JPS6198729A - Production of polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester having excellent transferability, abrasion resistance and surface properties, by reacting terephthalic acid (derivative) with an alkali or alkaline earth metal compound outside of the synthetic reaction system of polyester and adding the obtained particles together with a granular substance insoluble in the polycondensation system to the synthetic reaction system. CONSTITUTION:(A) 1mol of terephthalic acid (derivative) is mixed with (B) (i) 1-4 mol of an alkali or alkaline earth metal compound (e.gr. lithium acetate) and, if necessary, (ii) 0.5-4 mol of a phosphorus compound. The mixture is mixed with >=20 mol of ethylene glycol, etc., to form a slurry, made to react with each other preferably at 100-200 deg.C for 60-240 min, and the particles are separated e.g. by filtration, centrifugal separation, etc. The produced particles are added in combination with particles in-solu-ble in the polycondensation system (e.g. silicon dioxide) to the reaction system, and the polymerization of the monomer components is carried out to obtain the objective polyester. The amount of the produced particle and the insoluble particle is 0.005-2.0 wt% each based on the whole acid component of the aimed polyester.

Description

[Detailed Description of the Invention] [Technical Field] The present invention provides a method for improving runnability,
This invention relates to a method for producing polyester with improved abrasion resistance and surface properties.

[Prior art and its problems]

Polyester in general, and polyethylene terephthalate in particular, has excellent mechanical properties, heat resistance, and weather resistance.

Because of its electrical insulation and chemical resistance, it is widely used in the film field, including clothing and industrial textiles, as well as magnetic tape films, photographic films, electrical insulation films, and capacitor films.

When polyester is used in the film field, it needs to pass through the forming processes of melt extrusion, stretching, and heat treatment, or when forming a film, it needs to be rolled up, cut, surface coated with magnetic layers, etc., and incorporated into electrical parts. Considering the value as a final product such as properties such as properties, slipperiness of film products, abrasion resistance, and surface properties, we manufacture a polyester composition containing fine particles, which gives the surface an appropriate degree of roughness to give it surface slipperiness. It is common practice to improve film flow and improve surface properties and abrasion resistance.

Polyester compositions containing such fine particles include: ■ Polyester compositions obtained by adding and blending inert, insoluble fine particles such as silicon oxide, titanium dioxide, cal/rum carbonate, talc, clay, and organic polymers. (1) A polyester composition obtained by precipitating fine particles containing alkali, alkaline earth, or other metal compounds added to the polyester synthesis system, as well as phosphorus compounds as part of the constituent components during the polycondensation reaction process; etc. are known.

However, such known fine particle-containing polyester compositions have the following problems, and especially when formed into a film, it is difficult to obtain satisfactory properties such as slipperiness, abrasion resistance, surface condition, and film formability. I couldn't.

That is, in the polyester composition obtained by the above-mentioned method of adding insoluble fine particles, it is difficult to make the added particles fine,
In addition to the presence of coarse particles caused by agglomeration of particles and non-uniform particle diameters, these particles have relatively low compatibility with the polyester base material, so when molded into a film, etc. It may also become detached and cause other problems. In addition, coarse protrusions caused by coarse particles coexist, causing problems such as fisso/yuai and dropout, and government officials often add dispersants to prevent particles from agglomerating, which may affect the heat resistance of these polyesters. This results in disadvantages such as deterioration of electrical characteristics. Therefore, in order to finely disperse the particles, 911 is disclosed in 11J° Publication No. 55-425495, in which the added particles are finely dispersed and present in the polyester using a special stirring blade, but this method does not sufficiently meet the purpose. This has not yet been achieved.

On the other hand, polyester compositions containing particles obtained by the so-called fine particle precipitation method described in (1) above are difficult to control the particle size of the precipitated particles when the particle content is increased, and furthermore, in order to increase the particle amount, a catalytic metal compound is added. If the amount is increased, problems such as an increase in coarse particles due to aggregation of particles will occur. For example, Japanese Patent Application Laid-open No. 53-4103 discloses an example of precipitated particles containing lithium element, but it has not yet shown sufficient effects in the above-mentioned applications.

Particularly in recent years, the use of polyester in magnetic tape applications has increased significantly, and it has come to be used in many applications such as audio tapes, video tapes, and memory tapes, and the required properties are becoming increasingly sophisticated. Furthermore, in order to achieve smaller size and higher density, it is necessary to reduce the thickness of the magnetic tape.
There is an increasing demand for making the unevenness of the film surface more uniform and fine.

Furthermore, it is possible to obtain a polyester film by blending it with polyester that does not contain particles or has a small particle content.
In order to impart good surface properties to the polyester film and to form a molded product with excellent slipperiness, a raw material is required that is free of coarse particles and contains a large amount of fine particles. However, the finer these particles are and the larger the amount of particles, the more likely coarse particles will be produced due to aggregation of particles.

[Purpose of the invention]

In view of the above circumstances, an object of the present invention is to obtain a polyester that contains a large amount of uniform fine particles and is effective in improving the abrasion resistance and slipperiness of the film when formed into a film.

[Structure of the invention]

The purpose of the present invention described above is to carry out a transesterification or esterification reaction between terephthalic acid or its ester-forming derivative and a glycol, and then to carry out a polycondensation reaction to produce a polyester. Adding particles produced by the reaction of terephthalic acid or a terephthalic acid derivative with an alkali metal compound and/or an alkaline earth metal compound and particulate matter insoluble in the system at a point outside the polyester synthesis reaction system. This can be achieved by a polyester manufacturing method characterized by:

The polyester in the present invention is mainly composed of polyethylene terephthalate, which can be formed into fibers, films, and other molded products, and may be polyester, copolyester, or copolyester. The ingredients include diethylene glycol, propylene glycol, neopentyl glycol, polyalkylene glycol, p-quinrylene glycol, 1
．． Diol components such as 4-/clohexa/dimetatool, 5-sodium sulforesolone, dicarboxylic acid components such as acyhinic acid, sepanonic acid, phthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, and 5-sodium sulfoinophthalic acid. , polyfunctional dicarboxylic acid components such as trimellitic acid and pyromellitic acid, and oxy/carbo/acid components such as p-oxy/ethquin benzoic acid. When the dicarboxylic acid component is a dicarboxylic acid, after the esterification reaction with a glycol, and when the dicarboxylic acid ester is a dicarboxylic acid ester, after the transesterification reaction with a glycol, the obtained prepolymer is polycondensed at high temperature and under reduced pressure to form a polyester. shall be.

Terephthalic acid and terephthalic acid used to obtain particles produced by the reaction of terephthalic acid or terephthalic acid derivative with an alkali metal and/or alkaline earth metal compound outside the polyester synthesis reaction system used in the present invention. The derivative has a terephthaloyl skeleton, such as terephthalic acid (HOOC@cooH),
Bis-(mohydroquinoethyl)terephthalic acid direct HOC
H2CH20CO@C00C! H2CH20H), dimethyl terephthalate (CHgOCO@C00CH3),
Bis(hydroquine butyl) terephthalate (HOCH2
CH2CH2CH20CO@C0oCH2CH2CH2
CH20H), monohydroxyethyl terephthalate (
HOCH2 phthalate (HOCH2CH2CH2CH
20CO@C00H) and polyethylene terephthalate low polymerization [HO('-C!H2CH20Co@Co
o+nCH2CH20H (rl: 1-6)] and mixtures thereof.

In particular, the same ester-forming derivative as the target polyester does not reduce the quality of the polymer, so it can be suitably used.

Examples of the alkali metal and alkaline earth metal compounds used for particle generation include hydrides, alcolades, chlorides, hydroxides, carbonates, carboxylates, sulfates, and nitrates of alkali metals and alkaline earth metals. It will be done. Specifically, there are lithium acetate, lithium chloride, sodium acetate, lithium hydroxide, sodium hydroxide, calcium acetate, magnesium acetate/rum, manganese acetate, calcium chloride/rum, magnonium chloride, lithium carbonate, etc. Among these compounds, hydroxides and aliphatic carboxylates are preferably used because they suppress side reactions and are easy to post-process.

In producing the particles of the present invention, a phosphorus compound may be used in addition to terephthalic acid or a terephthalic acid derivative and an alkali metal and/or earth metal compound.

Examples of phosphorus compounds used in the platform include phosphoric acid, expanded phosphoric acid, methyl esters thereof, ethyl esters, phenyl esters, half-esters thereof, phosphonic acids, phosphinic acids, and esters thereof. , among these, not only one type but also two or more types can be used in combination.

Particles produced by reacting the above-mentioned terephthalic acid or terephthalic acid derivative with an alkali metal and/or alkaline earth metal compound in a solvent such as ethylene glycol at a temperature of 100°C to 200°C to produce the polyester of the present invention. is obtained. Furthermore, when using a phosphorus compound, terephthalic acid or a terephthalic acid derivative is reacted with an alkali metal and/or alkaline earth metal compound and a phosphorus compound in a solvent such as ethylene glycol at a temperature of 100°C to 200°C. obtained by doing.

Further, a preferred method for producing the product particles used in the production of the polyester of the present invention will be described.

That is, terephthalic acid or a terephthalic acid derivative was added to ethylene glycol in a molar amount of at least 20 times the terephthaloyl unit of terephthalic acid or a terephthalic acid derivative in a heating bath of 1'114 L, and the terephthalic acid derivative was heated in a heated bath. An alkali metal compound and/or alkaline earth metal compound is added in an amount of 1 to 4 times the mole per terephthaloyl unit, and the mixture is heated at 100 to 200°C, preferably at 15°C.
This is a method of reacting at a temperature of 0 to 190°C for 60 to 240 minutes.

In addition, when using a phosphorus compound, after the reaction described above, 0.5 to 4 times the mole of the phosphorus compound is added to the terephthaloyl unit of terephthalic acid or terephthalic acid derivative,
It is obtained by a method of reacting at a temperature of 100 to 190°C, preferably 150 to 180°C for 30 to 120 minutes.

In this case, the order of addition of the alkali metal compound and/or alkaline earth metal compound and the phosphorus compound may be reversed to the above-described order of addition, or in some cases, they may be added simultaneously.

Particles synthesized outside the reaction system from the terephthalic acid derivative obtained by such a method, an alkali metal/metal compound and/or an alkaline earth gold i1 compound, and further a phosphorus compound are prepared as a slurry. The generated particles can be used after being separated from the particle reaction system using a method such as transient separation or centrifugation, but the particle generation reaction solution may be used as it is, or after being diluted or concentrated. In the present invention, a terephthalic acid derivative and an alkali metal compound,
Insoluble particulate matter is added to the polyester synthesis reaction system together with particles generated outside the reaction system from the alkaline earth metal compound and further from the phosphorus compound. As particulate matter that is insoluble in such a polyester synthesis reaction system, inorganic particles such as silicon dioxide, calcium carbonate, magnesium carbonate, Merck, titanium dioxide, mica, calcium phosphate, and barium sulfate, and crosslinkable resin powders such as crosslinked polyester are used. , organic fine powder such as Teflon powder.

Further, among the above particulate substances, silicon dioxide, calcium carbonate, aluminum silicate, etc. can be particularly preferably used.

The specific surface area of particulate matter insoluble in the reaction system measured by the BET method is preferably 1 m'/S' or more, more preferably 30 m7
7 or more and 1000 m7S' or less, particularly preferably 80
m'/ii' or more and 800 rn'/g or less.

The specific surface area of particulate matter insoluble in the reaction system is 1 m'/S
If it is less than ', the dispersibility of particles in the polymer will decrease, making it impossible to have uniform fine particles.

The amount of rain particles added to the polyester is preferably 0.005 to 2.0% by weight, particularly preferably 0.001 to 1.0% by weight, based on the total acid components constituting the polyester.

In consideration of the reaction after the particles are added to the reaction system, it is preferable to prepare the particles as an ethylene glycol slurry in ethylene glycol. The ethylene glycol slurry can be prepared by a conventionally known preparation method, such as a method of finely dispersing the slurry using a special stirring blade as disclosed in Japanese Patent Laid-Open Publication No. 125495/1984. In this case, there are two methods: a method of dispersing the particulate material into an ethylene glycol slurry of synthetic particles obtained outside the polyester synthesis reaction system, a method of dispersing the ethylene glycol slurry of both particles separately, and a method of separately dispersing the ethylene glycol slurry of both particles. A method of mixing and dispersing the adjusted ethylene glycol slurry, etc.
It is necessary to prepare it by any method before adding it into the polyester polycondensation system.

The timing of adding the dispersed particles to the reaction system of the ethylene glycol slurry is preferably after the transesterification reaction or esterification reaction is substantially completed and before the start of the polycondensation reaction, but the timing is not limited to this. It may be done before the reaction is completed.

In addition, in the present invention, the esterification reaction or transesterification reaction includes catalyst 2111M such as alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium, calcium, strontium, and barium, and hydrides of zinc and manganese, Alcolade, Chlorides and glycol-soluble salts of heptanocarboxylic acids are preferably used as catalysts. Particularly preferred examples include lithium acetate, calcium acetate, strontium acetate, zinc acetate, manganese acetate, and manganese chloride.

Typical catalysts used for the polycondensation of bishydroquine alkyl esters of aromatic dicarboxylic acids are glycol-soluble antimony or germanium compounds, specifically antimony trioxide, potassium antimony tartrate, germanium oxide, etc. Preferably used.

〔Effect of the invention〕

The polyester of the present invention is characterized in that it contains a large amount of uniform, fine particles, and has an extremely small amount of coarse particles compared to polyesters obtained by conventional precipitate particle generation methods or addition methods.

Furthermore, it has good compatibility with polyester, and when producing fibers or films from the polyester, the following effects, which could not be achieved with conventional products, are exhibited.

■ Fibers and films with less clogging of filters during the melt-molding process into fibers and films and good workability in post-processing steps can be obtained.

■ Even if the film is formed into an extremely thin film with a thickness of 5μ or less, many uniformly fine particles remain in the film.
There is no blocking phenomenon between films, between films and metals, and between films and felts, and the polyester film has excellent slipperiness, good surface properties, and less particle shedding, and has excellent abrasion resistance. can get.

■ Also, since it contains a large amount of uniform fine particles, it can be used diluted, and in this case too, there is no film loss, and especially in magnetic tape applications, there are no dropouts, image unevenness, or sound skipping during playback, and it is extremely Useful.

The polyester obtained by the method of the present invention can be used for fibers such as multifilaments and staples, non-oriented, -axially oriented,
It can be preferably used not only for biaxially oriented films but also for monofilaments and plastics.

The present invention will be explained in more detail below using examples.

The characteristic values of the obtained polyester were measured according to the following method.

(A) Particle size in the polymer Lac polymer 20~ is sandwiched between two cover glasses and heated at 280°C.
After melt pressing and cooling, the particles were observed under a microscope and ranked based on the average particle diameter as follows.

A: Particle size 1.0μ B: Particle size ≧1.0μ, <5.0μ C: Particle size ≧3.0μ, <5.0μ D2 Particle size ≧5.0μ (l Particle dispersibility in polymer Sandwich polymer 20cm between two cover glasses and heat at 280℃.
After melt pressing and cooling, microscopic observation revealed that 5 present in 1-
The following judgment is made based on the number of coarse particles larger than μ.

1st class: less than 10/- coarse particles exceeding 5μ are present.

2nd grade: 10 to 30 coarse particles exceeding 3μ are present.

Grade 3: More than 30/- coarse particles with a size of more than 6μ are present.

(C) Intrinsic viscosity of polymer This is a value measured at 25°C using 0-chlorophenol as a solvent.

(D) Film properties (a) Film friction coefficient Measured using a slip tester according to ASTM-D-1894B method. The coefficient of static friction was used as a measure of the slipperiness of the film.

(b) Roughness of film surface irregularities The film surface was observed using a stylus type roughness meter, and the difference between the highest and lowest parts of the surface irregularities obtained was expressed in μ units.

Example 1 (Production of particles) Calcium acetate/rum was placed in a container equipped with a stirring device and a reflux tube.
5.4 parts by weight of hydrate, bis-(β-hydroquinethyl)
11.7 parts of terephthalate and 82.9 parts of ethylene glycol + Ji + E were charged, and the mixture was reacted at 190°C for 5 hours with stirring. The obtained particle generation slurry was stirred at a rotation speed of 5000 r, p using a high-speed stirrer.
The mixture was subjected to IH + high-speed stirring for 2 hours at m, to finely disperse the particles and obtain a particle slurry.

(Method for producing polyester) Dimethyl terephthalate 100Mmf# A transesterification reaction is carried out by a conventional method using 70 parts by weight of ethylene glycol and 0.04 parts by weight of manganese acetate tetrahydrate as a catalyst.
The product may be mixed with 0.06 parts by weight of antimony trioxide, 0.02 parts by weight of trimethyl phosphate, and 0.3 parts by weight of the ethylene glycol slurry of the particles produced above, and prepared in advance into an ethylene glycol slurry with a concentration of 10% by weight. The dispersibility of finely dispersed silicon dioxide (specific surface area: 200 m'/F) was first grade and good.

Implementation jl 2 (Production of particles) Bis=(β-
10Mz part of hydroquine (ethyl) terephthalate and 250 parts by weight of ethylene glycol were added and dissolved by heating. Next, 55 parts by weight of calcium acetate hydrate and 40 parts by weight of lithium acetate dihydrate were added while stirring, and the mixture was reacted at 190°C for 3 hours. Next, 200 parts by weight of ethylene glycol, parts by weight of trimethyl phosphate, and 10 parts by weight of phosphorous acid were added,
The reaction was carried out at 180°C for 1 hour. The obtained particle generation slurry was stirred using a high-speed stirrer at a rotation speed of 3000 r, p, m for 2
The mixture was stirred at high speed for hours to finely disperse the particles and obtain a particle slurry.

(Method for producing polyester) A transesterification reaction is carried out in a conventional manner using dimethyl terephthalate (100 M), 70 parts by weight of ethylene glycol, and 0.04 parts by weight of manganese acetate tetrahydrate as a catalyst,
The product contains 0.03 parts by weight of antimony trioxide, 0.02 parts by weight of trimethyl phosphate, 0.6 parts by weight of the ethylene glycol slurry of the particles produced above, and ethylene glycol slurry with a concentration of 10% by weight in advance. 0.2 parts by weight of well-dispersed silicon dioxide (specific surface area: 200 m2/9) was added, and polymerization was carried out in a conventional manner to obtain a polymer having an intrinsic viscosity of 0.627.

The particle size in the polymer was Parank, and the dispersibility was first grade, which was extremely good.

Comparative Example 1 In Example 2, after the transesterification reaction was completed, 0.3 parts by weight of lithium acetate, 0.2 parts by weight of trimethyl phosphate, and 0 parts by weight of antiseptane trioxide were added without adding the particles produced in Example 2. A polymer with an intrinsic viscosity of 0.6 (J9) was obtained in the same manner as in Example 2, except that only 0.03 parts by weight was added and reacted.

The particle size Ldc rank and dispersibility in the polymer were 6th grade, which was not preferable.

Examples 3 to 8 Polyesters were obtained in the same manner as in Example 2, except that the type and amount of the inert material particles were changed. Particle size and dispersibility in the polymer are shown in Table 1.

Example 9 The polyester composition obtained in Example 1 was processed into 29 by a conventional method.
Formed into a sheet at 0°C and longitudinally stretched at a magnification of 6.6 using a biaxial stretching machine.
After stretching at a transverse stretching ratio of s and 4@, heat treatment was performed at 215° C. to obtain a film with a thickness of 12 μm. Work stability during film formation was good, and there were no problems such as film breakage. The friction coefficient of the obtained film was 0.68, the average roughness of the film surface was 0.021μ, and the maximum roughness of the film surface was 0.2
It was 2μ, which was good.

Example 10 A film with a thickness of 12 μm was prepared in the same manner as in Example 9, except that the polyester obtained in Example IP112 was used.

Obtained. The obtained film had a coefficient of friction of 0.64, an average film surface roughness of 0.023μ, and a maximum film surface roughness of 0.24μ, which were good.

Comparative Example 2 A film with a thickness of 12 μm was obtained in the same manner as in Example 9 except that the polyester obtained in Comparative Example 1 was used. The obtained film had a friction coefficient of 0.56, an average film surface roughness of 0.058 μm, and a maximum film surface roughness of 0.59 μm, which were not preferable.

Example 11 In Example 2, after the transesterification reaction was completed, 0.03 parts by weight of antimony trioxide, 0.02 parts by weight of trimethyl phosphate, and the ethylene glycol slurry of the particles produced in Example 2 were added to the product. Then, 0.6 parts by weight of silicon dioxide (specific surface area 200 m'/fi'), which had been well-dispersed by slurrying ethylene glyfur at a concentration of 10% by weight, were added and polymerized by a conventional method. A polymer having an intrinsic viscosity of 0.605 was obtained.

The particle size in the polymer was A rank, and the dispersibility was 1st grade, which was good.

Implementation 1j12 The esterification reaction product was charged into an esterification reaction vessel equipped with a stirrer, a dephlegmator, and a raw material inlet, and the mixture was heated with N2 at 250°C.
Dissolved by heating in the presence of Ethylene glycol slurry of terephthalic acid with a molar ratio of ethylene glycol to terephthalic acid adjusted to 1.20 was continuously supplied to the reaction vessel, water was distilled off, and an esterification reaction was carried out.

105 parts by weight of the esterified product (equivalent to 100 parts by weight of ethylene terephthalate units) was charged into a polycondensation reactor and maintained at 250°C, and 0.2 parts by weight of the particle slurry obtained in Example 2 as particles, antimony dioxide. 0.03
Add 0.1 part by weight of well-finely dispersed silicon dioxide (specific surface area 200 m7!i') as an ethylene glycol slurry with a concentration of 10 parts by weight, and gradually reduce the pressure in the system to initiate a polycondensation reaction. And the intrinsic viscosity is 0.61
6 polymer was obtained. The particle size in the polymer was A rank, and the dispersibility was 1st grade, which was good.

(Margin below) Table 1

Claims (1)

[Claims] When manufacturing a polyester by transesterifying or esterifying terephthalic acid or its ester-forming derivative with a glycol and subsequently performing a polycondensation reaction, the polyester synthesis reaction system may be added at any time before the start of the polycondensation reaction. A method for producing polyester, which comprises adding particles produced by the reaction of terephthalic acid or a terephthalic acid derivative with an alkali metal compound and/or an alkaline earth metal compound outside, and particulate matter insoluble in the system. .