JPS621725A - Production of polyester - Google Patents

Abstract

PURPOSE:To produce a polyester capable of giving films having improved surface flatness and slipperiness and fibers, rich in water repellency and slightly causing yarn breakage, by incorporating a small amount of a fluorine-containing compound in a polyester consisting of ethylene terephthalate as main constituent units. CONSTITUTION:(B) One or more of fluorine-containing carboxylic acids expressed by formula I (Rf is m-valent fluorine-containing organic group; m is an integer 1-4), e.g. pentafluorobenzoic acid, and fluorine-containing compounds expressed by formula II, e.g. 2,4-fluorobenzyl alcohol, in an amount of 1mmol%-10mol% based on an acid component of a polyester are added to a production process of (A) the polyester consisting of ethylene terephthalate as main constituent units to afford the aimed polyester.

Description

[Detailed description of the invention] Field of application> The present invention has excellent flatness, slipperiness, crystallinity, and heat resistance.
It also relates to the production of modified polyesters with good electrical properties, and more specifically, by using a fluorine-containing metal compound, the surface properties of polynisnal molded products are improved, and r! ! , Kik, films, molding materials, etc. The present invention relates to a technology for producing polyester suitable for a wide variety of uses such as , Kik, films, and molding materials.

<Prior art> According to the prior art 6, in the production of cloth S-ble fiber, inorganic pigments such as titanium oxide are mixed in order to reduce the abrasion resistance of the fiber and prevent thread breakage, and furthermore, fiber processing is required. In order to reduce the metal abrasion resistance of the fiber surface, the manufacturing process is stabilized by applying an oil agent mainly composed of a surfactant.

Although these methods are effective means of process improvement,
Yarn breakage due to titanium oxide aggregates.

This causes other problems such as the generation of scum due to thermal decomposition of the oil.

In addition, in film applications, it is necessary to simultaneously satisfy the contradictory characteristics of surface flatness and slipperiness, so inorganic fillers such as titanium dioxide, calcium carbonate, kaolin, clay, and barium sulfate are added to polyester, or catalysts are added to the polyester. This characteristic has generally been imparted by adjusting the particle size and generation amount of insoluble particles due to metal residue. In these methods, the contamination of aggregated particles and coarse particles is unavoidable, which causes dropouts in applications such as video and audio. Separately, coating agents are used to impart slipperiness, but from a process perspective, the -1-ting method is less industrially efficient than the method of directly forming fine irregularities on the surface of the polyester film. It is hard to say that it is advantageous.

<Objective of the Invention> An object of the present invention is to produce a useful polyester having excellent properties such as good lubricity and a flat surface.

As a result of diligent efforts to achieve the above object, the present inventor discovered that the surface characteristics of polyester molded products can be greatly improved by incorporating a small amount of a fluorine-containing compound into polyester. , which led to the present invention. Moreover, in the method of the present invention, since a fluorine compound is added to the polynisder at the manufacturing stage, the polyester molded product can be easily handled during the processing process.

That is, the present invention provides a polyester whose main structural unit is ethylene terephthalate with the general formula (Rf +-+CC00)I) ------
Set (1) and (Rf +-4:OH)m
This is a method for producing a polyester containing at least one fluorine compound represented by the formula -.

The present invention will be explained.

The polyester used in the present invention does not mean that the main structural unit is ethylene terephthalate, but it can contain a copolymer component. The copolymer component is, for example, isophthal rlt + 5-Na sulfoisophthalic acid, 2
, 6-naphthalene dicarboxylic acid, 1,4-diphenyldicarboxylic acid, aliphatic dicarboxylic acid, or a dalicol component such as 1+4-butanediol and cyclohexane dimetatool.

The polyesters of the present invention can be used as homopolymers, copolymers, polymer blends, as well as antistatic agents.

It may also contain flame retardants, extinguishing agents, and lubricants.

In the present invention, J6 refers to the fluorine-containing carboxylic acid represented by the general formula (1), for example, as a benzoic acid visiting conductor, 2,4-bis(trifluoromethyll-fFa2+6
＃（／／）〃L5／'
(1) ' 2+3- :) Fluorobenzoic acid 215- # 2.6-difluorobenzoic acid 3.4- # 315- /' 2-fluoro-4-(trifluoromethyl)benzoic acid & 2-z-5 -(//n〃 3- -t -3-() tt4- u
-2-(n) tt4-n
-: t-() #ben difluorobenzoic acid 0, m, j) -fluorobenzoic acid 2-tallow-6-fluorobenzoic acid 2- and 3- and triple olomethylbenzoic acid aliphatic, rilubone CF*CJ b
o(Jl(+ rr-1\pukfluoropbutym, pentanol+'n rm acid, perfluorooctanoic acid-
Half-open Iff pionic acid, trifluoro c2 acetic acid,
2.4- and 3.5-bis(trifluoromethyl)phenylacetic acid.

2+3−- + 2+4 * z, s + 2+6
-difluorocinnamic acid, 3.4-, 3.5-difluorocinnamic acid, 2.3-, 2.4-, 2.5-,
2.6-difluorof, enyl acetic acid, 3I4-1315
-difluorophenyl acetic acid +2 +3 +4 fluorocinnamic acid +2 +3 +4-fluorophenyl acetic acid, hentafluoro-cinnamic acid.

2+, 3+, 4-()lifluoromethyl)cinnamic acid, 2+, 3+, 4-(trifluoromethyl)phenylacetic acid.

Examples of polycarboxylic acids include tetrafluorophthalene, fluorotrimerite 1
11I, fluoropyromellitic acid.

Fluorinated 4,4'-biphenyldicarboxylic acid.

Fluorinated 2,6-su7thalenedicarboxylic acid, and further as oxycarboxylic acids, tetrafluoro4-hydroxyphenylcarboxylic acid 17 dorafluoro2-human-
Examples include xyphenylcarboxylic acid, trifluoro-4-hydroxyisophthalic acid, hexa7fluoroglutarmethyl)mandelic acid, and the like.

-〇)1 As for the inclusions.

2,4-,3+5-bis(trifluoromethyl)benzyl alcohol + 2+3 + 2.4-+2,5 -
, 2.6-, 3.4-, 3.5-difluorobenzyl alcohol, 2,3*2+4*z
,s-,216-S 3+4-? 3.5-difluorophenol, 2-,4-fluorobenzyl alcohol, 2+,3+,4-fluorophenol, 2-fluoroP-4-(trifluoromethyl)phenol, 2-fluorop-5-()trifluoro methyl)phenol-4-fluora-2-(trifluoromethyl)phenol, 2-, 3-, 4-()
Rifluta methyl]phenol, pentafluorophenol, l-(pentafluorophenyl)ethanol +
2 + 3 t 5 s 6-titrafluorophenol, 3-,4-()lifluoromethyl)benzyl alcohol, and tetrafluoronohydroquinone, but the present invention is limited to these compounds. Needless to say, it is not.

The conditions for adding these fluorine compounds are not particularly limited, and they may be added at any point during the polyester manufacturing process, and there are no particular limitations on the evidence. The minimum effective amount is approximately 1
0mi! The maximum amount is 7 mol (mmol) φ, and the upper limit is 10 mol (mol)%.

The method for producing polyester according to the present invention does not require any special method other than using the above-mentioned additives, and either a transesterification method or a direct esterification method can be adopted. The fluorine compound can be added either singly or after being branched into glycol or the like.

<Operation and Effect> The purpose of the present invention is to improve the surface of polyester by adding a fluorine compound, which effectively utilizes the cohesive energy and surface tension of the fluorine compound, and improves water repellency and slipperiness. Improvements are brought about.

<Effects of the Invention> By using the polyester obtained by the present invention, a transparent film with improved surface flatness and slipperiness can be produced. In addition, it is possible to obtain water-repellent folded fibers with less frictional resistance and less yarn breakage.

Furthermore, from these properties, a molding material with improved stain resistance and mold releasability can be obtained.

<Example> The present invention will be explained in more detail below with reference to Examples.

In the examples, the contact angle is the advancing contact angle between the film and water measured with a goniometer. Frictional resistance was evaluated using a 75 denier/36 filament yarn using the copper wire breaking method and the relative ratio of the wear depth of the copper wire. (Yarn running speed s5om
/minute, time 30 minutes, thread tension 30 gr) Also, the static friction coefficient is the value between the film and the film, and is based on ASTM-
According to D-1894-1963 method.

Example 1 1 mol of dimethyltephthalate (DMT), 1.8 mol of ethylene glycol, 30 mol of manganese acetate
mmoA! % and antimony trioxide in an amount of 30 mmol, the transesterification reaction was completed while methanol was distilled off until the internal temperature reached 220° C., and then 33 mmol of trimethyl 7 osulfate was added.

Subsequently, 300 rILmo1% of pentafluorobenzoic acid was added to DMTK, and the temperature was increased to 290°C under high draft until the intrinsic viscosity was 0.610 + c.
olL=70.5+eoA! A polyester with b=4.5 + softening point of 262.2°C was obtained. This polyester unstretched film has a water contact angle of 81" and is a water repellent polymer with a water contact angle of 6.

Lie this bo + J 7- 75 do/36 fil
When yarn was formed using a K-sized spinning machine and the degree of abrasion due to copper wire breakage was evaluated using the method described above, the relative ratio was 0.
4 was good and rare.

Examples 2 to 9 Polyesters were produced using various fluorine compounds under the conditions shown in Table IK, and the physical properties were also listed in Table 11C.

From the results of the experiment, it was found that the physical properties of the °C polyester, especially the contact angle and friction, were improved by 1 compared to the comparative example.

Procedural amendment April 2, 1986

Claims (1)

[Claims] A polyester whose main structural unit is ethylene terephthalate has the general formula (Rf)-(COOH)m...(I) and (Rf)-(OH)m...(II) [Formula (I) In formula (II), Rf is an m-valent fluorine-containing organic group, and m is an integer of 1 to 4. ] A method for producing a polyester containing at least one fluorine compound represented by the following.