JPH0726003B2 - Polyester composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester composition, and more specifically, it relates to a titanium hydrated oxide or organic polymer fine particles coated with titanium oxide and having an average particle size of 0.01 to 5 μm. The present invention relates to a polyester composition containing the same.

[Prior Art] Polyesters, especially polyethylene terephthalate, have excellent physical and chemical properties, and are therefore widely used as fibers, films and other molded articles. However, contrary to its excellent characteristics, it is known that workability in the molding process for obtaining the above-mentioned molded product and handleability of the product become problems. In the film field, it is important to provide slipperiness, and if the surface is not slippery, the film-to-film adhesion phenomenon will occur, and not only the work efficiency will decrease during film formation or post-processing but also the winding appearance will deteriorate. This will cause problems such as a significant decrease in product value.

To address these problems, a number of methods have been proposed to improve the slipperiness of the surface of the molded product by adding fine particles to the surface of the molded product by incorporating fine particles into the polyester, and some of them have been put to practical use. ing. For example, inert inorganic particles such as titanium dioxide, silicon oxide, calcium carbonate, talc and kaolinite, or organic polymer fine particles such as benzoguanamine-formaldehyde resin, polytetrafluoroethylene-hexafluoropropylene copolymer, polyphenyl ester resin There is a method of adding to the polyester composition synthesis reaction system (for example, JP-A-55-133431,
JP-A-57-125247, etc.).

However, such inert inorganic particles do not have a sufficient affinity with polyester, and voids are generated around the particles during the molding of threads, films, etc., which easily causes peeling at the interface. As a result, when forming a yarn, it causes yarn breakage during spinning and drawing, and when it is made into a film, especially when it is used as a magnetic tape, it is a main cause of running abrasion, and in capacitor applications it causes a decrease in dielectric breakdown voltage. Become.

On the other hand, improving the slipperiness impairs the flatness of the surface of the molded product, and, for example, in the case of a film, winding defects such as acne-like protrusions are caused by the coarse protrusions on the surface. On the other hand, if the flatness is to be improved, problems such as poor winding property occur.

Further, in the organic polymer fine particles, the affinity for polyester is good, but generally the heat resistance is poor, and it is easy to soften during polyester polymerization or melt molding, which causes problems such as poor dispersion of organic particles in the polymer due to aggregation. Occurs.

In recent years, these problems have become apparent from the standpoint of higher quality requirements and improved productivity, and polymers that have improved these problems are required.

As a result of intensive studies to develop a polymer in which the above problems have been solved, the present inventors have found that particles in the polymer can be obtained by incorporating titanium hydrate oxide or organic polymer fine particles coated with titanium oxide into polyester. Has improved heat resistance and dispersibility, and has excellent flatness, slipperiness, and abrasion resistance when formed into a film, workability (winding property) during film formation, and electromagnetic conversion characteristics and electrical characteristics as a product. The present invention has been achieved by finding that the

[Problems to be Solved by the Invention] An object of the present invention is to improve the heat resistance and dispersibility of fine particles in a polymer by coating organic polymer fine particles with titanium hydrate oxide or titanium oxide, It is an object of the present invention to provide a polyester composition having excellent flatness, slipperiness, abrasion resistance and electric characteristics, which cannot be achieved by the above-mentioned conventional techniques.

Another object of the present invention is to provide a polyester composition suitable for a molded product which has good workability during molding. INDUSTRIAL APPLICABILITY The polyester composition of the present invention can provide, for example, a polyester film which has a good winding property at the time of molding in a film, does not cause winding wrinkles and acne-like projections, and has a good slit property.

[Means for Solving Problems] The object of the present invention is to provide a titanium hydrate oxide or titanium oxide in a polyester comprising a difunctional acid component mainly containing an aromatic dicarboxylic acid and at least one glycol component. It is achieved by a polyester composition containing coated organic polymer fine particles having an average particle size of 0.01 to 5 μm.

The difunctional acid component constituting the polyester of the present invention is mainly an aromatic dicarboxylic acid or an ester-forming derivative thereof, specifically, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 1,2- Bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, dimethyl terephthalate as its ester-forming derivative, 2,6-naphthalene dicarboxylic acid, 1,2-bis (2-chlorophenoxy)
Ethane-4,4 'dimethyl dicarboxylic acid and the like,
Of these, terephthalic acid or dimethyl terephthalate is preferable. Examples of the glycol component include ethylene glycol, butylene glycol, diethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol and the like, among which ethylene glycol is preferable. In addition to these dicarboxylic acids or their ester-forming derivatives and glycol components, other components may be copolymerized, and the components to be copolymerized are, for example, diethylene glycol, propylene glycol, neopentyl glycol, polyalkylene glycol, p-xylylene glycol. 1,4-cyclohexanedimethanol, diol component such as sodium sulforesorcin, adipic acid, sebacic acid, phthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 5-carboxylic acid component such as sodium sulfoisophthalic acid, Examples thereof include polyfunctional dicarboxylic acid components such as trimellitic acid and oxycarboxylic acid components such as p-oxyethoxybenzoic acid.

When the dicarboxylic acid component is a dicarboxylic acid, it is subjected to an esterification reaction with glycol, and in the case of a dicarboxylic acid ester, after transesterification reaction with glycol, polycondensation is performed at high temperature and reduced pressure to obtain a polyester.

Also, the prepolymer itself can be polycondensed as a starting material.

On the other hand, the organic polymer fine particles used for coating is not particularly limited as long as it is an organic polymer fine particle that can be coated with titanium hydrate oxide or titanium oxide, but crosslinked polystyrene, benzoguanamine-formaldehyde, silicone, poly Particles of tetrafluoroethylene, polyphenyl ester and the like are more preferably used. The amount of these titanium hydrated oxide or titanium oxide-coated organic polymer fine particles added to the polyester composition is a slipperiness when formed into a polyester molded product, particularly a film, and flatness, clogging of a filter in the melt molding process, From the viewpoint of film breakage, etc., 0.001 to 10% by weight is preferable, 0.005 to 2% by weight is more preferable, and 0.001 to 1% by weight is particularly preferable.

The average particle diameter of the organic polymer fine particles coated with titanium hydrate oxide or titanium oxide needs to be 0.01 to 5 μm, and more preferably 0.05 to 2 μm. If the average particle size is less than 0.01 μm, the slipperiness of the film is reduced. On the other hand, if the average particle diameter exceeds 5 μm, the abrasion resistance, the electric characteristics and the flatness of the film deteriorate due to the coarse particles.

The method for coating the titanium hydrated oxide or titanium oxide used in the present invention is carried out by suspending the organic polymer fine particles in an aqueous solution of titanyl sulfate or in a mixed solution of water methanol, water-ethanol and water ethylene glycol. A method of thermally hydrolyzing titanyl sulfate by heating in the presence of polymer particles to form a titanium hydrate oxide or a coating layer of titanium oxide on the surface of the organic polymer particles is preferably used. The method is not limited.

The hydrated titanium oxide or organic polymer fine particles coated with titanium oxide according to the present invention is obtained by partially or entirely coating the surface of the organic polymer fine particles with titanium hydrated oxide or titanium oxide. When the organic polymer fine particles are coated with titanium hydrate oxide or titanium oxide,
The heat resistance and dispersibility in the polymer are remarkably improved, and further the affinity with the polymer is improved. Therefore, when a biaxially stretched film is used, the abrasion resistance due to the tape running abrasion is improved and the voids around the particles are reduced. This film provides good electromagnetic conversion characteristics and dielectric breakdown voltage. Further, when formed into a film, the winding property during film formation is excellent, and the winding shape is good without acne-like protrusions due to winding wrinkles and coarse particles.

The timing and method of adding the organic polymer fine particles coated with titanium hydrated oxide or titanium oxide to the polyester are not particularly limited, but it is important to add the particles before the start of the polymerization and during the polymerization reaction in terms of particle dispersibility. Is particularly preferable.

The particles are preferably added in the state of slurry dispersed in ethylene glycol in the polyester production precursor step or polycondensation step.

As a dispersion method for a dispersion medium such as ethylene glycol, for example, a high speed disperser, an ultrasonic disperser, a sand mill, a roll mill or the like may be used.

When dispersed, phosphoric acid, phosphorous acid, phosphorus atom-containing compounds such as sodium hexametaphosphate, nitrogen atom-containing compounds such as tetraethylammonium hydroxide and hydroxylamine, surfactants such as cations, anions, or zwitterions The use of a dispersant is particularly preferred because it further improves the dispersibility of the hydrated titanium oxide or the organic polymer coated with titanium oxide in the polymer.

Further coated with a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium, and titanium which is usually used in the production of polyester, a phosphorus compound as a color preventing agent, a titanium hydrate oxide or a titanium oxide. Inorganic particles other than the prepared organic fine particles can be appropriately added if necessary.

[Examples] The present invention is described in detail below with reference to Examples. In addition,
The characteristic values of the polyester in the examples were measured according to the following methods.

(A) Average particle size of particles The average particle size was determined by the equivalent spherical diameter of the particles corresponding to the point of 50% volume measured by electron micrograph of the particles. The equivalent sphere diameter is the diameter of a sphere that has the same volume as the particle.

(B) Intrinsic viscosity of polymer Measured at 25 ° C using O-chlorophenol as a solvent.

(C) Particle Dispersion State in Polymer After the polymer was cut into an ultrathin section of about 800 L by an ultrathin film forming apparatus, the particle dispersion state in the polymer was observed with a transmission electron microscope.

The dispersed state was determined as follows.

◯: Almost no secondary aggregated particles were observed, and the purpose was achieved.

Δ: Secondary aggregation particles are slightly present and the purpose is not achieved.

X: Most of the particles are secondary agglomerated particles and therefore do not achieve the purpose.

(D) Film characteristics 1) Surface roughness: Ra (μm) Measured by a stylus surface roughness meter (cutoff value)
0.25 mm, measuring length 4 mm, but according to JIS-138601) The evaluation criteria are as follows.

A: Achieve the purpose with less than 0.02.

◯: The object is achieved with 0.02 or more and less than 0.05.

Δ: The object is not achieved when the value is 0.05 or more and less than 0.10.

×: The objective is not achieved at 0.10.

2) Sliding property According to ASTM-D-189413-63, the static friction coefficient (μs) and the dynamic friction coefficient (μd) were measured using a slip tester.

The evaluation criteria are as follows.

Sliding property (μs): ⊚: Less than 0.7 achieves the object.

○: Achieve the purpose with 0.7 or more and less than 1.0.

B: The object is not achieved when 1.0 or more and less than 1.6.

×: 1.6 or more does not achieve the purpose.

3) Abrasion resistance Using a tape running tester TBT-300 [manufactured by Yokohama System Laboratory Co., Ltd.], after repeatedly running 300 times in an atmosphere of 25 ° C and 50RH, white shavings adhered to the guide part. (White powder)
Is visually determined.

Here, the guide diameter is 8 mmφ and the guide material is SUS27.
(Surface roughness 0.2S), wrap angle is 180 degrees, tape running speed is 3.3cm / sec.

Criteria for judging the amount of white powder Very small ◎ Small ○ Slightly large △ Very large × 4) Electromagnetic conversion characteristics The following magnetic paints are applied to one side of the biaxially oriented film of the present invention, dried and cured to form a magnetic layer. It was

When the output signal when a 7000 Hz signal is recorded and reproduced on the magnetic recording medium manufactured in this way is viewed on one screen, the output signal is strong, the signal is strong, and the signal waveform is flat. Good, weak output signal or deformed signal waveform was determined as bad.

[Magnetic paint]

Ferromagnetic alloy powder (Fe-Co) 300 parts by weight Zinc powder (average particle size 2 μm) 25 parts by weight Cellulose acetate butyrate 30 parts by weight Polyisocyanate compound (Dismodule L-7)
5) 180 parts by weight Epoxy resin 25 parts by weight Silicone oil 4 parts by weight Lecithin 5 parts by weight Toluene (solvent) 200 parts by weight Methyl ethyl ketone (solvent) 200 parts by weight Ethyl acetate (solvent) 100 parts by weight 5) Void ratio Vertical stretching ratio 3.3 2x, horizontal 3.5x, draw ratio 5μ thickness biaxially oriented film stretched at 85-95 ° C is mounted on a slide glass with liquid paraffin, and the transmission optical microscope is darkfield and the area of high brightness part (white part) Image analyzer A (QTM900, made by Cambridge Instrument)
Ask in.

Next, the area B of the low-intensity part (gray to black part) in the same place as the above-mentioned high-intensity part was obtained by an image analyzer in the same manner as above with a phase contrast microscope, and the area ratio (B /
A) was defined as the void ratio.

The evaluation criteria are as follows.

Void ratio: ⊚: Achieve the purpose with less than 0.1.

○: Exceeds 0.13 to 0.1 and achieves the following objectives.

Δ: 0.2 to 0.13 is not achieved.

X: The object was not achieved because it exceeded 0.2.

6) Dielectric breakdown voltage (BDV) It measured according to JIS-C-2318 using an alternating current withstand voltage tester.

The evaluation criteria are as follows.

A: Achieve the purpose at 500 V / μ or more.

A: Achieve the purpose with a value of 400 to less than 500.

Δ: The object is not achieved when the value is less than 300 to 400.

X: Less than 300 does not achieve the purpose.

Example 1 (Preparation of particles) After 20 parts by weight of titanyl sulfate was dissolved in 1000 parts by weight of ion-exchanged water, 100 parts by weight of an aqueous solution of crosslinked polystyrene particles having an average particle size of 0.9 μ (10% by weight) was added. Then, the temperature was raised and the reaction was carried out at the boiling point for 6 hours to coat titanium dioxide around the crosslinked polystyrene particles. After the reaction
After washing with water and filtration, the obtained particles were added to ethylene glycol to obtain a 10 wt% ethylene glycol slurry.

(Polymerization of polyester) 100 parts by weight of dimethyl terephthalate and ethylene glycol 7
From 0 parts by weight and 0.09 parts by weight of calcium acetate as a catalyst, a transesterification reaction is carried out by a conventional method, and the product is 0.03 parts by weight of antimony trioxide, 0.3 parts by weight of lithium acetate, 0.2 parts by weight of trimethyl phosphate and 10% by weight. Dioxide particles coated with titanium dioxide dispersed as an ethylene glycol slurry with an average concentration of 1.0 μm
Add 0.1 parts by weight and polymerize by a conventional method to obtain an intrinsic viscosity of 0.6.
15, polyethylene terephthalate having a softening point of 260.9 ° C. was obtained. As a result of observing the particles in the polymer with a transmission electron microscope, it was observed that titanium dioxide was coated around the crosslinked polystyrene particles, and the particles were stably present. In addition, when looking at the particle dispersion state, there was no secondary agglomerated particles and they existed as almost primary particles.

The polymer was melt extruded at 290 ° C., and at 85 ° C. in the longitudinal direction 3.3
The film was stretched 3.5 times in the transverse direction at 95 ° C. After that, it was heat set at 205 ° C to obtain a biaxially stretched film with a thickness of 15 µm, which was 50 m /
It was rolled up in minutes. The windability and winding appearance (wrinkles, acne-like projections) were good. As a result of evaluating the film properties, the film was excellent in slipperiness and flatness, and was excellent in abrasion resistance and electromagnetic conversion properties (Table 1).

Examples 2 to 7 and Comparative Example 1 A biaxially oriented film of polyethylene terephthalate was prepared in the same manner as in Example 1, except that the type, average particle size and content of the titanium dioxide-coated organic polymer particles contained were changed. The winding property and winding appearance during film formation were good. Further, when the type, the average particle size, and the content of all the particles contained are within the scope of the present invention, when formed into a film, the slidability, flatness, abrasion resistance, and electromagnetic conversion characteristics are excellent ( Examples 2-7).

However, when the average particle size of the contained titanium dioxide-coated organic polymer particles was outside the scope of the present invention, it was not possible to satisfy all of the slidability, flatness, wear resistance, and electromagnetic conversion characteristics (comparative example). Example 1).

Comparative Examples 2 to 6 In the same manner as in Example 1, crosslinked polystyrene particles, silicone particles, benzoguanamine formaldehyde particles,
A biaxially oriented polyethylene terephthalate film containing colloidal silica particles and calcium carbonate particles was obtained.
The crosslinked polystyrene particles were dissolved in the polymer, and the silicone particles and the benzoguanamine / formaldehyde particles were heavily aggregated in the polymer and the film quality was poor (Comparative Examples 2 to 4). Further, in the case of colloidal silica and calcium carbonate particles, the winding property during film formation was good, but a large number of acne-like projections were generated and the winding shape was poor. In addition, as a result of evaluating the film characteristics, it was not possible to satisfy all of the slipperiness, flatness, abrasion resistance, and electromagnetic conversion characteristics in any case (Comparative Examples 5 and 6).

Examples 8 to 10 and Comparative Examples 7 and 8 A biaxially oriented film of polyethylene terephthalate having a thickness of 2 μm was produced in the same manner as in Example 1, except that the type of particles contained and the average particle size were changed. From Table 2, the film of the present invention had few voids, and had good slipperiness, flatness, and BDV. (Examples 8 to 10) On the other hand, when the particle species other than the present invention were used, voids were large and flatness and BDV were poor (Comparative Examples 7 and 8).

[Effects of the Invention] Since the polyester composition of the present invention contains titanium hydrate oxide or organic polymer fine particles coated with titanium oxide, the following excellent effects are exhibited.

(1) Since the organic polymer fine particles coated with titanium hydrated oxide or titanium oxide can be dispersed in the polymer extremely uniformly, the fibers, films or molded articles obtained from the composition of the present invention are Excellent in slipperiness,
During molding such as extrusion, troubles such as clogging of the molding machine, yarn breakage, and film tearing do not occur.

(2) When the film is formed into a film, it has excellent winding properties during film formation, no wrinkles are formed, and there is no pimple-like projection due to coarse particles, resulting in a good winding form.

(3) Since the heat resistance of particles is improved by coating the organic polymer particles with titanium hydrate oxide or titanium oxide, the particles can be easily molded by a normal molding method.

(4) Since the particles of the present invention are fine particles composed of an organic and inorganic composite component, it is considered that the particles and the polymer exhibit a unique interaction, but when the film is formed, the particles are less likely to fall off and a void is generated. Is also significantly less. Such a film is suitable for magnetic tape applications and capacitors.

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Claims (1)

[Claims] 1. An organic compound having an average particle size of 0.01 to 5 μm in which a polyester comprising a difunctional acid component mainly containing an aromatic dicarboxylic acid and at least one glycol component is coated with titanium hydrate oxide or titanium oxide. A polyester composition containing fine polymer particles.