JPS5941330A - Preparation of polyester composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition containing homogeneously dispersed powder for modification, and having the moldability of the base resin, by dispersing fine powder in a polyether compound, adding the resultant composition to the reaction system at a specific stage, and carrying out the polymerization of polyester. CONSTITUTION:Polyester is prepared by the direct polymerization of (A) a dicarboxylic acid and (B) a glycol. In the above process, a composition obtained by dispersing (C) powder having an average particle diameter of <=5mu (e.g. carbon black) in (D) a polyether compound (preferably polyethylene glycol etc. having a molecular weight of >=300) is added to the reaction system when the acid value of the reaction system is <=2,000eq/10<6>g, and the polymerization is completed to obtain the objective composition.

Description

Detailed Description of the Invention The present invention introduces powder into polyester to modify the polyester, improves the uniform dispersion of the powder, and eliminates obstacles in the molding process of the modified polyester. This is to contribute to improving the quality of the modified polyester by reducing the amount of polyester.

It has conventionally been known to introduce and add powder to polyester to modify it.

When forming the modified polyester into fibers or films,
If the powder is used as all or part of the constituent material of the fiber or film (unless it is used as a regenerating material), no matter how small the average diameter of the powder particles, agglomeration and association will occur and the fiber or film will become clogged during molding. , which promoted d^ to the nozzle [] gold and caused serious trouble.Therefore, a large ITJ decrease in productivity occurred.-10,000.

Non-uniform dispersion due to agglomeration and association of powder 1+ has been a cause of deterioration in quality of molded products such as fibers and films.

In order to obtain a polyester composition that can produce molded products such as ruts and films in which powder (+) is uniformly dispersed, in-depth studies and ωF
As a result of research, we have finally completed the present invention. In other words, the present invention produces polyester from dicarboxylic acid and glycol by the direct weight method! 8! When producing a composition, powder with an average particle diameter of 5 μ or less is dispersed in advance in a polyether thread compound.

This is a method for producing a polyester composition, which is characterized in that in the polymerization step of the polyester described in i+fJ, it is added when the acid value in the reaction system is 2000 eq/10'M' or less, and the polymerization of the polyester is completed.

The polyester used in the present invention may be mainly a polyester that can be formed into fibers or films, but 85 moles or more of the polyester may contain repeating aliphatic alkylene terephthalate (a terephthalic acid polyester with bamboo units). Aromatic dicarboxylic acid-based polyamide is preferred. Among glycols and dicarboxylic acids for forming polyester, the glycol is ethylene glycol.

Tetramethylene glycol, hexamethylene glycol, and 1,4-cyclohexanedimethanol are mainly used, but propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like are also used.

Terephthalic acid and its ester-forming derivative m1+ are mainly used as dicarboxylic acids.

Furthermore, isophthalic acid, phthalate-branched acid, 5-sulpoisophthalic acid, adipic acid, sebacic acid, hexahydroterephthalic acid, and ester-forming derivatives thereof are used.

Furthermore, p-oxybenzoic acid, p-oxyethoxybenzoic acid, ester-forming derivatives thereof, and the like are also used.

Note that the polyester in the present invention includes a polyfunctional crosslinking agent such as trimethylolpropane, pentaerythritol, glycerin, and trimesic acid, a monofunctional end-19 stopper such as monomethoxypolyethylene glycol, and naphthoic acid, polystyrene, and polyester. It may also contain additives such as phosphorus, polyether thread compounds, and other additives such as antioxidants, ray absorbers, retardants, and pigments.

The powder used in the present invention has an average particle diameter of 5μ or less, and specifically carbon black has a specific volume resistivity of 500·crn to 500Ω·C.
nl conductive carbon black (also available), oxidation 11 ships, tin oxide or zinc oxide simulated with titanium oxide, tin oxide coated with titanium oxide, and furthermore, the specific resistivity of the product is 100Ω.・OIL~1000Ω・CIn conductive zinc oxide and tin oxide.

Examples include calcium phosphate, calcium carbonate, zinc phosphate, silicic acid, zirconium oxyacetate, zirconium oxide, antimony oxide, gallium oxide, diarsenic trioxide, calcium oxide, aluminum oxide, silica dioxide, and λ linyl. The above powders can be used alone or
A mixture of two or more types may be used.

The BoIJ r-del yarn compound to which the powder fJfj is added in the present invention preferably has a molecular group of 300 or more, and includes polyethylene glycol 400, polyethylene glycol 20,000. Polyethylene glycols with hydroxyl groups at both ends, such as methoxypolyethylene glycol,
R-0+C like phenolic polyethylene glycol
A polyethylene glycol derivative having a hydroxyl group at one end and represented by H2CH20-) II.

Or a polyethylene glycol derivative in which the water V groups at both ends are blocked, such as R■-0+CH2-CIn2-0→mR■ (r<+ r<r I R■ is an argyl group,
(monovalent organic groups such as allyl group), fc/ma, polyethylene glycol or both ends of monovalent organic group containing cyanethyl group, amino-containing monovalent organic group, carbogylic group, epoxy-containing monovalent organic group A polyethylene glycol conductor substituted with an organic group, a monovalent organic group containing a vinyl group, or an IJ
(R1l+ is an organic residue such as an argyl group or allylva) or a general formula R' (-XO-3 .

(-YO-) A polyether compound represented by RV (RN, RV tJ: II, OH or a monovalent organic residue, x.

Y is inserted and '/c represents an unsubstituted algylene group or arylene group, which may be the same or different.)

(In addition, 11+ m+ p+ qt r+ S is a number of 0 or 1 or more, preferably a number such that the number of molecules of the polyether compound is 300 or more.) Next, in the present invention, the powder of 111 is treated with polyester. The method of dispersing the ether compound is not particularly limited, but for example, a polyether compound is heated and melted, 1 ml of a powder from a specified company is added while stirring, and then the polyester is polymerized. The composition may be added to the composition, or the composition may be cooled and solidified, and the composition may be crushed and added to the composition.

Although the reason for this is not clear, powder 1, which is the object of the present invention,
Modified by +FC. In order to obtain a polyester composition in which Powder 1+ is uniformly and finely dispersed, and which does not impair productivity during molding, it is necessary to use a powder that has been previously dispersed in a polyether compound, and to prepare a drink with this powder. It is necessary to simultaneously satisfy two conditions: the point of addition is during the polymerization process of polynisder, and the acid value in the reaction yarn is 2000 eq/106 r or less.

For example, the acid value during polyester polymerization is 2000 eq/
Even if the powder is less than 106r, the polyester composition of the present invention cannot be obtained even if the powder itself is added as it is or if it is added after being finely dispersed in ethylene glycol which is not a polyether compound. Furthermore, even if a composition in which powder is added and dispersed in advance to a polyether compound is used, the polyester composition of the present invention cannot be obtained if the powder is added at a point when the acid value exceeds 2000 eq/106F during polyester polymerization. As described above, by carrying out the method of the present invention having such a configuration, it is possible to obtain a polyester composition in which the powder is uniformly and finely dispersed and the productivity during molding is not poor.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.・Example 1 46.651ζf of prephthalic acid was placed in a polynisder reaction vessel.

Ethylene glycol 38.33 μm, triethylamine 0.3 mol% (based on terephthalic acid), and antimony trioxide as antimony atoms were charged at 0.05 mol% (based on terephthalic acid), and added with N2 gas at 2.51c9/oA. The thread was heated under pressure and reacted at 245°C for 100 minutes with stirring and distillation of water.

When the acid value of the reaction yarn reached 450 eq/106f', polyethylene glycol (average molecular fd
20000 ) with 50w of zinc oxide (average particle size 2μ)
The composition in which t% was added and dispersed was added to the reaction yarn in No. 111.
．． 6 kf was added. Thereafter, the pressure was gradually reduced and the temperature was increased to 275° C. and 0.4 lHr or less, polymerization was carried out for 60 minutes, the polymerization was completed, and chips were removed in one batch.

The ultimate bulk density 1d of the obtained polyester composition was 0.64. This polyester composition was heated at 80°C under reduced pressure for 6 hours.
It was dried at 130° C. for 16 hours. The dried polyester composition was discharged using a 0.228 #lIjφ-0,3 fine 1-12 hole nozzle, a three-layered filter consisting of one piece of NASLON 20 μm & 300 mesh wire mesh, and one piece of 60 mesh wire mesh, and the polymer discharge hole was 6. Spinning is performed under the conditions of Oy/min, spinning take-off speed of 900χ, and nozzle temperature of 275°C.
c.

As a result, the back pressure increase is Q, l (lCgloA) 10
A-[Ir.

[This unit indicates the increased differential pressure (ky/oA) over the filter of l tt per hour IIJI. ]
Met. Next, the obtained undrawn yarn was brought into contact with a hot plate at 110° C. and stretched 3.0 times to obtain a drawn yarn. 36000m
While obtaining the drawn yarn, no yarn breakage or fluffing occurred.

Note that FIG. 1 shows the appearance of the polyester composition obtained by the method described in sFjfJ when observed under a microscope at a magnification of 700 times. What appears black is zinc oxide, which is uniformly dispersed in the light.

Comparative Example 1 A composition in which 50 wt % of zinc oxide with an average particle size of 2 μm was dispersed in polyethylene glycol (half-uniform molecular weight M 20,000) was placed in a polyester reaction pot along with terephthalic acid, ethylene glycol, and triethylamine.

fc was processed in the same manner as in Example 1 except that it was initially prepared together with 5b203. The obtained polyester composition was poured in the same manner as in Example 1, and spinning was performed under the same conditions. As a result, the intrinsic viscosity was 0.65, and the back pressure increase was 15 [:ky/c
jA]/ctA-Hr.

Furthermore, when the obtained undrawn yarn was drawn in the same manner as in Example 1, the number of fluffs was about 1,000/36,000 m, and the number of yarn breaks was 25/36,000 m.

Note that FIG. 2 shows the polyester composition obtained by the above method, magnified 700 times. In Figure 2, coarse particles resulting from agglomeration and association of primary particles of zinc oxide can be seen.

Comparative Example 2゜Zinc oxide was added to ethylene glycol by 50wt% (10% by weight)
000r, p, m) dispersed by 1&? A polyester composition was obtained by processing in the same manner as in Example 1, except that ffl was used instead of the composition in which zinc oxide of Example 1 was dispersed in polyethylene glycol (semi-uniform molecular m20000).

The obtained chips were spun under the same conditions as in Example 1.

As a result, the increase in back pressure during spinning is l6 (Icy/ct
A]/czA・11r. Next, when the obtained undrawn yarn was stretched under the same conditions as in Example 1, the number of yarn breaks was h/36000.
m, and the number of fuzz is 750-800 pieces/36000m
Met.

In addition, the polyester composition obtained by the above method was
The enlarged view is shown in Fig. 3 a+b.

This also shows many coarse particles.

Examples 2-6. Comparative Examples 3 to 5 In Example 1, all the treatments were carried out in the same manner as in Example 1, except that the polyether compositions shown in Table 1 were added to the reaction system at a predetermined acid value.

As a result, the increase in back pressure during spinning and the number of yarn breakages during stretching of each of the obtained polyester compositions/36000 m
, number of fuzz/36000m are also listed in Table 1.

As is clear from Table 1, it can be seen that the polyester composition obtained according to the method of the present invention exhibits good moldability with less increase in back pressure during spinning and less yarn breakage.

[Brief explanation of the drawing]

This is a photograph of the Stell composition magnified 700 times using a microscope. Patent applicant: Toyobo Co., Ltd. Hitsuji l Figure--h-^-hehehe bill No. 21! l Akira 31! ] α Dream 3

Claims (1)

[Claims] (1) When producing polyester from dicarboxylic acid and glycol by the direct weight method, the average particle diameter is 5 μm.
A composition in which the following Powder 1+ was previously dispersed in a polyether yarn compound was added to the polyester undercarriage process in step 1, when the acid value in the anti-core yarn was 2000 eq/106f or less to prevent polymerization of the polyester. 1. A method for producing a polyester composition, characterized by completing the process. (2) The method for producing a polyester composition according to item 1, wherein the powder 1+ is carbon black. (3) A method for producing a polynyster layer 4 composition according to item 1, wherein the powder is zinc oxide or tin oxide. (4) The method for producing a polyester composition according to claim 1, wherein the powder is calcium oxide, zinc oxide, calcium carbonate, or zinc carbonate. (5) The powder is zirconium acetate or zirconium oxide. A method for producing a polyester composition according to claim 1. (6) A polyester composition according to claim 1, wherein the powder is antimony saponide, gallium oxide, and 1M calcium trioxide. (7) The method for producing a polyester composition according to claim 1, wherein the powder is aluminum oxide, silicon dioxide, or kaolinite.