JPH02180923A - Fine polyester particle and composition containing same - Google Patents

Abstract

PURPOSE:To obtain the title particle which can show excellent adhesiveness at the interface when added to a polyester resin of excellent heat resistance by using a specified acid component. CONSTITUTION:An acid component of the formula, for example, at least 20 equivalent % (desirably at least 50 equivalent % where high heat resistance is necessary) 1,2,3-benzenetricarboxylic acid is used to form a heat-resistant polyester particle (of a particle diameter <=50mum, desirably 0.1-1mum). 0.01-70wt.% said particles are added to a polyester to form a mixture, which is formed into a molding, a fiber, a film or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyester fine particles having excellent heat resistance.

[Prior Art] Known methods for producing polyester fine particles include pulverization, melting, or production from a solution state. As a method of pulverization, there is a method in which once solidified polyester is mechanically pulverized, as in Japanese Patent Application Laid-open No. 62-197424.

In addition, molten polymer is injected from a nozzle (Japanese Patent Application Laid-Open No. 56-157431), and precipitation from a solution (Japanese Patent Application Laid-open No. 8
2-101628. [)E2253361] Polyester fine particles can also be obtained.

In addition, as heat-resistant fine particles, inorganic fine particles and crosslinked fine particles of vinyl polymer are known, but when added to polyester resin, they have poor adhesive strength at the interface. Therefore,
Crosslinked fine particles of a vinyl polymer copolymerized with a polyester and a reactive group capable of covalent bonding are also being considered (Tokyo Patent Publication No. 62-58388).

[Problems to be Solved by the Invention] However, with the pulverization method, it is difficult to obtain submicron particles, the particle size distribution is wide, and the particle shapes vary, making it particularly difficult to obtain 1q of spherical particles. Furthermore, since crosslinked polymers cannot be used in methods of producing particles from a melt or solution state, fine particles with excellent heat resistance cannot be obtained.

Furthermore, crosslinked fine particles of a vinyl polymer copolymerized with the above-mentioned polyester and a reactive group capable of covalent bonding have to be pulverized, making it impossible to obtain particles with finely uniform particle sizes.

An object of the present invention is to provide polyester fine particles that have excellent heat resistance and excellent adhesion at the interface when added to a polyester resin.

[Means for Solving the Problems] The present invention provides polyester fine particles characterized by containing 20 equivalent % or more of the acid component.

In the present invention, -CO means 100CO CO , and specifically, 1,2.3-benzenetricarboxylic acid, 1,2.4-benzenetricarboxylic acid, 1,3.
It is based on 5-benzenetricarboxylic acid or derivatives thereof. This ingredient can be used depending on its purpose.
Although it can be made to take any value of 0 equivalent % or more, it is preferably 50 equivalent % or more when a high degree of heat resistance is required. .

The remaining O to 80% equivalent valve is based on dicarboxylic acid, which is a common raw material for polyester, or an acid derivative thereof, and may have a substituent on the nucleus. For example, those based on terephthalic acid, isophthalic acid, 2-chloroterephthalic acid or derivatives thereof.

In addition, the diol component may be either aromatic or aliphatic, such as ethylene glycol, cresol,
Examples include those based on bisphenol A and the like.

The polyester in the polyester composition containing polyester fine particles of the present invention refers to aromatic polyesters such as polyethylene terephthalate and polyphenylene terephthalate, or aliphatic polyesters.

The particle size of the Q fine particles of the present invention is preferably 50 μm or less, and 0.5 μm or less.
More preferably, the thickness is 0.05 μm or more and 10 μm or less.

More preferably, it is 0.1 or more and 1 μm or less.

The polyester microparticles of the present invention can be obtained by precipitation from a homogeneous polymerization system. The manufacturing method will be briefly explained. A solution containing a carboxylic acid dichloride and a solution containing a diol may be mixed under high speed stirring. At that time, the particle size and shape can be controlled by the stirring speed, the type and concentration of the solvent, catalyst, and monomer. For example, the following reactions can be mentioned: Triethylamine is added to a solution in which diol is dissolved, and the mixture is stirred at 2,000 rpm or more, and a solution in which dicarboxylic acid dichloride and tricarboxylic acid trichloride are separately dissolved is added dropwise. Fine particles and triethylamine hydrochloride will precipitate, and when filtered and washed, fine particles will be obtained.

It can also be obtained by direct polymerization of dicarboxylic acid and diol using a phosphoric acid catalyst, or by interfacial polymerization of carboxylic acid dichloride and an alkali metal salt of diol.

The fine particles obtained in this way are coated with polyester resin.
．． It is added in an amount of 01 to 70% by weight to form molded objects, fibers, and films. The amount added varies depending on the purpose, but if it is less than 0.01% by weight, the effect of addition will be small, and if it exceeds 70% by weight, the strength will be reduced. More preferably 0.
05 to 50% by weight. The particles may be added before or after polymerization, but in consideration of the dispersibility of the particles, addition before polymerization is preferred.

[Effects of the Invention] The fine particles of the present invention have excellent heat resistance and a fine particle size, and when added to a polyester resin, have excellent adhesion at the interface, and are used for molded bodies, films, fibers, etc.

[Examples] Next, Examples will be shown to explain the present invention more specifically, but the present invention is not limited thereto.

Example 1 Ethylene glycol 1.86Q (30 mm
o l>, triethylamine 12°Iq (120m
mol>, add 100 ml of tetrahydrofuran (THF), stir at 2000 rpm under nitrogen, and heat at 10'C in a water bath.
Terephthalic acid dichloride while cooling to 3.05
Q (15mm.

), trimesic acid trichloride 2.650 (1Qmm
o l ) dissolved in 100 ml of THF.
It took a few minutes to drip. Precipitation begins at the same time as the dropping begins.

After the dropwise addition was completed, stirring was continued for 60 minutes, and the precipitate was filtered off. This precipitate was washed several times with methanol and THF and heated to 100°C.
and dried under vacuum.

The average particle size of the obtained particles was 4.5 μm, and observation with an electron microscope revealed that they were approximately spherical and had a uniform particle size.

Furthermore, thermal analysis revealed that the particles had no melting point and had a 10% heat loss temperature of 355°C.

Example 2 A similar experiment was carried out in Example 1 except that all the acid components were replaced with trimesic acid chloride and the concentration was further reduced to 1/2. As a result, particles with a particle size of 1.1 μm and a 10% heat reduction fi temperature of 410° C. were obtained, which were extremely excellent in heat resistance. When polyethylene terephthalate was polymerized by adding 1.0 mold percent of these particles before polymerization, no agglomeration of the particles occurred during polymerization, and when this was formed into a film, no voids were generated by stretching and it was transparent. A film was obtained.

Example 3 Bisphenol A6.850 (30 mmo
I), sodium hydroxide 2.64C1 (66mmo
I), Triton (X-100) 2g,
Add 100ml of distilled water. Stir at 2000 rpm under nitrogen, and add 5.31 Q (2
A solution of 0 mmol I> dissolved in 150 ml of chloroform was added dropwise over 30 minutes. Precipitation begins at the same time as the dropping begins. After the dropwise addition was completed, stirring was continued for 60 minutes, and the precipitate was filtered off. The precipitate was washed several times with distilled water, methanol, and chloroform, and dried under vacuum at 100°C. The average particle diameter of the obtained particles was 0.7 μm, and observation with an electron microscope revealed that they were approximately spherical and had uniform particle diameters.

Comparative Example 1 In Example 1, trimesic acid trichloride was
Particles were prepared in the same manner as in Example 1, except that the chloride was changed to 5.18 <] (26 mmol).
Although particles with a uniform particle size of 4.0 μm were obtained, 2
It melted at 95°C. Although this was added before polymerization in the same manner as in Example 2, the particles agglomerated during the polymerization.

Comparative Example 2 Polyethylene terephthalate obtained from ethylene glycol and terephthalic acid was dissolved in γ-butyrolactam at 10% by weight, and precipitated in methanol in the form of a mist. This was filtered and dried to remove particles.

The particle size was 1.5 μm and the particle size was well matched, but at 260'C
It melted. This was added before polymerization in the same manner as in Example 2, but no effect was obtained.

Claims (2)

[Claims] (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Polyester fine particles characterized by containing 20 equivalent percent or more of the acid component. (2) Polyester fine particles according to claim 1 of 0.01 to
A polyester composition characterized by containing 70% by weight.