KR890001056B1 - Polyester yarn's making method - Google Patents

Abstract

The method treats polyester yarns with an alkali attenuating process to form fine irregularities on the yarn surface for better color setting and clarity. When reacting a dibasic acid having terephthalic acid as the principal component, or an ester forming derivative of the dibasic acid, with at least one of alkylene glycols to synthesize polyester, the reaction mixture is arranged to contain a 5-valent phosphorus compound having thiophosphoryl group in 0.1-4 mol% to the dibasic acid and the total equivalent of metal to the phosphorus compound in the ratio of 0.5-3.5 times so that the phosphorus compound and metal compounds being added without advance reaction continuously synthesize polyester chip to be dried to 0.003% water content for use in known process of yarn production.

Description

Manufacturing method of polyester company

1 is a scanning electron micrograph taken at 5,000 times the cross section of a polyester yarn obtained by the method of Example 1 of the present invention.

2 is a comparative photograph obtained by the method of Comparative Example 2.

The present invention relates to a method for producing a novel polyester yarn that can exhibit a remarkable deep color effect and clarity as compared to the general polyester yarn when colored by having a number of fine irregularities on the fiber surface after the alkali reduction process. In general, polyester is widely used as a synthetic fiber because it has many excellent properties.

However, polyester fibers have a drawback in that they are poor in color and lack of sharpness when colored compared to other fibers such as acetate, biscous rayon, wool, silk, and acrylic fibers.

Conventionally, in order to solve these drawbacks, there have been attempts to improve dyes and chemically modify polyesters, but there are no effective results yet.

In particular, as a representative method of improving the defect of such a polyester, (1) a method of coating a low refractive index resin on the polyester fiber surface.

(2) A method of imparting fine concavities and convexities to the fiber surface by performing plasma irradiation on the surface of the fabric and knitted fabric.

(3) A method of forming an excellent fine unevenness on the surface of the fiber by alkali-reducing the polyester fiber to which 0.1-10% by weight of inorganic fine particles such as silica sol is added is proposed.

Among them, the method of (1) reduces the fraction of white light reflected on the surface of the fiber, so the effect of improving the color is recognized, but the low refractive index resin coated on the surface is easily dropped off by washing or the like, and its durability is very poor. There is this. In addition, the method of electricity (2) is a costly plasma discharge facility, which can cause a cost increase, and the effect of improving color performance is not sufficient, and the fiber surface behind the plasma irradiation does not have irregularities, so that the fiber structure during coloring There is a drawback that the smooth fiber surface comes out to the surface and causes color spots by the movement of the fibers in the interior.

On the other hand, the fiber produced by the method (3) does not have a deep color effect, and irregular irregularities are randomly distributed on the surface of the fiber. There is a drawback of causing color spots as a cause. The present inventors have made the polyester fiber to produce a polyester fiber having no defects as described above and further improving color depth and sharpness by forming a myriad of uniform micropores in the length direction of 0.1-1.0 micron in the polyester fiber. Results of the exception of polyester fibers containing phosphorus-containing metals precipitated by the reaction of phosphorus and metal compounds during the ester polymerization process and the surface irregularities and color improvement effects of the fiber after alkali reduction I was able to figure out the following.

That is, in the conventional method, a compound consisting of atoms Phosphoryl (III) and (V) groups, which are the centers as phosphorus compounds, alone or in combination, reacts the phosphorus compound with a metal compound capable of reacting precipitation during the polyester polymerization process. Many methods have been proposed to precipitate phosphorus-containing metals, but in this case, the size of the precipitated particles is not only uniform but also coarse, so that the size of the surface irregularities after alkali reduction is irregular. As a result of roughening, it was found that not only the effect of improving the color was insufficient, but also the fibril resistance was reduced.

Therefore, in view of this fact, the present inventors use a sulfur-containing phosphorus compound having a central valence thiophosphoryl group, so that the precipitated particles are not only uniform in size but less reaggregated and have finer uniform particles. It was found that polyesters containing could be produced.

In order to prevent re-agglomeration of the polyester chip thus produced by high temperature drying at normal pressure, low temperature drying is performed under a specified reduced pressure so that the uniformity and size of the microparticles distributed on the chip after the completion of polymerization are not maintained. Alkaline treatment of the fibers obtained under normal spinning conditions by drying the chips dried under these specific conditions allows the deep color effect and sharpness to be achieved when the length of the fiber surface irregularities in the longitudinal direction is dyed in the range of 0.1-1.0 micron. It was found that polyester fabrics and knitted fabrics with improved fibrillation resistance could be obtained.

That is, the present invention is any time until the completion of the production reaction when the polyester is synthesized by reacting at least one alkylene glycol with a dibasic acid or an ester-forming derivative thereof containing terephthalic acid as a main component. (A) contains a thiophosphoryl group represented by the following general formula (I) of 0.1-4 mol% to the dibasic acid,

(Wherein R1 and R2 are hydrogen atoms or monovalent organic groups, R ₁ and R ₂ may be the same or different, X is -OH, -OR, OM or monovalent organic group M is an alkali metal or an alkaline earth metal) , Where M is 1 for alkali metals and 1/2 for alkali earth metals). The hexavalent phosphorus or metal phosphorus compound and (b) are equivalent to the total number of equivalents of the metals used for the compound. The total amount is 0.5-3.5 times the number of moles of the above-mentioned phosphorus compound, and the corresponding phosphorus compound and the metal compound are added without reacting beforehand, followed by the completion of the polyester synthesis. Under specific drying conditions, dry it sufficiently until the chip moisture level is 0.003% or less.

It is a method for producing a polyester, characterized in that the fiber is formed under normal production conditions and then weight-reduced with an aqueous solution of an alkali compound.

In the present invention, polyesters include terephthalic acid, ester forming derivatives thereof, and polyethylene terephthalate synthesized from ethylene glycol, but not more than 30 mol% of components. Other dicarbohic acid component glycol (Glycol) component and Oxycarbonic acid component may be copolymerized in the range which does not exist.

Specific examples of the copolymerization components include isophthalic acid, naphthalene dicar-bonic acid, diphenyl sulfone dicarbonic acid, and 5-sodium sulfo isophthalic acid. Dicar-bonic acid, such as adipic acid and sebacic acid, tetramethylene glycol, tetramethylene glycol, neophenthy glycol 1,4-cyclohexanedimetallic bisphenol A (1,4-Cyclhexane dimethanol, bisphenol A) Aliphatic, alicyclic, aromatic diols, such as bisphenol S (bisphenols), oxycarbonic acid, such as P-hydroxy ethoxy benzoic acid acid).

Examples of the phosphorus compound having a thiophosphorl group used in the present invention are phosphorus compounds represented by the above general formula (I), wherein R ₁ and R ₂ are hydrogen atoms or monovalent organisms. Among them, monovalent organisms are preferred. This monovalent organism is specifically an alkyl group, an aryl group, and R <_1> , R <_2> may be same or different. X is -OH, -OR, -OM or a monovalent organic group, and -OR is especially preferable.

M is particularly preferably an alkali metal or an alkaline earth metal, and more preferably Li, K, Mg l / 2, Ca l / 2, Ba 1/2, and the like, and Li and Ca 1/2 are particularly preferable. As monovalent organic group in X, it is the same as that of the definition of an organic group in said R <_1> and R <_2> , and R <_1> , R <_2> may be same or different.

Such sulfur-containing phosphorus compounds include phosphorothioic acid, trimethyl phosphorothioate, triethyl phosphorothioate, tributyl phosphorothioate, and tributyl phosphorothioate. Thiophosphate, phosphonothioic acid, such as triphenyl phosphorothioate, lauryl diphenyl phosphorothioate, stearyl diphenyl phosphorothioate, etc. phosphonothioic acid), 0.0-dimethyl methyl phosphonothioate, 0.0-diethyl ethyl phosphonothioate, 0.0-dibutylbutylphosphothioate (0.0 -dibutyl butyl phosphonothioate), 0.0-diphenyl phenyl phosphonothioate, 0.0-di Thiophosphonates such as 0.0-dilauryl phenyl phosphonothiate, 0.0-distearyl phenyl phosphonothioate, and the like, and the like. Alkali metal compounds such as Li, K, Na or sulfur-containing metal phosphorus compounds obtained by addition reaction during the polymerization of the polyester and alkaline earth metal compounds such as Mg, Ca, Ba or in an organic solvent such as EG in advance It is characterized by adding in a prescribed metal compound and a reaction system to complete superposition | polymerization.

In the preparation of the specified sulfur-containing metal phosphorus compound, it is obtained by heating and reacting the phosphorus compound and the chemically equivalent metal compound in the presence of an appropriate solvent. As a solvent, diol used as a raw material of the target polyester is used. It is best to use the ingredients. Alkali and alkaline earth metal compounds used in combination with the phosphorus compounds of the above provisions are not particularly limited as long as they can be carried out with the phosphorus compounds to form insoluble salts in the polyester, and are alkoxides, organic carbonates, oxides and halogens soluble in EG. Cargo etc. are good and especially an alkoxide thing and an organic carbonate are especially preferable.

In addition, Li is an alkali metal and Ca is particularly preferable as an alkaline earth metal.

The said metal compound may be used individually by 1 type, or may be used together 2 or more types. In this way, sulfur-containing phosphorus compounds and metal compounds are added to the reaction system to form insoluble salts in the polyester, or the compounds of the sulfur-containing alloy group chemically equivalently bonded as shown in the above formula (I) by reacting these compounds in advance. The chip prepared by adding the reaction solution of the above to the specified metal compound is dried under a lower temperature than the normal condition until the chip moisture content is 0.003% or less under specific drying conditions as in the above formula (II).

The drying temperature needs to be 150 ° C. or less, and when the temperature is exceeded, insoluble fine particles dispersed and dispersed in a fine size in the chip after completion of the polymerization process receive sufficient heat from the outside and diffuse and move within the polymer to reaggregate. There is a concern that ultimately coarsening, and when processing at 90 ℃ or less, there is a need to dry for a long time even in the low vacuum state of the dryer, so there is a problem that the operating cost increases and the productivity decreases.

In addition, even when the drying pressure is 2 Torr or more, since the desorption rate of moisture at low temperature is low, drying for a long time requires the same problem as described above.

Preferably,

It is good to set to.

It is necessary to limit the amount of the metal compound used for the sulfur-containing phosphorus compound and the amount of the phosphorus compound in order to give excellent color depth, clarity and friction durability by performing alkali reduction treatment on the fibers obtained under the above production conditions. .

If the addition amount of the specific phosphorus compound used in the present invention is too small, the deep color effect and sharpness of the polyester fiber obtained are insufficient, and if too large, the lack of deep color effect due to coarsening of the precipitated particles and the wear resistance will be reduced.

For this reason, the range of 0.1-4 mol% is suitable for the addition amount of a specific phosphorus compound with respect to the dibasic acid component which comprises polyester.

In addition, when the total amount of the metal compound added is less than 0.5 times the molar number of the phosphorus compound, the precipitated particles are solubilized to the polyester and the amount of precipitated particles is also increased. Not only the deep color effect of the polyester fiber obtained is insufficient, but also the softening point of the produced polyester may fall. On the contrary, when the amount of the metal compound is more than 3.5 times, coarse particles are produced and the pack pressure is increased during spinning, resulting in poor processability and lowering of deep fiber effect and friction durability of the obtained fiber. Done. For this reason, it is necessary to make the content of the metal compound with respect to the number-of-moles of the said phosphorus compound and the equivalent number of the metal in the said phosphorus compound into the range 0.5-3.5 times.

It is necessary to add the phosphorus compound and the metal compound in the above range to the polyester reaction system without reacting in advance, thereby making it possible to easily produce insoluble particles uniformly in the ultrafine dispersion state in the polyester. However, when the above-mentioned phosphorus compound and the metal compound are reacted in advance and precipitated into easy particles, and then added to the polyester reaction system, the dispersibility of the undesired particles in the polyester becomes poor and coarse aggregated particles are not contained.

The addition of the phosphorus compound and the metal compound of the above provision can be performed in any order at any time until the polyester synthesis is completed.

However, if only the phosphorus compound specified above is added at the end of the first stage reaction, the reaction of the first stage may be inhibited, and if only the metal compound is added before completion of the first stage reaction, the reaction is esterified. In the case of the reaction, coarse particles are generated during this reaction, and in the case of the transesterification reaction, the reaction proceeds ideally rapidly and causes a dolby phenomenon. Substantially, the addition time of the phosphorus compound and the metal compound is preferably after the end of the first step reaction of the polyester synthesis.

In addition, since the dispersibility decreases as the viscosity in the reaction system rapidly increases in the stage where the phosphorus compound and the metal compound are added to some extent, the coagulation and coarsening of the particles tend to occur. It is necessary to set it before the ultimate viscosity of the reaction compound reaches 0.2 dl / g.

The method of dividing recovery and addition in addition of the phosphorus compound and metal compound of the above provision is not specifically defined. In the present invention, the reaction of the first step, in particular the transesterification reaction, may have a catalytic activity of the reaction. When using such a mixture before the start of the reaction, it is not necessary to use a catalyst separately, and the metal compound may be used as the first It can be used as a catalyst either before or during the start of the step reaction, but as described above, the amount of use is within the range of the conventionally known addition amount as the first step reaction catalyst because it may cause a dolby phenomenon in the transesterification reaction. It is better to divide in.

On the other hand, the second-stage reaction catalyst used is a high-temperature active catalyst that can be used generally, but is not particularly limited. Phosphorous compounds having a thiophosphoryl group used for precipitation of insoluble fine particles are generally highly reducible. Antimony) compound may cause the problem that the polymer produced easily reduced by the phosphorus compound is agglomerated, so it is preferable to use other polycondensation catalyst which does not cause color change by the phosphorus compound.

As such a catalyst, a Lewis acid system such as Germanium, Titan, a zinc compound, or Bronsted acid such as an aromatic sulfonic acid compound may be used. Meanwhile, a method of using phosphoric acid and its ester compound having a phosphoryl (III) (V) group in place of the phosphorus compound of the thiophosphoryl group of the above-mentioned provisions used in the present invention is already known. Not only the particle size is uneven but also easy to coarse, so the surface state after alkali reduction tends to be coarse.

However, by using a sulfur-containing phosphorus compound having a thiophosphoryl group, it is possible not only to reduce the size of the precipitated particles but also to prepare a polyester containing uniform fine particles, which may be a P = S, double bond. The change in the electrophilicity of the atom, which is the center, is recognized and influenced by the difference in the ease of nucleophilic substitution reaction involved in the particle precipitation reaction therefrom.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

First, before entering the embodiment, the necessary matters are described.

The color and precipitate particle size of the obtained polyester chip and the deep color and frictional discoloration when the yarn obtained after spinning the chip was fabricated were measured by the following method.

“Polymer (L, b) of polymer” The polymer chips were heat treated at 150 ° C. ± 2 ° C. for 2 hours and then measured using a colorimeter.

L value is better as white degree, b value is yellowish blue color (+ yellow color is strong). “Precipitated particle size in polymer” 3 mg of the polymer was pressed between cover glasses on a heat tube heated to 280 ° C. to obtain a flaky sample, which was observed using a 300 × phase contrast microscope and analyzed by an image analyzer. The results were classified into the following five levels.

"Deep color of deep woven fabrics" Weaving the same fabric against the standard fabric (using Routine SB) made of satin tissue using 50d / 36f yarn and then dyeing them under the same conditions was observed in open air under the following conditions. Twenty judges were selected based on the same criteria as above, and the sensory test was carried out.

As a test device for "friction-resistant discoloration of deep blue weaving yarns", using a crock meter, the frictional weight of the dyestuff specified in KSK 0650 is tested according to the test method with a size of 20 × 10 cm. The degree of occurrence of is determined on a gray scale. If the wear resistance is very low, class 1, if extremely high class 5 is. Practically, level 4 or above is required.

Example 1

100 parts of dimethyl terephthalate (hereinafter referred to as parts by weight) 0.06 parts of zinc acetate (Zinc Acetate) in 70 parts of ethylene glycol was used as a transesterification catalyst while the methanol produced by raising the temperature from 140 ° C to 240 ° C in the reaction system was discharged out of the system. The first stage reaction was completed in accordance with conventional methods.

Subsequently, 0.7 parts of lithium acetate and 2.04 parts of triethyl phosphorothioate were added to the obtained reaction product as a fine particle forming agent, and 0.03 parts of GeO ₂ was added as a polycondensation catalyst. The second step reaction was carried out.

The value of the intrinsic viscosity which measured the obtained chip in 35 degreeC oxo chlorophenol (0rtho Chlorophenol) was 0.65 de / g.

The chip was vacuum dried at a low temperature of 120 ° C. and a vacuum degree of 0.02 Torr for 6 hours in a vacuum rotary dryer.

The moisture content of the chips taken out was 0.002%, and the color of the raw chips and the size of the fine particles contained before and after drying were specified in the first table. Subsequently, 50 D / 36 f of yarn was manufactured under the spinning conditions obtained by the usual method. The yarn is inclined at S-T 240T / m, and the weft is Z-Tin at 800T / m, and weaved into satin tissue to make it raw material. Boiling was performed with 5% aqueous sodium hydroxide solution so as to be 20%.

The fabric after the alkali weight loss treatment was dyed at high pressure in black by a conventional method, and the deep color and frictional resistance of the deep red cloth were measured and shown in the first table.

Example 2

In Example 1 instead of 0.7 parts of lithium acetate, 2.04 parts of triethyl phosphoro thioate, 4.07 parts of calcium acetate, 0.0-dilauyl phenyl phosphonothioate (0.0-dilauyl phenyl phosphonothioate) 6.58 parts were added, and 0.03 parts of dibutyl tinoxide was added to 0.03 parts of Para-Chlorobenezene sulphonic acid instead of 0.03 parts of GeO ₂ as a polycondensation catalyst. .

The results in the above are shown in Table 1.

(Comparative Example 1)

In Example 2, 0.03 parts of antimony trioxide was added instead of 0.03 parts of dibutyl tinoxide and 0.02 parts of parachlorobenzene sulphonic acid as polycondensation catalysts.

Other than that is the same as Example 2. The results in the above are shown in Table 1.

(Comparative Example 2)

In Example 1, drying was performed at 165 degreeC instead of having made the internal temperature of the vacuum rotary dryer 120 degreeC.

Other than that is the same as Example 1. The results in the above are shown in Table 1.

(Comparative Example 3)

In Example 1, the amount of the phosphorus compound added was 0.51 parts instead of the amount of triethyl phosphorothioate added 2.04 parts. Other than that is the same as Example 1.

The results in the above are shown in Table 1.

(Comparative Example 4)

In Example 1, the addition amount of the phosphorus compound was 4.59 parts instead of 2.04 parts of the triethyl phosphorothioate.

Other than that is the same as Example 1.

The results in the above are shown in Table 1.

(Comparative Example 5)

In Example 1, the amount of the metal compound added was 0.2 parts instead of 0.7 parts of the lithium acetate added. Other than that is the same as Example 1.

The results in the above are shown in Table 1.

(Comparative Example 6)

In Example 1, the amount of the metal compound added was 2.72 parts instead of 0.7 parts of the lithium acetate.

Other than that is the same as Example 1.

The results in the above are shown in Table 1.

Example 3

In Example 1, instead of 2.04 parts of triethyl phosphorothioate, 1.67 parts of trimeth phosphorothioate and 0.68 parts of Lithium Acetate (molar ratio 1: 1) under EG solvent Heating reaction was added.

(Fiber in the present invention is a generic term for monofilament or multifilament or filament yarn made by them)

TABLE 1

Claims (1)

When synthesizing a polyester by reacting a dibasic acid or an ester-forming derivative thereof having terephthalic acid as a main component with at least one alkylene glycol, at any time until the production reaction is completed, the dibasic acid is added to the dibasic acid. A pentavalent phosphorus compound or a metal phosphorus compound containing a thiophosphoryl group represented by the following formula (I) of 0.1-4 mol% relative to the above-mentioned phosphorus compound, and the total number of equivalent metals used above The total amount of is added to 0.5-3.5 times the number of moles of the phosphorus compound as defined above, and the above-mentioned phosphorus compound and the metal compound are added without prior reaction, and then the synthesis of the polyester is completed. Under certain drying conditions, such as Ⅱ), the number of alkali compounds after drying sufficiently to form fibers under ordinary spinning conditions until the moisture content is 0.003% or less. The method of dichroic core and island fame, characterized in that the fluid-loss treatment with enhanced novel polyester's production. next

(Where, R ₁ and R ₂ is a hydrogen atom or a monovalent organic group, R ₁ and R ₂ may be the same or different, X is -OH, -OR, -OM or a monovalent organic group and M is an alkali metal or alkaline Earth metal, M being 1 for alkaline metals and 1/2 for alkaline earth metals)

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