JPS6056531A - Oriented polyester film - Google Patents

Abstract

PURPOSE:To manufacture an oriented polyester film, in which a specific inorganic compound is compounded at a predetermined ratio, which has excellent sliding properties and abrasion resistance, in which there are few coarse grains and which is suitable for a use to a magnetic tape base film, etc. CONSTITUTION:Kaolinite and/or talc, mean grain size therof extends over 0.01- 0.5mu (A), and one kind or more of inactive particulates (B) selected from silica, titanium dioxide or barium sulfate are used. That is, said component (A) and component (B) are compounded to polyester containing a polyethylene terephthalate unit of approximately 80mol% or more so that relationship shown by formula I , formula II and formula III [(A)+(B) represent the total weight % of both components, (A)/(B) the weight ratio of both components and DA/DB the mean grain size ratio of both components] is satisfied simultaneously. A polyester composition obtained is changed into a film, and biaxially-stretched and oriented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides smooth, slippery and I? This is similar to an oriented polynisdel film which has excellent abrasion resistance and has a small number of coarse particles.

In general, polyesters such as Boligre/terephthalate are excellent products! Because of its purpose and chemical properties, it is widely used in a variety of applications, including for fibers, molded products, magnetic tape, photography, condensers, packaging, and other films. When used for these films, the slipperiness and abrasion resistance properties are determined by the film manufacturing process and the processing in each application.
This is a major factor in this. Further, the fill 1 is required to have a small number of large particles. Coarse 1ζ7
．． If the number of 4'- is large, breakage in the film forming process will increase, and the forming V,
This is undesirable because it causes a decrease in operability and a decrease in electrical characteristics. In particular, when four magnetic layers are applied to the surface of a polyester film and used as a magnetic tape, the presence of Japanese particles in the filter causes magnetic h'! Even after blowing 11, protrusions are formed on the surface of the magnetic layer, and when the magnetic nop is run, a space gap is generated between the magnetic node and the magnetic node, and the magnetic node is missing; ■Oishi because it leads to l-ronopout drawbacks! Is there a need to reduce the number of steps?

When used as a magnetic tape, it has good tear resistance and resistance! ? - Abrasion resistance is also an extremely important property. For example, slippage Vl and resistance I
I? If wear 1!1 is poor, friction between the core 1-ink + 1-ru and the surface of the fill 11 and p7- will occur when applying the magnetic layer.
The abrasion is extremely severe and therefore wrinkles and scratches on the film surface are likely to occur.

In addition, the film after applying the magnetic layer can be slit to create a tape for use in computers, videos or computers.
- Even after recording, significant friction and wear may occur between the guide parts, playback heads, etc. when pulling out reels, cassettes, etc., pulling them out, and other operations.
(; The generation of scratches and distortion, as well as the production of white powdery substances due to scratches on the poly:I-thral file surface, etc., often become a major cause of blowouts.

Furthermore, when used as a magnetic tape, it is required that the surface be smooth. Particularly in the use of cutting bits, there is increasing demand from the market for the mold-hole characteristics required for straight and double-tee cutting.

In general, to improve the slipperiness and 1111 abrasion properties of the film surface, the contact area between the film surface IVii and the guide roll etc. can be reduced by making irregularities (・ILJ), t<
A method of tightening the fill l, lGi is adopted.
For example, a method in which insoluble particles are precipitated from a catalyst residue of 1°, 1 z, 1 molecule used for this purpose, or a method in which an inert inorganic layer is added are used. These IIif #S[
I Niji + Molecule's f) Ning is its size, large culm, sliding bamboo improvement effect, large, general, magnetic tape, bamboo bidet > H River, etc., and its particles are suitable for precision applications. Being too large can cause defects such as trottle-out, so the unevenness on the film surface needs to be as fine as possible, and at the same time it has contradictory physical properties: +'+
The current situation is that certain demands are being made.

The present inventors have discovered that, especially in recent years, the density of magnetic recording has been further promoted, and the smoothness of the base film for i-zu, t;
Risei, 1llII111 bill V1 and i11 Oishi! In view of the current situation where improvements such as a reduction in the number of children are being demanded, the present invention was arrived at as a result of diligent efforts to reduce the number of children. That is, in the present invention, El-barrel t'1: 7 is: 1. 31 in polynisdel consisting of Ch1/ngref crate.
Component (8) consisting of kaolizite and/or talc with a uniform diameter of 0.01 to 0.5μ, and at least i+ selected from silica, titanium dioxide, and barium sulfur.
The inertness of it consists of the inertness f ())) component and the ten (
1) Adding equations 1) and (II) at the same time 11:
The average diameter satisfying the following formula (ll[) (I diameter ratio is 3
This is an oriented poly:1-stool film.

0.2≦ (8)-to (If)≦ 2.0...
・ ・・・・・・・・・ ・・・ ・・・・・・(I)0.
1≦(8)/(0)≦10 ・・・ ・・・ ・・
・・・ ・・・ ・・・ ・・・ (II) 0.5≦
1) 8/I) +1≦10 ・・・ ・・・ ・・・
・ ... ... (III) [In the formula, (8) + (1
1) is the (+”l) component expressed in weight% and <li
) component and ノ'+'+ r+';lj' 0) combination; ii
j, itl, (8) / (IIH; t (8) component to (II) component;, 1 ratio, 1) 8 / I) II
is the average diameter ratio of the (8) component and the (1+) component. ] Oriented polynisdelfil of the present invention!・Has excellent surface smoothness, slipperiness and 1+-- tag resistance, ll: 4
There are significantly less scratches and white powder generation, and I'11
It has the characteristic of having a low ζI value, making it particularly suitable as a base film for magnetic disks.

The characteristics of the oriented Boriesun Lusolum in the present invention are 0
．． Component (8) consisting of 01 to 0.5 μm kaolileite and/or talc, and at least one inert element selected from silica, titano dioxide, and barium sulfate.
Component (I3) consisting of D-shaped particles is mixed with silk having a constant average particle size of 11 and a specific amount of 01.

Already the slipperiness of the film surface and ll1III/abrasion t/l
In order to make the direction 1°, two types of 31゛1 inert ladle with different diameters are used. 1! It is known that the method of adding mechanical particles is self-effective. Among them, two scales with different particle shapes;
It is known that the method of making ri's little 1☆ child 01 river is particularly sloppy. These methods are definitely the best! ! or 1lIII11-Is it self-effective as a means to improve magnetism, or is it possible that the surface smoothness is severely affected by the known method since W?
'; I < , and it was difficult to add 714 children at the same time to Special Electricity Ii, which had only 811 children for the 11th person.

Due to the limited articles (11) included in the present invention,
For the first time, the contradictory film properties of 11.
You can add i;(+ to it.

In the present invention, the orientation, ``edge sprue fill l,'' is 1
M Make, 1! Liessol is the main repeating l'i
, 80 mol % or more of -r-tylene derephthalate, j! Rico 1. The other (11η components include dicarboxylic acids copolymerized with it, glycol-1-alta-1, or-1-sino-norbono acid salt 1, etc.) at 20 mol%. f J (polymerized one may also be used. In addition, the oriented filter may be a double oriented filtration filter.
or particularly suitable.

The average f☆ diameter of the fine particles to be added in the present invention is 0,
OI~0. ”: III m range is required and 0.0
5 to 0.3 μn1 or better.

0.01μ ■Not! i'? For i, slip 11 [and resistance 1
This is not preferable because the -1° effect for the 1f note Vl is insufficient. On the other hand, if it exceeds 0.5 II In, the effect of improving l; So I don't like it.

The relationship between the average diameter of the (Δ) component and the (1() component is (
1) As shown in 2, it is necessary to maintain the ratio of the average particle size of the component (Δ) to the average particle size of the component (n) from 0.5 to 0. A range of 0.8 to 2.0 is particularly preferred.

If it is less than 0.5, it is undesirable because the number of children produced increases. On the other hand, if it exceeds 10, it will have ti7 resistance or resistance 11.
The improvement in z1 wear and tear pl will be insufficient, so it is better.

The content of these fine particles is the sum of the content of component (8) and component (1).
It is necessary to select L in the range of 0.2 to 20% by weight.

0. :(The range of 1.0 tons to 111% is particularly preferable.

If it is less than 0.2% by weight, l:'t resistance and l! I4 wear 1
It is not preferable because the effect of 1° in the direction of /1 is insufficient. On the other hand, if it exceeds 11% (20 small), the
1 wear t'l direction 1 effect reaches a plateau, and the child's surface smoothness 111 worsens (7, and the number of kumite \lr'- increases, which is preferable).

Also, as shown in equation (II), (for the <(+1) component)
^) The content of the components is 0.1 to 1.
Ono1li1! I need J Tatsumi to surround it. A range of 0.3 to 5 is particularly preferred.

If it is less than 0.1, it is not preferable because the TRR tag resistance deteriorates. On the other hand, if it exceeds 1O, the slipperiness decreases, which is not preferable. In addition, from the surface of the sliding property direction −L, the gold platinum 1 of the component (B)
It is particularly preferable to select 0.1 weight 111% or more. The above formulas (1) to (III) must be satisfied at the same time.

These fine particles may be used either without surface treatment or with surface treatment.

Further, the dispersion aid and anti-aggregation agent (1) and (4) are not limited to (4).

Here, 11-31' average stone I diameter (Yo) refers to the diameter that falls at the cumulative 50% point of the equivalent spherical ablation distribution calculated based on the Stokes equation. ,1
The method for adding it to the slurry is that it can be added at any stage 144 in the 1 tericose sill filling (", -, but it should be added before the initial 1 υj reaction reaches 1'). is preferable for !ll+.

In addition, in the method of adding 7 μm of fine particles to the Poly:1-Snorl product process, it is possible to add them in either slurry or powder form, but it is important to prevent scattering of the particles, improve feeding accuracy, and improve uniformity. It is preferable to add it in the form of a slurry and disperse it from the viewpoint of its properties, and it is particularly preferable to add it as a 1.:G slurry. When dispersing into a slurry, it is necessary to achieve a uniform dispersion that reproduces as much as possible the primary ladle of each ladle.

Further, in order to obtain particles having a predetermined average particle size of 91J, it is possible to adopt a pulverization treatment or a classification operation of commercially available fine particles.

In addition, when adding rK to the "b" process made of poly J-sphere as a slurry of the particles, the slurry of component (8) and (I(
) Even if the slurry of the components is added at the same time, J, I, J
They may also be added separately.

t-I to the extent that it does not increase the number of coarse particles and does not have a negative effect on the -1' surface slipperiness. Child diameter and this number I+
i; If i, polynisful is overproduced IYte ai +
It does not matter if it contains small particles, so-called internal particles. As mentioned above, the film of the present invention is particularly suitable for use as a base film for magnetic tapes, but is not limited thereto;
4: It can also be widely applied to the field of immortality.

Next, Examples and Comparative Examples of the present invention will be shown. All parts in the examples mean parts by weight unless otherwise specified.

Furthermore, the measurement method used is shown above.

(1) Average particle size: Use the value at the cumulative 50% point of the equivalent particle size particle diameter I11 obtained using a centrifugal sedimentation type particle size analyzer J7111I manufactured by Shima II Seisakusho.

(2) Surface smoothness of fill l ~ 411 Surfcom 300A type surface roughness! Using I, ≦“1 diameter 1
μ, force u in 0.07g, measurement base Q11*
0.8m1I J171-1: Displayed as center line average roughness (RA) measured under the conditions of IO, 08+n.

(:() Fill!・Slip and abrasion resistance II
F The amount of white powder generated on the surface was evaluated on a five-point scale, and the following rank (-I) was given.

Smoothness Grade 1: Tension applied (many scratches) Grade 2: Slight tension (quite a lot of scratches) Grade 3: Medium tension ((some scratches observed) Grade 4: Slightly low tension (some scratches observed) Scratches ζJ Tondonashi) Grade 5・
・・During tension (no scratches at all) Abrasion resistance 1st grade ・White powder generation J1 Always a lot of 2nd grade ・White powder generation often occurs 0 grade ・White powder generation is slightly observed 4th grade ・White powder generation is rare None Grade 5: White powder has been generated (no/1) Number of coarse particles in the film: Place a small amount of the film between two cover glasses.
After melt pressing at 0°C and cooling, the temperature was 41X'.

-8'1 Observation using a microscope, image analysis processing 711 device Luzeno/S 500 (12 I book: T made by Leku)
The number of particles with a maximum length of 5 μm or more in the Tetri-j' image is counted, and the number of particles is evaluated on a three-level scale, and expressed as follows:

1st grade, 1.1 pieces or more, J: / 4.811nr 2nd grade...
・4 to 10 pieces/4.8m+++'3 grade...0 to 3 pieces/
4. (1++Re?Example 1゜A continuous system consisting of a two-stage complete mixing tank equipped with a stirrer, a mixing device, a feed inlet, and a product outlet.
- The first esterification reaction f using a stellation reactor
li;f-stellation reaction product (?TI)
' The molar ratio of IEG to A was adjusted to 1.7: a;
P A O) r,: G slurry was continuously supplied.

At the same time, TI'A+>G slurry supply 1-1]-1, magnesyl acetate, tetrahydrate E G
In the reaction product that passes the ICG solution of #j solution and acetic acid triuno into the reaction vessel, "τ Liesglu 111th position;
M g IG per L knit! r and N a
Continuously feed at 100 PPM and 10 pp11 as a bii powder, with an average residence time of 4.
．． The reaction was carried out for 5 hours at a temperature of 255°C.

This reaction product is continuously taken out of the system, and 0.5 parts of EG and IE G solution i1k as 1) atom
84 ppm and an average particle size of 0.34/Z m”
Linite's EG slurry and average f-base diameter is 0.30μm
The EG slurry of silica was 0.30 and 0.40Φ as Kaorilite and silica, respectively; 11,
% from a separate supply port, and the reaction was carried out at normal pressure for an average residence time of 5.0 hours and at a temperature of 260°C.

The Nisderization reaction product was subjected to stirring using a stirrer, partial condensation: (g, IG
A small synthesis is carried out by continuously feeding a two-stage continuous 1R combined reactor with a feed charge 1 and a product outlet. .The 1! remer was melt extruded at 290°C, and then heated to 0°C.
Table 1 shows the filter characteristics 1/1 of a 15 μm film obtained by stretching 3.5 times in the machine direction and 3.5 times in the transverse direction at 130° C. and then heat-treating it at 220° C.

In this major example? 1. ) is the surface smoothness,
Sliding 11I: , 111 wear resistance and the first
Any property of numbers ('I is also very good! Ir, i-;
I can tell that it's because of her hair.

Comparative Example 1 In Example 1, except for adding silica and reducing IL.
%) obtained using the same method as in Example 1, the properties are shown in Table 1.
Shita.

The filter obtained in this comparative example °C had extremely poor slipperiness. Is it resistant again?・Wear 1!1 is also inferior.

Comparative example λ Implementation 1! The fill obtained with the same force as in Example 1 except that the addition of 1 point of horn was added at +'i 1. , 1, ll characteristics are shown in Table 1.

In the soft example of this ratio, the soil (11) has poor abrasion resistance.

In Comparative Examples 3 to 1 (Example 1, Example 1), Table 1 shows the results when the amount of 1 lilyte added, the average particle size of silica, and the type of addition 111 were changed.

When the strip A of the present invention is removed, the surface) 1 and the slide ↑'l
, W') Suli, tit l! ? It can be seen that it is not possible to obtain a high quality film due to the abrasion resistance and 111 particle count A. Example 2 and Comparative Examples 7 to 9 In the same method as Example 1, Table 1 shows the results when kaolileite and titanium dioxide were used.

Only when the conditions of the present invention are satisfied, Table 11) 1・II slipperiness, t
;': All 1. '
It can be seen that a high quality film with r property added to i+1'f can be obtained.

Examples 3 and 4 The results are shown in Table 1 when using the same method as in Example 1, using barium and talc, and when using talc and silica.

It can be seen that all of the examples are made of high quality film.

Continuing from page 1 ■Int, C1,' Identification code Office serial number F 6681-4J Procedural rectification document (spontaneous) Rare 1, Indication of incident Patent application No. 167169/1983 λ Name of invention Oriented polyester film 3 , Make an amendment 41 Relationship to the case Patent applicant LS Hama 2-chome 1, Kita-ku, Osaka City 2 No. 8 S3 Specification: 4115 of the detailed description of the invention of jX, Contents of the amendment (1) Meiwa 11 Page 10, line 14, insert the following sentence after "Add separately at °C."

If they are added at the same time, they may be added from separate supply ports, or they may be added after uniformly mixing both slurries before adding them to the polyester manufacturing process. A polyester containing a high concentration of particles may be prepared separately in advance, and then blended to a predetermined particle concentration.'' ■ Page 10, lines 18 to 19, ``So-called internal particles Insert the following sentence after ".

``In addition, if the purpose of the film is such that the height of the surface comes into contact with a metal roll, only the contact surface should contain the inert inorganic particles of the present invention, and the other surface should contain the inert inorganic particles. (3) Same page 11, line 15, line 1.'' (3) Corrected r (RA)J to ``(RA).'' do.

(4) Table 1, page 17 "Surface smoothness R.A. of (/l　m)　J "Surface type To R I am corrected.

(μm) J -1 d

Claims (1)

[Scope of Claims] The main mound is composed of ethylene terephthalate, and the average particle size is 0.01 to 0.5 μm.
<A) consisting of kaolite and/or talc.
Ingredients include silica, titanium dioxide, and barium sulfate, with at least bi, r:Ii and less than iW. The (mouth) component consisting of fine particles is the following (1) and (!1).
j, 1 which simultaneously satisfies the formula and an average grain size ratio which satisfies the above formula (Ill), J! Polyester film 0.2≦(^)+(I+)≦2.0・・・・・・・・・
・・・・・・・・・・・・(I)0.1≦(8)/(
+1)≦10 ・・・・・・・・・・・・・・・・・・
(■) 0.5≦ 1) 8/1. ) 11≦10
・・・・・・・・・・・・・・・・・・ (III
) [In the formula, (^) 10 (11> is 1l-) j The sum of 3 to 11 of the component (^) indicated by 6 and (11) 411 amount, (8) / (U) is (8 ) component and (b) component small I+
1. Ratio, I) ^/ I) +1 is (8) component and (13)
It shows the average particle size ratio with the components. ]