JPS61278558A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives black spun-dyed yarn and black solution-dyed film having excellent surface properties, light screening properties and easy slipperiness, by incorporating fine titanium nitride powder in a polyester composed of a bifunctional acid component mainly composed of an arom. dicarboxylic acid and a glycol component. CONSTITUTION:0.01-20wt% fine titanium nitride powder having the max. particle size of 10mu or below, obtd. by heating metallic titanium or titanium oxide in N2 gas, is dispersed in a raw material consisting of an arom. dicarboxylic acid component such as terephthalic acid contg. not more than 20mol% of a comonomer such as isophthalic acid and a glycol component mainly composed of ethylene glycol and optionally a comonomer such as butylene glycol. A polymn. reaction is then carried out.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a polyester composition comprising a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component. The present invention also relates to a black spun-dyed polyester composition that has excellent light-shielding properties and is suitable for use in fibers, films, and other molded products.

[Prior art and its problems] Polyesters produced industrially today, such as polyesters based on polyethylene terephthalate, have excellent physical and chemical properties and are suitable for use in fibers, films, and other moldings. It is widely used as a product.

Manufacture these polyester fibers or films,
During further processing, it is necessary for molded products such as fibers or films to have slipperiness. For this reason, fine particles such as titanium dioxide and silica are blended into polyester to give the surface of the molded product an appropriate level of roughness. It is common practice to improve the surface smoothness of.

In order to increase the added value of polyester molded products by coloring polyester black or imparting light-shielding properties, for example, JP-A-48-93648, JP-A-50
It is known to add carbon black, such as in -62296@publication.

However, carbon black has extremely strong agglomeration properties, and therefore has the disadvantage of insufficient dispersion when added during the polyester manufacturing process. The presence of aggregated particles in the polymer causes thread breakage during spinning, causes problems such as abrasion of guides and spinnerets, and causes coarse protrusions, fish eyes, etc. in films. Especially in fibers, fine denier is progressing,
For films, such as magnetic recording films, high performance film surfaces are required, and black coloring and light-shielding properties are required.
At present, there is a long-awaited demand for a polyester having good particle dispersibility.

As a result of intensive studies in view of the above-mentioned circumstances, the inventors of the present invention have found that fine particulate titanium nitride has excellent dispersibility in polymers, black adhesion, light shielding properties, and imparting slipperiness. This is an invention.

[Object of the Invention] An object of the present invention is to provide a polyester composition that has black coloring and light-shielding properties that could not be achieved with the conventional techniques described above, and also has excellent particle dispersibility. Yet another object is to provide a polyester composition with excellent slipperiness.

[Structure of the Invention] The object of the present invention is to provide a polyester composition comprising a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, and containing fine particulate titanium nitride. It can be achieved.

Aromatic dicarboxylic acid components used in the present invention include terephthalic acid, 2,6-naphthalene dicarboxylic acid,
1,2-bis(2-chlorophenoxy)ethane-4,4
'-carboxylic acids, and may contain up to 20 mol % of copolymerized components such as inphthalic acid, 5-sodium sulfo-isophthalic acid, and adipic acid.

The glycol component mainly contains ethylene glycol, but may also contain butylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, 1,4-cyclohexane dimetatool, etc. as a main component or as a copolymer component.

The fine particle titanium nitride used in the present invention has a maximum particle size of 10 μm or less, preferably 5 μm or less, and is usually obtained by heating metallic titanium or titanium oxide in nitrogen.

In the present invention, the amount of finely divided titanium nitride contained in the polyester is o, oi to 20% by weight, preferably 0.05% by weight.
~10% by weight.

Addition of titanium nitride can be carried out at any stage of the polyester manufacturing process and by any method. However, before the start of polymerization, a step of producing relatively low molecular weight intermediates through esterification or transesterification, or a polycondensation reaction of these intermediates under reduced pressure or an inert gas flow, produces a high polymer capable of forming fibers or films. It is operationally advantageous to add it before the start of polyester polymerization and during the polymerization reaction, such as in the step of obtaining . At this time, it is preferable to add it in the form of a slurry uniformly dispersed in various dispersion media, generally ethylene glycol.

For dispersion in a dispersion medium such as ethylene glycol, various dispersion methods can be used, such as a high-speed dispersion machine, an ultra-high-speed dispersion machine, a colloid mill, an ultraturrex, a homogenizer, a sand mill, an attritor, a roll mill, etc. preferable. In particular, a dispersing machine such as an ultrasonic dispersing machine, a sand mill, or a roll mill is advantageous and preferable because it can finely disperse aggregated particles.

Most preferably, a medium agitation type dispersion method is employed. As the medium particles used in the medium stirring type dispersion, glass beads, ceramic particles made of zirconia, titania, etc. are used. The particles are preferably larger than titanium nitride particles, and more preferably have an average particle diameter of 0.5.
mm or less, 0.01 mm or more, more preferably o:
smm or less and 0.02 mm or more. Further, it is preferable to cause particulate matter to coexist with the dispersed particles, and to disperse the particles under high-speed stirring at a circumferential speed of 6 m/sec or more, preferably B111/sec or more.

In addition, when dispersing, using a dispersing agent such as phosphoric acid, an alkali compound, or polyalkylene glycol can prevent re-agglomeration of titanium nitride in the slurry and polymer, which is particularly preferred. .1
Slurry containing ~50% by weight, more preferably 1~30% by weight
Preferably, it is prepared as a slurry containing % by weight.

Furthermore, the method of mixing during melt molding of polyester is also simple.

[Effects of the Invention] As described above, the present invention is a composition comprising fine particulate titanium nitride in a polyester consisting of a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one glycol component, The composition of the present invention exhibits the following effects.

(1) Fine particles of titanium nitride can be dispersed extremely uniformly in polyester, so fibers, films, or molded products obtained from the composition of the present invention have excellent mutual slipping properties, and operations such as winding It is easy to use, and troubles such as clogging of the molding machine and thread breakage do not occur during molding such as extrusion.

(2) Since the composition of the present invention contains titanium nitride, there is no inferiority in the softening point or degree of polymerization of polyester, and therefore, the composition of the present invention can be easily molded by ordinary molding methods.

(3) Since the dispersibility is better than that of carbon black, it is possible to produce black spun-dyed yarn, black spun-dyed film, and light-shielding film with good surface properties and less shedding.

Next, the present invention will be explained with reference to Examples.
η] is the intrinsic viscosity determined at 30° C. in a mixed solvent of 1:1 (weight ratio) phenol:tetrachloroethane.

Example 1 Average particle size: 0.2 μm 1 Maximum particle size: 1.0 μm
10 parts of titanium nitride and 100 parts of ethylene glycol were added and stirred at high speed with a homogenizer to prepare a slurry.

The slurry was processed with a sand grinder manufactured by Igarashi Kikai Co., Ltd. to prepare an ethylene glycol slurry of titanium nitride. Subsequently, the slurry was filtered through a filter with a 1 μm opening. When the particle size distribution of the obtained slurry particles was measured using a centrifugal particle size measuring device (CAPA 500 manufactured by Horiba, Ltd.), the average particle size was 0.2 μm.

100 parts of dimethyl terephthalate and 65 parts of ethylene glycol, 0.038 part of manganese acetate as a catalyst, (0,
030 mol% to dimedimethyl terephthalate plus 15
The transesterification reaction was carried out at 0 to 240'C for 4 hours while distilling methanol off. Next, 11 parts of the prepared glycol slurry of titanium nitride (1% by weight as titanium nitride to dimethyl terephthalate), 0.02 parts of trimethyl phosphate
After adding 2 parts of antimony trioxide and 0.04 parts of antimony trioxide as a polymerization catalyst, a polycondensation reaction was carried out for 3.5 hours under a high vacuum of 1 ml 1 H (II or less) [η] = 0.640, softening point = 262. A polymer was obtained at 8°C.The L value of the polymer measured using a Hunter color difference meter was 14.0.The a value was -0.3, the b value was -0.3, and it was excellent as a black color. there were.

In addition, the polymer was sandwiched between two cover glasses and heated to 280°C.
After melt pressing and quenching, microscopic observation revealed that the particles were uniformly distributed, with no aggregated particles or coarse particles larger than 1 μm.

Comparative Example 1 A slurry was prepared in the same manner as in Example 1, except that carbon black with a primary particle size of 0.1 μm was used instead of titanium nitride. The slurry was filtered through a filter with an opening of 1 .mu.m, but the slurry became clogged and could not be filtered, so it was filtered with a filter with an opening of 5 .mu.m.

As a result of measuring the particle size distribution of the obtained slurry particles, the average particle size was 0.7 μm.

Next, using a carbon black slurry, the carbon black content was 1% by weight, [η] =
A polymer with a softening point of 0.643° C. and a softening point of 262.5° C. was obtained.

The L value measured using a Hunter type color difference meter is 20. O,a
The value was +0.1, the b value was -1.1, and the blackness was insufficient. Furthermore, as a result of observing the dispersion state of particles in the polymer in the same manner as in Example 1, many aggregated particles exceeding 3 μm were scattered, and the dispersibility of the particles was poor.

Example 2 10 parts of titanium nitride with an average primary particle size of 0.1 μm and a maximum particle size of 0.8 μm, 100 parts of ethylene glycol, and phosphorus i
1 part of 1 O and 0.06 part of tetraethylammonium hydroxide were added, and 100 parts of glass beads having an average diameter of 0.1 mm were added thereto, followed by stirring at 30 oorpm for 3 hours to prepare a slurry.

After stirring, the glass beads were separated using a 400-mesh wire mesh, and the resulting slurry of titanium nitride in ethylene glycol was filtered through a filter with an opening of 1.0 μm.

The particle size distribution of the particles in the obtained slurry was measured in the same manner as in Example 1, and the average particle size was 0.12 μm.

176 parts of bis-β-hydroxyethyl terephthalate with a molar ratio of ethylene glycol unit/terephthalic acid unit of 1.2 and a reaction rate of 98% was stored in a reactor at 240°C, and 144 parts of terephthalic acid and 6 parts of ethylene glycol were added at normal pressure.
4.6 parts (ethylene glycol/terephthalic acid molar ratio 1
．． 20> of the slurry was continuously fed at a constant rate over a period of 3 hours and 45 minutes. During slurry supply, the reaction system is heated to 230-24
While the reaction was controlled at 5° C., the water produced was continuously distilled off through a rectification column. After finishing slurry supply,
The reaction was continued for 1 hour while controlling the reaction temperature at 245°C to complete the reaction.

After the completion of the reaction, 50% by weight (176 parts) of the reaction product was transferred to the next reaction tank, and after adding 0.021 part of phosphoric acid (40 ppHl based on the amount of phosphorus atoms produced in the polymer), 0.05 parts of antimony oxide (addition based on the amount of antimony atoms formed in the polymer 1250
18.4 parts of an ethylene glycol slurry of titanium nitride (1% by weight based on the polymer produced as titanium nitride) was then added to 0.03 mm Hg over 70 minutes. 13 at the same time as decompressing
Temperature increased to 288℃ in 0 minutes, 288℃, 0.03mm
Polycondensation under @g, [η] = 0.653, softening point =
A polymer having a temperature of 261.5°C was obtained. The L value measured using a Hunter type color difference meter is 1B, 0. The a value was -0.2, the b value was OIO, and it was an excellent black color.

Furthermore, the dispersion state of the particles in the polymer was observed in the same manner as in Example 1, and as a result, the particles were uniformly distributed, and there were no coarse agglomerated particles exceeding 1 μm.

Example 3 and Comparative Example 2 After drying the polymer obtained in Example 2 at 120°C in a nitrogen atmosphere for 5 hours, using an extruder type melt spinning machine, the polymer was heated at a melting temperature of 290°C, a residence time of 20 minutes, and a spinning speed of 6000 m.
A multifilament yarn was obtained by spinning at 12 nozzle holes per minute.

The spinnability was good, and no yarn breakage occurred even after spinning for two days or more. Moreover, the pressure inside the spinning machine hardly increased.

Furthermore, the obtained filament had an L value of 18.0 and a suitable black color.

On the other hand, when spinning was performed in the same manner using the polymer obtained in Comparative Example 1, yarn breakage occurred frequently and the internal pressure of the spinning machine was 1.
It rose sharply by day.

Example 4 and Comparative Example 3 The polymer obtained in Example 1 was melt extruded at 290°C and extruded at 90°C.
The film was stretched 3.0 times in the longitudinal direction and 3.0 times in the transverse direction at 130° C., and then heat treated at 220° C. to produce a film with a thickness of 50 μm. The resulting film had a transmittance of 1.0% at 900 parts m, and had sufficient light-shielding properties.

Claims (1)

[Claims] A polyester composition comprising a bifunctional acid component mainly consisting of an aromatic dicarboxylic acid and at least one type of glycol component, and containing particulate titanium nitride.