out using trimethylchlorosilane ((CH3)3si CQ) and Ar(7)1 gas instead of Ar gas in an actual IM@8. The conditions for low-temperature plasma are gas composition ratio Ar: (trimethylchlorosilane)=
70 mol% = 30 mol%, gas pressure 0, 15 To'
The test was carried out under the same conditions as in Example 8 except that the negative side output voltage was 3 KV.

The film thus obtained was slightly devitrified, but the second
As shown in the table, good pickling properties were exhibited.

The adhesion between the low-temperature plasma-treated side of the film and the magnetic paint was not good, but the porcelain tape with the low-temperature plasma-treated side of the film as the back side and the magnetic paint applied to the back of the low-temperature plasma-treated side was good. It showed excellent sliding and electromagnetic conversion characteristics.

Table 2 Example 16 The polyethylene terephthalate resin used in Example 8 was
A sheet that was melt-extruded at 85°C, cast on a cooling drum at 60°C to form a non-stretched sheet, and then stretched 3.3 times in the longitudinal direction at 90°C between a pair of rolls with a peripheral speed difference. One side of the sample was treated with low-temperature plasma using the same method and conditions as in Example 8. Next, the treated sheet was sent into a tenter, held at both ends with clips, stretched 3.5 times in the horizontal (width) direction at 95°C, and then heat-treated at 218°C while being relaxed by 5% in the width direction in the same tenter. and thickness 1
A 5 μm polyethylene terephthalate biaxially oriented film was obtained.

The surface roughness and slipperiness of this film were measured, and the surface was found to be smooth with Ra of 0.01 μm and us of 0.73, and excellent slipperiness.

Patent Applicant Toshi Co., Ltd. Director General of the Patent Office Manabu Shiga 1. Indication of the Case 1980 Patent Application No. 67473 2. Title of Invention Method for Manufacturing Polymer Resin Film] 4. Order for Amendment Date of Motto 7, Contents of amendment (1) Specification page 1, line 11, page 3, line 10, page 10, line 1
"Porcelain tape" in line 3 and line 17 on page 30 are respectively corrected to "11 ki tape."

(2) "Naka" on page 6, line 8 of the same book is corrected to "chu".

(3) “10-2” on page 9, lines 6, 7 and 12 of the same book.
” are each corrected to r 10-3 J.

(4) In page 9, line 9 of the same book, ``there is a risk of deterioration'' is corrected to ``1 deterioration''.

(5) “5 TOrr” on page 9, line 12 of the same book is 15
At Xl 0-I Torr,” the correction was made.

<6) "Discharge and" on page 9, line 14 of the same book is corrected to "discharge".

(7) rll on page 10, line 9 of the same book! I am corrected by saying, ``In addition to ``processing''.

(8) rAr, Co, J on page 12, line 9 of the same book
, N2, Co, and J.

(9) In the same book, page 12, line 19, "30 mol% or less" should be amended to "30 mol% or less, as low as possible."

(10) ``Surface properties generally required for film surfaces'' on page 14, lines 6-7 of the same document is corrected to [general surface properties required for film surfaces].

(11) ``45% or less'' of the same - 15th member 12th bank [4
Correct with j as low as possible, below 5%.

(12) “50W-Ill/Tl12” on page 25, lines 19-20 and page 26, line 9 of the same book, respectively [50W・m
Correct it to in/712J.

(13) Correct rAfLJ of Example 1 in Table 1, page 27 of the same book, to rAr J.

(14) Change “Example” on page 28, line 10 of the same publication to “Example 1”
” he corrected.

(15) Add the following sentence between lines 3 and 4 on page 30 of the same book.

[Comparative Example 11 After making the polyethylene terephthalate resin used in Example 8 into a non-stretched sheet under the same conditions as Example 8, the discharge output was 5
KW・sin/m'', followed by two-wheel stretching and heat treatment under the same conditions as in Example 8 to obtain a two-wheel stretched polyester film.The winding properties of this film were very poor;
It was not possible to wind up a long film into an O-roll shape.

Although the surface roughness of the film was very smooth with Ra: 0.001 μ-, the slipperiness was so large that μS measurement was impossible, and no improvement in slipperiness was observed. ” Procedural amendment Manabu Shiga, Commissioner of the Patent Office1, Indication of the case, 1982 Patent Application No. 674732, Name of the invention, Process for manufacturing polymeric resin film Representative Director and President Masatoshi Ito4, Date of amendment order Voluntary action 5. Number of inventions increased by amendment None 6. Column (1) of [Detailed Description of the Invention J] of the specification to be amended, page 116, line 10 of the specification "1°1 to 1.
The 5x stretch J is corrected as follows.

[Stretch 1.1 to 1.5 times in the transverse direction, or stretch 1.05 to 2.0 times in each axis at a temperature of 120°C to 165°C, and have an area magnification of 1.5 to 4.0 times. Like "simultaneous two-wheel stretching"

Claims (1)

[Claims] (1) A method for producing a polymer resin film, which comprises treating an unstretched or stretched polymer resin sheet with low-temperature plasma, and then stretching the sheet at least once.