JPS59210968A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide a linear polyester compsn. capable of forming a film having excellent evenness, slipperiness and electrical characteristics, by blending a specified fluoropolymer and a higher aliph. monocarboxylate salt. CONSTITUTION:0.01-10pts.wt. fluoropolymer having a m.p. of 120-255 deg.C, such as polyvinylidene fluoride or a trifluoroethylene/ethylene copolymer, and 0.005- 2pts.wt. C18-C33 higher aliph. monocarboxylate (partial) salt compd., such as magnesium stearate or sodium montanate, are blended with 100pts.wt. polyester mainly composed of ethylene terephthalate repeating units.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved polynisder compositions.
i Engineering L < is a flat layer 1 containing a specified fluorine-containing polymer and a higher aliphatic monocarboxylic acid component] 1, smooth +! ,1
and a wire υ (concerning a polyester composition) that can be used to make a film with excellent electrical properties.

[Prior art and its problems] In recent years, polyethylene terephthalate films have been widely used in the fields of magnetic tapes, photographs, condensers, packaging, and microfilms.

17 However, if the surface of a polyester composition is not slippery, adhesion between films will occur, which will not only reduce work efficiency during film formation or post-pressing, but also cause problems in the rolled shape. This can lead to problems such as a significant drop in product value due to poor customer loyalty.

On the other hand, when used as a magnetic recording medium such as a magnetic tape, one of the most important properties is that it has excellent so-called flatness, with little surface irregularity, and excellent lubricity.

Improved lubricity and electrical properties are important for use in plastics and condensers.

Many one-on-one technologies have been proposed and implemented to improve these problems, but they can be roughly divided into: (1) -Titanium dioxide, talc, kaolinite, nonol/umium carbonate, silicon oxide A polyester synthesis reaction system such as (a method of adding inert fine particles. (referred to as inert particle addition method) (2) Part or all of the catalyst, colored anti-mountain agent, etc. used during polyester synthesis. A method in which particles are precipitated during the reaction process and exist as fine particles.

(This is called internal particle generation method) There is.

However, the method of adding inert particles has the following drawbacks when trying to obtain sufficient wettability and Y compatibility.

i.e. - titanium oxide and dry/lica J:UVC
In the case of fine particles, if Jl is not added to a large amount of tIf, the lubricity or fjJ will be reduced, and if a large amount of Jl is added, transparency + li will be damaged/stiff, and the secondary agglomeration of the neck particles will cause Japanese dog protrusions. This occurs and flatness cannot be obtained.

11c, t In the case of talc, kaolin, etc., since these are particles obtained by crushing and classifying natural minerals, adding 1k, which is necessary to obtain lubricity, increases the proportion of coarse particles mixed in, the roughness of the average particle size, and It is difficult to obtain good flatness due to aggregation or the like.

First, in the internal particle generation method, Ml of the inert particle addition method
The t point is improved to some extent. Examples of using Cal/Ram and/or lithium as an internal calf composition are already known, and the resulting particles have a relatively small diameter and have sufficient affinity for the crushed polyester.

However, in the case of the internal particles generated here, there are still many large particles mixed together, probably due to the strong cohesive force between the particles, and these Japanese particles cause the flatness of the film. This not only worsens the quality of the film, but also causes filter defects and film tearing even after a short period of melt molding.

Japanese Patent Publication No. 1983-5144 states that when 1 liter of phosphorus compound is used, the allenone earth metal salt particles of terephthalic acid are actually reduced. This is due to the fact that the internal particles produced become finer due to the addition of phosphorus compounds. For this reason, the obtained film was produced by Transparent Film, Ping Jl! , 1. l'-1:
It is 1 love at f'ζ, but the sliding property is insufficient and the winding is 44. j (I put it in til and made it into a block, and there was one polish.

In this way, the internal particle generation method (r, [generated particles bj, λ
The disadvantage is that it is difficult to know if the '3'lr offspring are variable and slippery conotrols.

[Purpose of the invention]

The object of the present invention is to create a linear polyester composition capable of producing a film that has properties that cannot be achieved using these conventional techniques and also has properties such as earth properties, Y-compatibility, and electrical properties.

[Structure of the invention]

[1] The object of the present invention is the main repetition [~"1'
Polynisdel 1, one can consisting of ethyleneterephthalate
00+l! jii, 'f'il, (Δ) fluorine-containing polymer 00 having a melting point of 120°C to 255°C
1 to 10 parts by weight, 4, - (B) Metal salt of a compound consisting of a higher aliphatic monocarboxylic acid component having 18 to 33 carbon atoms as a main component Compound size or partial metal j High compound at least - (I wo 000
This can be achieved by using a polyester composition containing 5 to 2 parts by weight.

The ease of the polyester composition according to the present invention is 1 sub point 25
Identification of fluorine-containing nail coalescing and specific higher fatty acid compounds having a temperature of 5°C or less: By impregnating them, polyester molded products and polyester films, which could not be obtained with sheep-only ingredients, were produced. The main points are to improve the smoothness, smoothness, and linear addition of 2t+.

Next, the present invention will be explained in detail. The polynisdel used in the present invention is mainly composed of polyethylene terephthalate that can be molded into fibers, films, and other molded products, and the polynisdel used in the present invention is mainly composed of polyethylene terephthalate that can be molded into fibers, films, and other molded products. It is produced by a reluctant method. Of course, these polyesters may be polyesters or copolyesters, and examples of the copolyester include, for example, Jetile/Dary-I Ruafropylene gelicol, I, Opentyl glycol, Polyalkylenoglycol, ρ Ki/
Relenoglycol, 1,4-'y clo\-\゛7.
/methanol, diol components such as 5-sulfurol, 11-sulfolone, adipic acid.

Dicarbonoic acid components such as sepa/noic acid, fucuric acid, inophthalic acid, 2,6-twophthalinodicarboxylic acid, and 5-stria inophthalic acid, polyfunctional dicarbonoic acid components such as trinolinodoic acid and hyromelinotic acid, p-= Examples include carboxylic acid components such as carboxylic acid, carboxylic acid, and benzoic acid.

If the dicarphono acid component is a dicarboxylic acid, use
-Le,! : After the esterification reaction, or in the case of /carboxylic acid ester, after the transesterification reaction with glycol,
The obtained prepolymer was heated by Naomasa, vacuum 1, V trowel 1r1. Condensed polyester. It is also possible to carry out polycondensation using Ushitanrevolima itself as a starting material.

As the fluorine-based polymer, polyvinyritenofluoride,
Vinylidene fluoride/tetrafluoride, :l TJ ethylene copolymer, 47-fluorinated ethylene/ethylene copolymer, 4-fluorinated ethylene/6-fluorinated propylene copolymer, 7.3-fluorinated ethylene/ethylene copolymer, etc. #i
! i! The points are 120'C-255'C.

1 eclipse point is 255'C, and when it grows, the surface of the molded product will disappear in the next life because the minute 11 female human being in polyester will become inferior.

Moreover, when the temperature is lower than 120°C, the slipperiness is insufficient.

10 parts by weight of the polyester of the present invention (the content of the fluorine-containing polymer is 0.01 to 10 tlj, i1
1 part, preferably 0.5 to 5 parts by weight.

Fluorine-containing polymer has 001 heavy use parts and 411! In the case of +, the molded product will not be easily slippery, and if it exceeds 10 tons or 13, the mechanical thermal properties of polyester will become low I, and aluminum metal etc. In the case of l-deposition, the vapor deposition strength decreases and the secondary processability becomes poor.

The higher fatty acid compound contained in the polyester of the present invention is a metal base compound of a compound consisting of a higher aliphatic monocarboxylic acid having 18 to 6 carbon atoms as a main component, a partially metallic compound, and a FL body side. 2% of stearic acid, nonatecano acid, araginic acid, carnaubic acid, lignoceric acid, cerotinoic acid, heptanoic acid, petroselic acid, oleic acid, erucic acid, linoleic acid and acid mixtures containing these were obtained, and 2% of gold salt was obtained.・As A seconds (d alkali and 7 dimensions are alkaline earth metals, 1 row is lithium, sodium, potassium, barium 1. mada non/um,
Carnoum and stronotium are extracted a%, and a particularly delicate compound is snow〕'phosphoric acid''! Gufu/Umu, Nananotan 1 immersion Cal/tsul\, Sodium heptinate,
Monotanoic acid Cal/Uno 3. Examples include zitorium erucate.

In addition, a fatty acid with a periphery is partially Nisdell-ized with a divalent alcohol containing 2 to 4 carbons in the alkylene group, and then an oxide of a metal with two or more hydroxides or a hydroxyl is added with a divalent alcohol. #4'I can also be used properly by doing 11.

The effects of these commercial grade fatty acid metal salt compounds are enhanced by the presence of the specific fluorine-containing polymer of the present invention! The surface of molded products such as films and fibers that are shaped like I-columns has excellent lubricity despite the fact that VC is flat.

However, if the number of carbon atoms in the fatty acid compound is less than 18, or if the amount added exceeds 2 parts by weight (unfortunately, bleed-out to the surface of the molded product is severe). 1) If the amount added is less than 0.005 parts by weight, the property will not be affected.

A particularly suitable addition amount range is 0.01 to 10 parts by weight (j; parts,
More preferably, it is 005 to 0.5-i; f i □j part.

The fluorine-containing polymer and the higher fatty acid metal 171a compound may be added to the polynisdel before the polyester polymerization reaction, during the polymerization reaction, after the polymerization reaction is completed, or may be added during melt extrusion molding. .

As a method for obtaining the composition of the present invention, the composition of the present invention may include:) a nitrogen-based compound and a higher fatty acid metal 1:W7. τ for each compound separately
polyethylene prephthalate (6) prepared separately and kneaded with two kneads, or by diluting polyethylene prephthalate containing a large amount of fluorine-based intermediates and (7) or higher fatty acid metal (J) crystal compounds. The method is also preferably adopted. .

1. The polyester composition of the present invention (-1) Within the scope of the scope of the present invention, some or all of the catalysts, coloring and anti-coloring, etc. used in the synthesis of poly'-Sual may be used in the course of the reaction. Precipitated by +1 particles, i.e. internal particles and/or silicon chloride, calcium carbonate/
Barium silicate, aluminum silicate + 4m Barium phosphate, Cal/Um phosphate, Talc, Titanium dioxide, Cal/Um terephthalate.

Inert particles such as calcium silicate can be used in combination.

You can also use 01 rivers such as size, face, 1, dye, static electricity 1υ) heavy punishment, coordinating agent, etc.

[Effects of the Invention] The composition of the present invention may be formed into a film by any of a non-4x stretched film, a -axially stretched film, and a 2111bIL stretched film. In particular, a 2111111 stretched film exhibits a remarkable effect. .

The production of the 2dQb stretched film can be carried out, for example, by melt-extruding the composition to obtain a notebook autumn product at 70°C to 140°C in the longitudinal direction.
The film is biaxially stretched by 2.5 (54 to 5.5 i7ζ stretching) and then 3 to 4.51 l in the width direction.

The advantage of the polyester composition of the present invention is that it contains a specific amount of a fluorine-containing polymer and a higher fatty acid metal salt compound, and the following excellent effects are exhibited.

(1) The film has excellent flatness on the surface, and is extremely useful in magnetic tape applications, as it has fewer drawbacks such as dropouts and skipping during playback.

(2) Good electrical characteristics.

(3) It has good friction properties, so it is easy to pass through the process and is easy to handle.

(4) There is less clogging of the filter and less tearing of the film during the melt-molding process of the film.

As described above, the polyester composition of the present invention can be applied to fiber M1, unstretched film, stretched film, and Bujistinok III.
As the moon comes to light, there is a light in the temple.
It is very suitable as a composition for 11QI+ stretched film.

The present invention will be further described with reference to examples.

In addition, 11i11 of each poetic type of polyester in the examples
Constant t1. This was done in the following manner.

A, Aluminum metal evaporation strength Gold dopa evaporation surface VC polynisdel laminate Dave attached,
The state when this IL is decapitated is shown in the following 5 step method/
child.

1: I+ (At is 7.11 on the adhesive tape side without resistance)
Meat 11! do.

2:50 1- part is 88 on the adhesive tape side! be separated.

3: 10 to 50% of the area is peeled off to the adhesive tape side.

4: The part to be peeled off to the adhesive tape side is 10% lower.

5: Not peeled off to the adhesive tape side.

A trunk rank of 6 or higher is a practically preferable level.

B, Phil 1, Haze Measured according to I\STM-D1003-52.

c, ai friction coefficient Srinoff manufactured by Toyo Tester [using tester, 8S TM
-Measure according to method D-1894B.

In addition, the film's slipperiness and 1. The coefficient of static friction was used.

]), film surface roughness: The film surface mj was measured using a stylus blade (4 sides from l'c), and the maximum roughness and average roughness μ) were determined.

E. Dielectric breakdown voltage was measured using an AC voltage distribution tester using a JIS-C-2 filter 18V (1.

Example 1 A transesterification reaction was carried out using 100 parts by weight of dimethyl terephthalate, 62 parts by weight of ethylene glycol, and 1 part by weight of 0.09 parts by weight of calcium acetate, and the product was mixed with 11 parts of antimono trioxide 006. , and 0.043 parts of trimethyl phosphate were added, and polycondensation was finally carried out at 28 DC under reduced pressure according to a conventional method, and when the intrinsic viscosity reached approximately 0.60 ItcL, 1.Polymer x x te/l/ 100 Middle iji part VCl'J'
Polyvinylithia fluoride 03 with a melting point of 165°C and monothanic acid 103 tun i:
1 part and then heated at 280'C under reduced pressure 1' for 30 minutes.
Mixing was performed while stirring 1'l-L.

The thus produced polyester was discharged from a condensation reactor and made into chips.

Drawing h: After drying, the -J-Nof was melt-extruded at 285°C, cast on a cooling drum at 60°C, bound in a non-stretched notebook, and then stretched in the longitudinal direction by 3.3 cm in the usual manner. i'τ
The film was stretched in the width-to-edge direction VC5,5, and then heat-treated at 215C while being slightly relaxed, to obtain a polyethylene derephthalate-'Ilη11 stretched film having a thickness of 12μ.

(a) The static friction coefficient of the exposed film is 0.44, the average surface roughness of the film is 0.009μ, and the film S trr
The maximum roughness of i was 017μ, and both flatness and slipperiness were good.

Unfortunately, when aluminum was vapor-deposited on the surface of the film and the adhesion of the vapor-deposited film was examined, it was found to be in contact.

Comparative Example 1 A biaxially stretched film 4' of which 1.05 parts by weight per 100 parts of polyester was added with only borinated vinyl ribo by the same knob method as in Example 1! +-tl(, although the flatness is good, the static j early rubbing coefficient is 12,
No smoothness was obtained at all.

Comparative Example 2 Thorium monothanate kra+ was prepared in the same manner as in Example 1.
Add J1. only to 100 parts by weight of polyester. The biaxial OL elongated film containing 1 part of -103 weight h had good properties as in Comparative Example 1, but had a static friction coefficient of 091 and poor lubricity.

Example 2 100 parts by weight of dimethyl terephthalate, 62 parts by weight of ethylene glycol, and Cal/Rum 009! A transesterification reaction is carried out by a conventional method using the if part as a catalyst, and the product is 70,03 ton 1if part, '/
Table 1, in which 0.08 parts by weight of methylphenylphospho7ic acid was added, the conventional method VCQ'i was finally polycondensed at 28[]°C under reduced pressure. No,'
In the same manner as in Example 1, a (vinylyso fluoride 765 mol%/te)rafluoroethylene 765 mol%) copolymer O6 having a melting point of 1%, 111 part, 1...'', bimonotanoic acid tutorium salt 0.07 ton -: ([Borysdeltinog having 6 parts (47), using the same method as in Example 1 θ, and 6μ of -j II 1119 and medium soil l, 1.
″Ji+9□ Rubber u &1: 0.55 f, 71.
Lum people + f + i LJ) ・l' yunIllsa001
1μ, maximum phase of film surface o18μ and flat J↓11(
11, ::; Both LJ1 are good, and the insulation of the film (9'break''lLj], fF, I: 502 V /
It was μ.

Comparative actual hIMI 115 Fluorine-containing hand coalescence was carried out in the same manner as in Example 2, and -2tll+ was added with 1-tonic acid sonol/T-num having an average particle size of 25μ instead of sodium heptanoate.
Although the stretched film had a static friction coefficient of VC of 0.62, its dielectric breakdown voltage was poor at 412 V/μ.

Example 6 In Table 1, d (each, iu product j) was prepared in the same manner as in Example 1.
! Introducing the film that shows 121J, each! l! j
1J-1 was calculated.

Experiment A61 (Sogo Example 1), NoIJ5.ノ1(7,)1
θ9 is the eleventh product of the present invention.

Experiments, 5, 8, 8, because the content of cylindrical fatty acid metal crystal compounds and fluorine-containing polymers exceeds the scope of the present invention, there is a drawback that the adhesive strength (lζ) with aluminum metal is inferior.

In experiments A+ and 3, the number of carbon atoms in the higher fatty acid metal salt compound was less than 18! 4, and as mentioned above, there is a drawback that the adhesive strength V with aluminum and metal is poor.

In addition, in Experiment &4, the melting point of the fluorine-containing polymer exceeds the range of the present invention, and the flatness of the film/L film cannot be obtained, and the melting point is significantly below the range of the present invention. 6) Smoothness cannot be obtained in (experiment).

堝-o’r Applicant: Toshi Co., Ltd.

Claims (1)

[Claims] 1/, : repeat q (Polynis del 100 tons 4 consisting of ethylene derephthalate;
, (A) 17ill 1 point 120℃~255℃)
', Ni 7 No element system intermediate coalescence 001 to 10 double leaves, and (S) = 1' component having 18 to 33 carbon atoms, 1) metal salt of a compound consisting of a deficient seven-carbon compound. is at least 0 of the partial metal mass compound
, 005 to a polynisdel composition containing a double-layer compound.