JPH01155A - polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Application in the Mi Industry] The present invention relates to a polyester composition, and more specifically, it has excellent dispersibility of one particle, and when formed into a film, has extremely few coarse protrusions on the surface. The present invention relates to a polyester composition containing ethylene-11,6-naphthalate as a main repeating unit, which has excellent slipperiness, good winding properties, and abrasion resistance.

[Problems to be solved by conventional technology and invention]

Biaxially stretched polyester films, especially polyethylene terephthalate, have excellent physical and chemical properties and are used as base materials in a wide range of industrial fields, including magnetic tapes, capacitors, packaging, and plate-making. .

Incidentally, in recent years, there has been a strong desire for electrical and electronic equipment to be smaller, lighter, and higher in performance, and as a result, the characteristics required for the films used have become more severe. For example, this includes improvements in mechanical strength and heat resistance due to thinning. Even with polyethylene terephthalate, it is possible to expect some improvement in mechanical properties by changing the stretching recipe, for example by applying a re-stretching method, but it is impossible to achieve a significant improvement, and improvements in heat resistance are deeply related to the molecular structure. I have to say that it is extremely difficult to come to terms with this.

Under these circumstances, biaxially stretched films of polyethylene 11,6-naphthalate have been attracting attention, and it is clear that the mechanical strength and heat resistance of this film are superior to those of biaxially stretched polyethylene terephthalate films. has been done.

As in the case of polyethylene terephthalate film,
In the case of biaxially oriented polyethylene/-2,4-naphthalate films, smoothness must be improved so as not to affect process passability and winding properties during the film manufacturing process, and handleability during post-processing processes such as coating and vapor deposition. There is a need to.

For this purpose, in the case of polyethylene terephthalate, fine particles are incorporated into the polymer.

A technique has been used to improve the slipperiness of the film by imparting appropriate irregularities to the surface of the film, and this technique can also be applied to polyethylene 1-1,6-naphthalate films.

One method of incorporating fine particles into polyester is to add particles to complete the polycondensation reaction during polyester polycondensation reaction.The particles used here include talc, kaolin, silica, and carbonic acid. Inorganic compound particles, such as calcium, titanium dioxide, and lithium fluoride, which are substantially insoluble and inactive in polyester are well known. However, although these inorganic particles are usually obtained by crushing natural minerals or synthesizing them, it is extremely difficult to avoid the inclusion of coarse particles or aggregated particles.

If coarse particles or agglomerated particles are contained in polyester, the filter will become severely clogged during the extrusion process during film formation.
Furthermore, the film tends to break during the stretching process.

Furthermore, from the viewpoint of film quality, minute defects called fish eyes occur in the film, causing problems such as dropouts in magnetic tapes and poor withstand voltage in capacitors.

On the other hand, the dispersibility of the particles in Borienether is also important; if the particles aggregate, it will cause the problems mentioned above, but in the case of polyethylene-2,6-naphthalate, the dispersibility of the particles is more important than in the case of polyethylene terephthalate. It is known that if it is frozen, -・.

In order to solve the above-mentioned problems, various methods are used to remove coarse particles and agglomerated particles contained in inorganic compound particles by pulverizing, classifying, and filtering them, and to improve their dispersibility in polyester. The method of
The results are not necessarily satisfactory.

The recent trend toward miniaturization and higher performance of electrical and electronic equipment requires that the surface of polyester film has almost no visible eye and that the irregularities on the surface be even and finer. This is difficult to achieve with conventional technology.

Incidentally, various products of silica particles having different average particle sizes are commercially available. However, even if the silica particles were incorporated into polyester to form a film, it did not satisfy the above-mentioned strict requirements. In other words, particles such as silica particles, which have relatively high surface activity and are fine, tend to form secondary agglomerated particles, making it difficult to completely disperse them in a dispersion medium. Particle aggregation occurs even after addition to the reaction system, and as a result, coarse agglomerated particles are contained in the polyester, causing problems during film formation and deterioration of film quality as described above. It was.

[Means for solving problems]

The present inventors focused on silica particles as particles to be added and contained in polyester, and found silica particles that do not contain coarse or aggregated particles and have good dispersibility in polyester, especially polyethylene-2,6-naphthalate. I considered it carefully.

As a result, the fine particles of amorphous silica obtained by hydrolyzing and condensing alkoxysilane using a specific catalyst have an extremely sharp particle size distribution, do not contain coarse or aggregated particles, and are free from media such as ethylene glycol. It has excellent dispersibility in polyester, and when formed into a film, it gives a very uniform surface with very little surface scratches, and has excellent slipperiness, good winding properties, and abrasion resistance. They have discovered that this is the case and have completed the present invention.

That is, the gist of the present invention is to provide a polyester having ethylene-2,4-naphthalate as a main repeating unit, which is substantially amorphous and has an average particle size of o, which is obtained by W water decomposition reaction and condensation reaction of alkoxysilane. oi~2
．． A polyester composition is characterized in that it contains 0.00/-3 parts by weight of spherical silica fine particles having a diameter of 0 μm and a particle size distribution satisfying the following formula (I).

/, /≦CLio/aq□〕≦:r,t (I
) represents the ratio of particle sizes. ) Hereinafter, the present invention will be explained in detail.

Polyester in the present invention refers to naphthalene ya, b
- After performing esterification or transesterification using dicarboxylic acid or its alkyl ester as the main acid component and using ethylene glycol as the main glycol component,
It refers to polyester obtained by performing a polycondensation reaction, but a part of it may be replaced with other components.

For example, part of the acid component may be replaced with naphthalene-2, coudicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, p-hydroxybenzoic acid or a lower alkyl ester thereof; A portion of the glycol component may be replaced with trimetele/glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, /, +1-cyclohexane dimetatool, and the like. In any case, the polyester referred to in the present invention is 0 mol % or more, preferably 9 mol % or more.
It refers to a polyester in which 0 mol% or more is ethylene-6-naphthalate units.

In the present invention, the additive particles that are incorporated into the polyester to improve the surface properties and slip properties of the film are silica particles with an average particle diameter of 0.0/~3 μm, which are made from alkoxysilane as a starting material. It is obtained by a hydrolysis reaction and a condensation reaction using an amine catalyst.

As an alkoxysilane compound (OnHzn+xO)
It is a compound represented by a81 (n=7 to 1), and specifically, compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane are preferably used. As a catalyst for the hydrolysis reaction and condensation reaction, ammonia, trimethylamine, aqueous tetraethylammonium solution, urea, etc. can be used, but ammonia aqueous solution is preferable.

For example, silica particles are synthesized as follows.

That is, a solution of tetramethoxysilane dissolved in methanol solvent (referred to as solution A) is prepared, and a separate solution of water and ammonia aqueous solution dissolved in methanol (referred to as solution B) is prepared. Both solutions have a predetermined temperature, e.g. 20 to 30
℃, add solution A while vigorously stirring solution B, then maintain at a predetermined temperature for several hours, centrifuge, wash with alcohol as a solvent, dry, and then disperse in ethylene glycol, or Silica particles are obtained by adding ethylene glycol to a suspension of silica particles after the reaction is completed, and then distilling the suspension to remove excess ammonia, alcohol, and water. In any case, it is preferable that the spherical silica of the present invention is finally made into an ethylene glycol slurry and made by UdA. Incidentally, at this time, the water content in the ethylene glycol slurry must be kept below 0.i%.

The concentration of spherical silica particles in the ethylene glycol prepared in this way is preferably less than 20% by weight, preferably less than 70% by weight, particularly preferably from 0.2 to 5% by weight. -0
If it exceeds % by weight, it is undesirable because it tends to cause aggregation when added to the polycondensation reaction system. If the O,S content is less than % by weight,
Too much ethylene glycol is used, which is economically disadvantageous.

Particle size ratio of silica particles obtained by hydrolysis reaction and condensation reaction of alkoxysilane in the present invention [d10
The value of /d90] needs to be in the range /, /~ko, ri. Exceeding 0 or 0 means a wide particle size distribution, which is not preferable because the surface of the film will be lost.

The particle size of the spherical silica particles used in the present invention is 0.0/
~3.0 μm, preferably o,
oiS-1 .mu.m1, more preferably 0.oi to/.mu.m. 0.0! If it is less than μm, the effect of improving the surface properties and slipperiness of the film will not be sufficient. If it exceeds 3.0μm,
This is not good because the surface roughness of the film becomes too large or coarse particles become mixed in, which deteriorates the quality of the film.

In the present invention, the content of spherical silica particles in the polyester composition must be 0.00/-j weight-It%, preferably 00007 to 2 weight%, more preferably 0.00/-/ ″fJLfJL amount%0.00/I
If the amount is less than J%, the effect of improving the slipperiness of the film will be insufficient, and if it exceeds 3% by weight, the surface roughness of the film will become too large or agglomeration may occur, which is not preferable.

The spherical silica particles used in the present invention have an extremely sharp particle size distribution and have excellent dispersibility in ethylene glycol, so no special dispersion treatment or classification treatment is required, and the slurry filter has excellent porosity. ing.

In producing the polyester composition of the present invention, the spherical silica particles are preferably added as an ethylene glycol slurry during the polyester synthesis reaction, but it is particularly preferably added at any time before the start of the polycondensation reaction. .

The polyester obtained by the present invention may contain fine particles such as silica particles, calcium carbonate, amorphous zeolite, titanium dioxide, kaolin, talc, lithium fluoride, etc., as long as the gist of the present invention is not impaired. , fine particles precipitated by the reaction between catalyst residue and phosphorus compound in the polyester polycondensation reaction system, such as calcium and lithium 41A.
It may be used in combination with a compound consisting of a lino compound, a compound consisting of a kotoba calcium z'r phosphorus compound, and the like.

The preferred intrinsic viscosity of the polyethylene-2,6-naphthalate composition is 0.2 to 0, more preferably 0.
35~O, DE. However, since the melt viscosity of polyethylene-2,6-naphthalate is much higher than that of polyethylene terephthalate, it is difficult to use the batch reactor used in the production of polyethylene terephthalate. Polyethylene--6-7 talate is produced with great difficulty. Therefore, to produce polyethylene 12,6-naphthalate with a desirable intrinsic viscosity, a solid phase polymerization method is used. That is, a melt polymerization method is carried out in a batch reactor to obtain an intrinsic viscosity of O1q~
0.3 prepolymer is obtained. This is it, o~igo
Pre-crystallization at 10°C to 190°C, followed by solid phase polymerization at 10°C to 3θ°C for a predetermined time under reduced pressure or a nitrogen stream. , 6-naphthalate are obtained and are suitably used as film raw materials.

The specific resistance of the obtained polyester when it is melted is also important (hereinafter, specific resistance simply refers to the specific resistance when it is melted).

In the case of polyethylene terephthalate, when the sheet-like material melted and extruded from the extrusion die during film formation is rapidly cooled in a rotating cooling drum by ℃, an electrostatic charge is applied to the second side of the sheet-like material to bring the sheet-like material into close contact with the cooling surface. The so-called electrostatic application cooling method is widely used, and it is known that the lower the resistivity of polyester, the stronger the adhesion, and this also applies to polyethylene-6-naphthalate.

For example, when applying polyethylene-2,6-naphthalate film to magnetic tape, it is necessary to strictly control the thickness accuracy, and the electrostatic cooling method must be effectively applied. For, resistivity! It is necessary to set it to less than x10''Ω·a, preferably less than 1×10BΩ·α.

It has been found that in order to lower the specific resistance, it is sufficient to solubilize the metal compound in the polyester and, if necessary, add a phosphorus compound in an amount of 0.3 to 0.9 times the mole of the metal contained in the polyester. Served. It is particularly preferable to add these metal compounds and phosphorus compounds as an ethylene glycol solution before the start of polycondensation. Therefore, polyester has a low specific resistance and can be effectively applied to the electrostatic cooling method.
can get.

On the other hand, when polyethylene co- or A-naphthalate film is used as an electrical insulating material, the specific resistance is 1xios ~
7 X/fl) 10Ω・I, preferably S×/0
It is preferable to set it to ``~!r
Furthermore, if the resistivity is too high, the electrostatic cooling method cannot be effectively applied, resulting in a film with poor thickness accuracy. In order to control the resistivity within the range of /X/0"~7X7010Ω・I, the above-mentioned method is adopted when the resistivity is low, and conversely, when the resistivity is high, it is possible to use polyester. Either the amount of the soluble metal compound added may be reduced, or the phosphorus compound may be added in an equivalent molar amount or more relative to the metal element of the added metal compound.

The polyester mainly composed of polyethylene-6-naphthalate obtained as described above can be made into a biaxially stretched film by the following method.

That is, the polyester composition is usually extruded into a sheet from an extruder at -50 to 310°C, rapidly cooled to below 0°C to form a substantially amorphous sheet, and then the sheet is at least A biaxially stretched film is obtained by stretching the film to an extent that the area magnification is doubled, and the film is further heat-treated at a temperature in the range of 120-30°C. The thickness of the film is Ol-~300 μm1.
Shifu amount, <1 piece θ, 3~2ρρme Otojima force KJ b
s.

The biaxially stretched film obtained from the polyester composition of the present invention has higher mechanical strength and heat resistance than polyethylene terephthalate film, so it can be used in a wider range of fields than polyethylene terephthalate film, and can be used in industrial applications. It is extremely useful.

〔Example〕

The present invention will be explained in more detail below using Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. "Parts" in Examples and Comparative Examples indicate "parts by weight." The negative definite method used is shown below.

(1) Average particle size (d, tO) Spherical silica particles are measured using an electron microscope; pond particles are measured using a high-filtration centrifugal sedimentation type particle size distribution analyzer 8A-OP.
Obtained by J.

(2) Particle size distribution (eLtol&to) As in the case of the average particle size, for spherical silica particles, a photographic method using an electron microscope was used, and the ratio to the particle size at 90% of the pond was used.

(3) Intrinsic viscosity [re] Polymer /, O9 was dissolved in phenol / tetrachloro I ethane = so, /; o (weight ratio) mixed solvent ioo - and measured at 30 ° C. - (4) When melted Resistivity [British Journal Op Applied Fixtures (Br1t, I, Appl, Phys, )
/7. //ll9-//! Gu,/? A method described in [AA] was used. However, in this case, the # line temperature of the polymer is 29! DC ioo at r°C.

The value immediately after applying V was taken as the specific resistance at the time of melting.

(5) Surface roughness of film Measured according to the method described in J. For the measurement, we used a surface roughness measuring machine model SR- manufactured by Koita Institute.
7F, the stylus diameter is μm, the stylus load is 30 m9, the cutoff value is o, the measurement length is 2. ! It was expressed as center line average roughness (Ra) measured as zz.

(Ra) The slipperiness of the film is represented by the friction coefficient μd, and the friction coefficient is A8TMD-/19
The measurement was carried out in accordance with the method described in No. 17, which was modified so that it could be measured using a tape-shaped sample. The sample at the time of measurement was width/3u,
length/! The test was carried out under an atmosphere of 65°C and 5% humidity, with a tensile speed of JOIl/min, and a measurement temperature of 65°C/fu'c.

(7) Dispersion of particles in the film The dispersion state of particles in the biaxially stretched film was determined by microscopic observation of the inside of the film.

(8) Number of coarse protrusions Aluminum was deposited on the surface of the film, and the number was measured using a two-beam method using an interference microscope. Measurement wavelength t lIo nm
Protrusions exhibiting third-order or higher interference fringes (protrusion height o, tiμm
Please check the number of items (above)! 1 was converted into a hit.

(9) Winding Characteristics The appearance of the roll surface and roll end face when the film was wound up into a roll was evaluated as follows.

○: Low/I/The roll end face is even with almost no wrinkles or lump-like defects on the surface.

Δ: There are almost no wrinkles on the roll surface, but there are some lump-like defects and the roll end face is slightly uneven.

X: Wrinkles appear on the roll surface, or the roll end face is uneven.

α0 Abrasion Property (Evaluation of White Powder) The film was run at °C over a length of zooyL using the running system shown in FIG. 1, and the amount of worn white powder adhering to the hard chrome fixing pin shown in (I) was visually evaluated.

◎: Does not adhere at all ○: Slightly adheres △: Little fj: (more than ○) adheres It was dissolved in methanol and kept at 20°C (liquid A).

On the other hand, 10 g of water was added to methanol, mixed with 3 g of g% ammonia aqueous solution, and kept at 0°C (B#
). Next, a stirring device was attached to Solution B, and Solution A was added while stirring. Immediately after the addition, a hydrolysis reaction and a condensation reaction occurred, and the inside of the reaction system became cloudy. After adding liquid A, add 1 more
After stirring and maintaining for an hour, ethylene glycol-gig was added and heated under reduced pressure to distill off excess water, methanol, and ammonia to obtain an ethylene glycol slurry containing spherical silica at a concentration of 1%. After drying the ethylene glycol slurry, a photograph was taken using an electron microscope and the average particle size was d10. The particle size distribution alo/dqo was determined. d! rls
l is 0.30μmb, A / 0 /A 90 is /j
Met. The obtained silica particles were uniform spherical particles with extremely uniform particle sizes. The slurry was subjected to filtration treatment using a filter having a 3 μm cut-off precision, and the filter had good passability. Moreover, the water content was 0.01%.

Production of polyester composition> 2,6-naphthalene dicarboxylic acid dimethyl ester 10
0 parts of ethylene glycol, 60 parts of ethylene glycol, and 0.09 parts of magnesium acetate tetrasalt were placed in a reactor and heated to raise the temperature, and a transesterification reaction was carried out while methanol was distilled off.

After about 7 hours from the start of the reaction, the temperature was allowed to reach -30°C, and the transesterification reaction was substantially completed. Next, after adding o and oy parts of ethyl acid phosphate, the above average particle size was 0.
．． A slurry of spherical silica particles of 30 μm was added so that the content of spherical silica particles was 0.3% based on the polyester, and after further addition of antimony dioxide o and ol I parts, the temperature was gradually increased to a final concentration of 2 g at 5°C. The pressure was gradually reduced from normal pressure until it reached /1i1Hg.

The reaction was stopped 3 hours after the start of the reaction, and polyethylene and 6-naphthalate were discharged under nitrogen pressure. Obtained polyethylene-2. The intrinsic viscosity of A-naphthalate is o, lIb, and the specific resistance when melted is t, 1Ixio
”It was Ω-no.

This polymer was pre-crystallized at 770° C. for 2 hours under nitrogen treatment, and further dried at 770° C. for 11 g and 0.30° C. for 0.3 hours. Solid state polymerization was carried out at 0°C for 1 hour.

The intrinsic viscosity of the obtained polyester was 0.6/.

Production of polyester film> Polyethylene-2,6-naphthalate containing spherical silica particles obtained by solid-phase polymerization was extruded into a sheet form from an extruder at 6°C, and the thickness was 110 μm using an electrostatic cooling method.
An amorphous sheet was obtained. The film was then stretched by a factor of a,0 in the machine direction, and by a factor of q, o in the transverse direction, and heat-set at -10° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 7 μm.

These results are summarized in the seventh section along with the following examples and comparative examples.
Shown on clothing.

Example - In Example 1, spherical silica particles with various average particles and particle size distributions were prepared in the same manner as in Example 1 except that the mixing ratio of methanol, water, and aqueous ammonia solution in solution B was changed. It was synthesized and examined in the same manner as in Example. In addition, in Example D, the amount of particles added to the polyester was also changed.

EXAMPLE The same study as in Example 1 was conducted except that the amount of particles added was 0.4%.

Example 6 Ethyl acid phosphate 0 after completion of transesterification reaction
．． The same study as in Example 1 was conducted except that 0.01 part of magnesium acetate tetrahydrate and 0.09 part of magnesium acetate tetrahydrate were added. The specific resistance during melting is lower than that of Example/! ;, /X10
After completion of the quester exchange reaction in Example 0, which was 7Ω・I, ethyl acid phosphate) (
The same study as in Example 1 was conducted except that part of 7,7 was added. The specific resistance during melting was higher than in Example 1, and was 3.2 x 10''Ω·α.

Comparative Example 1 Silica particles obtained by dry method (-defective particle size (7, Q Q
14Wh) in ethylene glycol using a homomixer manufactured by Tokushu Kika Kogyo / 0000 rl) m ”e1
Time-distributed processing was performed. 7μ of the obtained 3% slurry
Although it was passed through the mouth using an m-cut filter, it was difficult to pass through the mouth. The average particle size 47θ of this slurry determined by centrifugal sedimentation was o, and the iiμm1 particle size distribution eLlo/Aqo was λ, 9. The same study as in Example 1 was conducted except for using the slurry.

Comparative example λ Silica particles obtained by wet method (-defective particle size Q, Q j
, #I-) in ethylene glycol using a Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. at /0000 rpm for 1 hour. The obtained slurry with a concentration of 3% was passed through a filter with a cut of 10 μm, but it was difficult to pass through the mouth.

The average particle diameter djO of this slurry determined by centrifugal sedimentation is 0.
Konoμm1 particle size distribution dlo/eLqo was 3.3. The same study as in Example 1 was conducted except for using the slurry.

Comparative Example 3 Silica particles obtained by gelation of silicic acid were mixed in ethylene glycol using a homo mixer at the Tokushu Kika Kogyo Exhibition.
Dispersion treatment was performed at 0000 ram for 1 hour. Got it!
% concentration slurry was passed through a filter with a 20 μm cut, but it was difficult to pass through the mouth. The average particle size dSO of this slurry determined by centrifugal sedimentation is i, and the particle size distribution Aio, lq.

It was ko, ri. Using this slurry, the same study as in Example 1 was conducted except that the amount of particles added was Q, %.

All of the above comparative examples have poor dispersibility and a large number of coarse protrusions, which are not preferable.

Comparative example Hiro average particle diameter d, lto is o, qottm, particle size distribution d10
/d90 is 2. The same study as in Example 1 was conducted except that 0.3% of spherical silica particles were added to the polyester.

〔Effect of the invention〕

As explained above, according to the present invention, the particles have excellent dispersibility, and when formed into a film, there are very few coarse protrusions on the surface (and excellent slipperiness).

Ethylene-2,6- provides good winding properties and wear resistance
A polyester composition containing naphthalate as the main repeating unit is obtained, which is of great industrial significance.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the running system for evaluating wear resistance.
I) is a 6ml hard chrome fixed bottle, (n) is Tenshi 1
1 meter and θ is 130°.

Claims (1)

[Claims] (1) A polyester whose main repeating unit is ethylene-2,6-naphthalate, obtained by hydrolysis reaction and condensation reaction of alkoxysilane, is substantially amorphous and has an average particle size of 0.01 to 3.0 μm. Spherical silica fine particles that are large and have a particle size distribution that satisfies the following formula (I) are
．． A polyester composition characterized by containing 0.001 to 5% by weight. 1.1≦[d10/d90]≦2.7(I) (In the above formula, [d10/d90] is the particle size when the cumulative number of particles is 10% relative to the particle size when the cumulative number of particles is 90%. represents the ratio.)