JPS5852345A - Polyester composition - Google Patents

Abstract

PURPOSE:To improve crystallizability of polyesters and to impart crystallization velocity suitable for injection molding, by blending a salt derived from an Mg or Zn compd. and a phosphorus compd. to a polyester. CONSTITUTION:A dicarboxylic acid component composed mainly of an arom. dicarboxylic acid and a glycol component composed mainly of an aliph. glycol are reacted to obtain a polyester. At a stage prior to the early stage of the polycondensation, an Mg or Zn compd. such as zine acetate and a phosphorus compd. selected from phosphonous acid, phosphonic acid, phosphinic acid and esters thereof in an about eguimolar ratio are added to the reaction mixture, whereby 0.05-2wt% (based on the formed polyester) magnesium or zinc salt of the phosphorus compd. is formed in the reaction system. Further, the polycondensation reaction is conducted to obtain the desired polyester compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester compositions. More specifically, it relates to polyester compositions with good crystallinity.In recent years, polyesters (especially polyalkylene terephthalate) have been gaining popularity in engineering due to their good heat resistance and relatively low cost. Its use in the field of plastics is rapidly progressing. However, polyester, particularly polyethylene terephthalate, has poor crystallinity, and its use in injection molding applications that require a high degree of moldability is severely limited.

Therefore, inorganic powders such as talc and other poly! Attempts have been made to modify IIo@* by blending -, but so far no product with sufficiently satisfactory crystallinity has been obtained.

The present inventors searched for a crystal nucleating agent that was more efficient than inorganic powder in order to improve the crystallinity of polyester and give it a crystallization rate that could be used particularly for injection molding applications. It was O who came up with the invention.

That is, the present invention provides a polyester obtained by a direct esterification method from a dicarboxylic acid component mainly consisting of an aromatic dicarboxylic acid and a glycol component mainly consisting of an aliphatic glycol, and a polyester containing at least 1 product of magnesium and zinc. Metal compounds and phos7onic acid, phosphonous acid,
This is a polyester composition characterized in that #io, on-2 weight ratio is blended with at least one phosphorus compound selected from phosphinic acids and their esters.

The composition according to the present invention has excellent crystallinity due to the combination of both compounds. Even more surprisingly, when at least one metal compound selected from lithium, sodium, potassium, etc. and at least one metal compound I#O selected from magnesium and zinc are used together, it is even more efficient. This helps improve the crystallinity of polyester.

As a measure to improve the crystallinity of polyester, a method of blending natural inorganic powder such as talc is already known. However, as in the present invention, a specific O metal compound, a phosphorus compound and an O
It is not yet known that JJ has excellent properties as a crystal nucleating agent.The feature of the present invention is that a dicarboxylic acid component mainly composed of aromatic dicarboxylic acids and a glycol mainly composed of aliphatic glycols are used. Ingredients: A specific crystal nucleating agent may be added to the polyester obtained by direct esterification.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 1. I-su7thalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, bis(4-carboxyphenyl)
Methane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)ketone 1. l,! -bis(4-carboxy7enyl)ethane and the like. Among these, terephthalic acid is particularly preferably used. Other dicarboxylic acid components that may be used in small amounts include dicarboxylic acid components other than dicarmenic acid, which is used as the main component, such as 4-hydroxybenzoic acid, ink-sodium sulfoisophthalic acid, etc. O aromatic oxycarmene alcohol or aromatic dicarboxylic acid component, adipic acid,
Examples include aliphatic dicarboxylic acid components such as azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid, and alicyclic dicarboxylic acid components such as cyclohexanedicarboxylic acid and 414'-methylenebiscitaphexanedicarboxylic acid.

These may be used as a mixture of 8 or more kinds.≠0 As the glycol component in the present invention, the total amount of dalicol is ethylene glycol, tetramethylene glycol, or cyclohexane dimenol. Other glycol components that can be used in small amounts include glycols other than the glycol used as the main component among the above glycols, trimethylene glycol, hexmethylene glycol, diethylene glycol, triethylene glycol, -(L'-Hitorekijetoxy)-phenyl] νpan, bis(+-(e-Hitorekijetoxy)-phenyl]sulfone, bis(a-
(g-Hydroxyethoxy)-3,s-Zig Sodium 7EL] Prepan, Bis[4-(2- and Do4xyethoxy)
-S,S-diglemophenyl]sulfone, etc. These may be used as a mixture of two or more.

There are no particular limitations on the structure of the polyester.

For example, a dicarboxylic acid component and a glycol component are directly esterified in the presence of a suitable catalyst, and then heated and polycondensed under reduced pressure until a predetermined melt viscosity is obtained. The polymerization temperature is determined by the melting point, heat resistance, etc. of the resulting polymer. eThe method of adding a metal salt of a phosphorus compound, which is a crystal nucleating agent specified in the present invention, to a polyester is a method of adding and mixing a metal salt of a phosphorus compound, which is a crystal nucleating agent specified in the present invention. Methods include adding and mixing the powder during the polyester manufacturing process, attaching the powder to chips of the manufactured polyester, or melting and mixing the powder afterward, but the most preferred method is to add one metal to the polyester before the initial stage of the polycondensation process. This is a method in which a compound and a phosphorus compound are added simultaneously or separately, and the two are reacted in polyester to form a salt.
It is a compound. These metal compounds usually include organic acid salts and alcolades. Particular preference is given to -o#i zinc compounds. Even better results can be obtained when the metal compound of the present invention is used in combination with a monovalent metal compound such as sodium, potassium, or lithium. The mixing ratio of both O is preferably about 171 O to 10/l in terms of molar ratio. Especially l
/3 to 3/l is preferable.

As a phosphorus compound, organic phos-7-ionic acid, organic DX7ε
V-so pot W 艷U. Specific examples include 4.78 nylphos-7onate, naphthylphos-7onate, p-tolylphos-7onate, o-tolylphos-7onate, benzylphos-7onate, methylphos-7onate, ethylphos-7onate, butylphos-7onate,
Octyl phosphonite, benzyl phosphonite, p
- Noodle phos7onic acids such as tolyl 7-onite, methylphos7onite, butyl 7-onite, phosphines such as diphenylphosphinic acid, dicyclohexylphosphinic acid, didodecylphosphine lIO #! or their alkyl, aryl, and hydroxyalkyl esters. In particular, favorable results are obtained when using a phos-7-oic acid or a phosphous-7-oic acid containing a swelling hydrogen group 1 (x or more benzene nuclei) directly bonded to a phosphorus atom.

Metal salts such as phos-7-oic acid, phosphous-7-oic acid, and phosphinic acid are prepared by mixing or mixing a phosphorus compound dissolved in a suitable solvent such as ethylene glycol. (by post-heating). When adopting a method in which both compounds are added during polyester O polycondensation to form a salt, the above solutions are added simultaneously or separately and mixed for a predetermined time, usually at normal pressure, to form a salt. rear,
Polycondensation is performed under reduced pressure. When adding the internal solution, better results can be obtained by adding the metal compound solution first.

Further, when the polycondensation is carried out to some extent and is added at a cold stage, a solvent having good heat resistance such as diphenyl ether and having no functional groups such as active hydrogen is necessarily used as a solvent.

The amount of the metal salt used is o, oa-z, o weight percent as salt based on the produced polyester. Particularly preferable amount 2
When used only as a valence O metal compound, 0, XI to 1.
i weight arc, and when a monovalent metal compound and a single stroke metal compound are used together, O, Oa -1 weight≦. If the amount is small, it is ineffective as a crystal nucleating agent, and if the amount is too large, the above-mentioned salt will precipitate during polycondensation, causing foaming and clogging of the glycol outflow pipe. Poly again! - The heat resistance also deteriorates. Depending on the purpose, the compositions according to the invention may further contain other inorganic and/or organic crystallization promoters.
In addition, an inorganic OMM-like reinforcing agent, an impact strength improver such as an elastomer, a mold release agent, a sliding property improver, etc. can be added to the thermoplastic resin.

As described above, according to the present invention, a polyester having excellent crystallinity can be obtained, and the molded articles molded from the composition I#Jt have excellent surface properties and cutting effects.The effects thereof will be explained in detail in the following examples. do.

However, the present invention is not limited to these mirrors.

In addition, various measurements were performed according to the following methods. In addition, the weight in the examples is based on weight unless it differs from weight.

L Intrinsic viscosity solvent: 7/-/l, z, t, tt-tetratap ethane 674 double-lid ratio temperature: 30°C z M point (τM) and tertiary crystallization temperature (To, >
Measurement and evaluation of crystallinity The sample was placed at 40 wI in O differential thermal analysis device manufactured by Karasu Seisakusho.
1, and raise the temperature at a heating rate of 10"G. The position of the endothermic peak, which is related to the melting of the crystal, is Tm. After holding at a temperature 10°C higher than T!1 for 6 minutes, 1oV11I+
The temperature is lowered at a rate of Poly! Let Tol be the position of the heating beater for crystallization of -. Chart
il 2. B-1, the sensitivity is *gao, V.

z-+) Tlm-'ra, (°C) The smaller the value is, the faster the crystallization rate is judged to be.

sharpness of the secondary crystallization peak &/1)
If) The height from the base twin of the exothermic peak accompanying the secondary crystallization obtained in the above measurement was taken as b, the half width of the 11 peak, and the a/b value was used as a measure of sharpness. The higher this value, the more poly! - is judged to have good crystallinity. Example L 1 terephthal@! in a 21 autoclave kept at 66°C in advance! 1199, ethylene glycol 370-, triethylamine O,St- and antimony trioxide in ethylene glycol solution (1,2% w/v) 19- and 9.8. The dehydration reaction is carried out for 110 minutes under the pressure of Sl. After the reaction is completed, the pressure is returned to normal and the acetic acid sub-dihydrate is dissolved at 1,49
Add the ethylene glycol solution containing 9 and stir for 6 minutes. Furthermore, Ksy enylphos 7-ionic acid is 1.0? After adding an ethylene glycol solution containing 51 and stirring for 6 minutes, the pressure was gradually reduced. The pressure was reduced to 0 and 1-Hgt for 4 Is minutes, during which time the temperature was raised to tqh'ct. The polycondensation reaction continues until the t-predetermined melt viscosity is reached! After that, the pressure was returned to normal using nitrogen gas, and the polymer was extruded into water through a pore installed at the bottom of the autoclave using nitrogen gas pressure, and cut into chips using a cutter.

The resulting polymer has an intrinsic viscosity tfo of 6Q and a melting point of 25.
9℃, secondary crystallization temperature is gio'c, teho-〒afu#
The temperature was 39°C, a/ba a#1lit, and O.

Example 2 Nucleating agent 01 and different types of polymers were obtained in the same manner as in Example. The L remer composition is shown in Table 951, and the crystallinity evaluation results are shown in Table 2.

Table 1 111 Foaming was intense during polycondensation, and it was difficult to obtain a polymer.

◆8 Table 2 showing molar ratios Example a Poly! 0 poly got -! - Evaluation results of composition and crystallinity are shown in the third
Shown in the table.

#I3 table Special fraud applicant: Toyobo Co., Ltd. Kinsha

Claims (1)

[Scope of Claims] L A polyester obtained by a direct esterification method from a dicarboxylic acid component mainly composed of aromatic dicarboxylic acid and a dalicol component mainly composed of aliphatic dalicol, Y
At least 41 O metal compounds different from danesium and zinc and at least 1 selected from phos-7-oic acids, phos-7o-acids, phosphinic acids and their esters.
>Salts with phosphorus compounds 0. A polyester composition characterized by blending OR-, -* outside weight. At a stage prior to the initial stage of polycondensation in the synthesis of Listester 0, P1x equimolar O metal compound and phosphorus compound were simultaneously KS
The polyester composition according to claim 1, wherein the metal compound is an organic acid salt of a metal and/or an alcoholade. 2. Polyester composition according to item 2. A part of the metal compound is replaced with at least one kind of alkali metal compound selected from lithium, sodium, and potassium compounds. Briester composition.