JPS6143625A - Preparation of polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester capable of being fibers having good color and feeling and transparent films having good slipperiness, by adding a specific phosphorus compound, alkali (earth) metal compound and ammonium compound to a polyester reaction system. CONSTITUTION:A bifunctional carboxylic acid consisting essentially of terephthalic acid is reacted with an alkylene glycol. In the process, 0.1-5mol%, based on the above-mentioned carboxylic acid component, phosphorus compound expressed by the formula (R is H or monofunctional organic group; X is OH, OR' or monofunctional organic group; R' is monofunctional organic group; Q is metal, H or monofunctional organic group; n is 1 or 0) and 0.001-0.5mol% (in an amount to give the total of equivalents of the above-mentioned phosphorus compound and the metal 2-3.2 times of the number of phosphorus compound mol) ammonium compound expressed by the formula [NH4]<+>A<-> (A is anion residue) are added to the polyester reaction system to give the aimed polyester containing uniformly dispersed insoluble fine particles.

Description

[Detailed description of the invention] a. Field of use The present invention relates to a method for producing polynisdel.

More specifically, the particle dispersibility is improved, and when made into a film, it has excellent transparency and slipperiness, and when it is made into ff1M and subjected to alkali reduction, extremely fine irregularities are formed on the fiber surface, and when dyed, The present invention relates to a method for producing polyester suitable for obtaining a woven or knitted fabric exhibiting excellent color depth and clarity, as well as having excellent rayon-like drapability and triacetate-like dry touch feel.

b. Prior Art Polyester has many excellent properties and is therefore widely used as fibers and films. however,
Compared to natural fibers such as wool and silk, cellulose fibers such as rayon and acetate, and acrylic fibers, polyester fibers have the disadvantage that when colored, they lack depth of color and are inferior in color development and clarity. .

Conventionally, attempts have been made to improve dyes, chemically modify polyester, etc. in an attempt to overcome this drawback, but none of them have been sufficiently effective. In addition, we have developed a method for forming a transparent thin film on the surface of polyester fibers, and a method for forming transparent thin films on the surface of polyester fibers, and
A method has been proposed in which fine irregularities are formed on the fiber surface by applying plasma irradiation at 500 mA and see/di. However, even with these methods,
The effect of improving the depth of color is insufficient, and in addition, the transparent thin film formed on the fiber surface easily falls off when washed, etc., and its durability is insufficient. Because there are no irregularities on the surface of the fibers in the fiber parts that are in the shadow, the smooth fiber surface is created by the rolling of threads within the fiber structure that occurs during wear! ! ? [There is a drawback that color spots appear in K.

On the other hand, as a method for imparting irregularities to the surface of polyester fibers, fibers made of polyester blended with polyoxyethylene glycol or polyoxyethylene glycol tosulfone compounds are treated with an alkaline aqueous solution to form wrinkles arranged in the fiber axis direction. A method for producing hygroscopic fibers in which micropores are formed on the fiber surface, or polyester fibers obtained by adding fine particles of inert inorganic substances such as zinc oxide, calcium phosphate, etc. There have been proposals for producing hygroscopic fibers by treating them with water to elute inorganic fine particles (forming finer pores). However, the fibers obtained by these methods have no effect on improving the depth of color. This is not observed, and on the contrary, a decrease in visual density is observed.

That is, in these methods, when the treatment with the alkaline aqueous solution is not sufficient, no effect of improving the depth of color is observed, and when the treatment with the alkaline aqueous solution is sufficient, the depth of one color is not improved; Perhaps due to the diffused reflection of light by the micropores, the visibility level decreases, and the whole color is colored, making it look whitish.1.The strength of the resulting fibers is significantly reduced, and K
It becomes impractical.

In addition, fibers made of polyester containing inorganic fine particles such as silica with a particle diameter of 80 mμ or less are subjected to an alkali weight reduction treatment to provide irregular irregularities of 0.2 to 0.7 μm on the fiber surface, and 50 μm within these irregularities. A method has been proposed to improve the depth of color by creating fine irregularities of ~200 mμ. However, even with this method, the effect of improving the depth of color is insufficient, and on top of that, perhaps because of the extremely complex uneven shape, the unevenness is destroyed by external physical effects such as friction, and the destroyed parts However, there are disadvantages in that the color changes significantly compared to other undestructed parts, there is a difference in gloss, and furthermore, it easily fibrils.

On the other hand, rayon-like texture is an unexplored field for polyester fibers, and especially in the women's wear field, there is a demand for rayon-like textures that have excellent drape and stiffness and can express a luxurious and romantic silhouette. There is. However, it has not been possible to obtain L-fiber polyester fibers that have both the high drape properties and stiffness of such legnons.

On the other hand, there is a demand for polyester fibers that have triacetate-like vivid dyeability and luster as well as a dry-touch texture and are rich in coolness, but such polyester fibers have not been available to date.

C1 Purpose of the Invention The present inventor has conducted intensive studies to provide polyester fibers that do not have the above-mentioned drawbacks and have excellent color depth and clarity by adding micropores to polyester fibers. A phosphorus compound of By treating polyester fibers with alkali, it is possible to form special irregularities that are smaller than the wavelength of visible light on the entire surface of the fibers, resulting in excellent color depth and clarity when colored. In addition, it was discovered that polyester fibers with sufficiently low discoloration due to friction and excellent fibril resistance could be obtained, and the present invention was previously proposed.

As a result of further studies on the processing method and properties of the polyester fibers, it was discovered that, in addition to the above-mentioned color effect, the drape properties of woven and knitted fabrics were significantly improved, especially under high alkali weight loss rates.

However, when the above-mentioned polyester fiber is modified into a type dyeable with cationic dyes by copolymerizing an isophthalic acid component having an alkali metal sulfonate group, the size of the micropores formed tends to become coarse, especially in high alkali Under the weight loss rate, the coarsening of micropores progresses significantly;
Five problems were identified in which it was difficult to obtain the above-mentioned color and texture effects.

The inventors of the present invention have made extensive studies to solve this problem by further improving the fine dispersibility of precipitated particles in polynisdel, and have found that the use of a compound containing inorganic ammonium ions in combination with a compound containing an inorganic ammonium ion has led to a reduction in precipitation in polyester. Particle dispersibility has been significantly improved and extremely fine particle dispersibility has been achieved, making it possible to achieve high alkali weight loss and weight reduction not only for regular polyester fibers but also for modified polyester fibers dyeable with cationic dyes. It has been found that by forming fine surface irregularities on the surface of the fabric, it is possible to achieve not only a color improvement effect but also a significant improvement in gloss, drapability, and dry texture imparting effect.

In addition, since the polyester obtained by the present invention has improved particle dispersibility as described above, it can be made into a film with excellent transparency and slipperiness, and can be used for magnetic applications such as audio, video, and computer applications. For tapes, for magnetic recording media such as floppy disks, for photographs, for graphics 7-
For to! For stamping wheels.

It has been found that it is extremely useful as a raw material for decorative threads such as gold and silver threads, and films for electrical materials such as capacitors.

The present invention was completed as a result of further studies based on these findings.

That is, in the present invention, when producing a polyester by reacting a difunctional carboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof with at least one kind of alkylene glycol, any optional steps until the production reaction is completed. (at 0.1 to 0.1 to the difunctional carboxylic acid component)
54: Phosphorus compound represented by the following general formula (I) (Oln RO-P~OQ <11, (b) number of equivalents of metals (a) and (b) The total amount of
f1) an alkaline earth metal compound and/or alkali metal compound in an amount of 2.0 to 3.2 times the number of moles of the phosphorus compound; 00
1 to 0.5 mol of the following general formula (1) [Shu,] 10A-・
This is a method for producing polyester in which insoluble fine particles are uniformly dispersed, characterized by adding and blending (11 [where A represents an anionic group]).

The polyester referred to in the present invention has terephthalic acid as its main acid component, and its main glycol component is at least 1 m of fullylene glycol carried from at least one glycol, preferably ethylene glycol, natrimethylene glycol, or tetramethylene glycol. The main target is polyester.

It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component (and/or
Alternatively, it may be a polyester in which part of the glycol component is replaced with the above-mentioned glycol other than the main component or another diol component.

Examples of difunctional carboxylic acids other than prephthalic acid used here include inphthalic acid, naphthalene dicarboxylic acid, nphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, -Sodium sulfoisophthalate, 7
Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as dipic acid and sepacif 2,1,4-cyclo-Nxanedicarboxylic acid. In addition, examples of diol compounds other than the above-mentioned glycols include cyclohexane-1
, 4-dimetatool, neopentyl glycol, bisphenol A, bisphenol S, aliphatic, alicyclic,
Examples include aromatic diol compounds and polyoxyalkylene glycols. In particular, a modified polyester in which 1 to 7 moles of the difunctional carboxylic acid component is replaced with an inphthalic acid component containing an alkali metal sulfonate group such as 5-sodium sulfoisophthalic acid is a preferred polyester because the effect of the present invention is remarkable. be.

Further, as long as the polyester is substantially linear, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as trimethylolpropane, pentaerythritol, etc. can be used.

Such polyesters may be synthesized by any method. For example, regarding polyethylene terephthalate, 1. Usually, terephthalic acid and ethylene glyfur are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol are transesterified, or terephthalic acid and ethylene glycol are transesterified. The first stage reaction is to react with ethylene oxide to produce a glycol ester of terephthalic acid and/or its low polymer, and the first stage reaction product is heated under reduced pressure to reach the desired degree of polymerization. It is produced by a second step of polycondensation reaction.

The phosphorus compound used in the present invention has the following general formula (I) cIn RO-P -OQ ......+11
It is a phosphorus compound represented by the following formula, where R is H or a -valent organic group, and a -valent organic group is particularly preferred.

Specifically, this -valent organic group is a furkyl group or an aryl group.

Aralkyl group or ((CH,)JO)kR' (where W is H, furkyl group, aryl group or aralkyl group,
l is an integer of 2 or more, k is an integer of 1 or more), etc. are preferable a
X is OH, OR' or a -valent organic group, R' is the same as the definition of the monovalent organic group in RK above, and R'
and R may be the same or different, and the -valent organic group is the same as the definition of the organic group for R above, and may be the same or different from R. Q is a metal, H or a -valent organic group, with metal being preferred. Q.K.
! As the metal in 6, alkaline earth metals and alkali metals are preferable, and Ll, Na, x, Mgx are more preferable.
/2. cat/z, sr1/2. nat/z can be increased, and Cal/2 is particularly preferred. The monovalent organic group in Q is.

Same as the definition of the organic group in R and R′ above,
It may be the same as or different from R and R'. n is 1 or 0
It is.

Examples of such phosphorus compounds include phosphoric acid triesters such as sulfuric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphenyl phosphate! Methyl acid phosphate, ethyl and phosphate nisopropyl acid phosphate.

Phosphate moss such as butyl acid phosphate:,/I
lt d 9-X T tk + ll! 7702
! """Sulfite triesters such as trimethyl, triethyl phosphite, tributyl phosphite! Phosphite such as methyl acid phosphite, ethyl and phosphite, impudivir acid phosphate, butyl acid phosphite Mono- and diesters, phosphonic acids such as methylphosphonic acid and phenylphosphonic acid, phosphonic acid esters such as dimethyl methylphosphonate and dimethyl phenylphosphonate, phosphorus compounds obtained by reacting the above-mentioned phosphorus compounds with glycol and/or water, and further the above-mentioned phosphorus compounds. 1 m selected from metal-containing phosphorus compounds obtained by reacting a phosphorus compound with a predetermined amount of an alkali metal compound such as Ll, Na, or alkaline earth metal compound such as Mg, Ca, Sr, and Ba. The above phosphorus compounds can be used.

To produce the above-mentioned metal-containing phosphorus compound.

Usually a compound of sulfuric acid, sulfuric acid, phosphonic acid, phosphoric acid ester (mono, di, or tri), phosphorous ester (mono, di, or tri), or phosphonic acid ester and a specified amount of the corresponding metal. can be easily obtained by reacting in the presence of a solvent and heating if necessary. In this case, it is most preferable to use glycol, which is used as a raw material for the target polyester, as the solvent.

In the present invention, the metal compound used in combination with the phosphorus compound is not particularly limited as long as it is an alkaline earth metal and/or alkali metal compound that reacts with the phosphorus compound to form a salt insoluble in polyester. , Ca,
Alkaline earth metals such as Sr and Ba, Ll.

Organic carboxylates and sulfates of alkali metals such as Na, K, acetates, pentarates, benzoates, heptatarates, stearates.

Inorganic acid salts such as sulfates, silicates, carbonates, 9-bicarbonates, hagnides such as chlorides, chelate compounds such as ethylenedi7minetetraacetic acid complexes, hydroxides, oxides, methylates, ν ethylates, and glycolates. Examples include alcoholades, phenolates, etc. Particularly preferred are organic carboxylates, p-genides, quinto compounds, and alcoholades that are soluble in ethylene glycol, and among them, organic carboxylates are particularly preferred.

Furthermore, Ca is particularly preferred as the alkaline earth metal. Even if the above metal compound is used alone for 1'm,
Two or more types may be used in combination. 1. When blending the above-mentioned phosphorus compound and metal compound, excellent color depth can be obtained by subjecting the resulting fiber to an alkali weight loss treatment.

In order to provide sharpness and excellent drapeability, as well as excellent transparency and slipperiness to the obtained film, the amount of phosphorus compound used and the ratio of the amount of metal compound used to the amount of phosphorus compound used must be adjusted. need to be specified. That is, if the amount of the phosphorus compound used in the present invention is too small, the resulting polyester fibers will have insufficient depth, drapability, and film slipperiness; on the other hand, if it is too large, the transparency and durability of the fibers and films will be insufficient. Friction durability begins to decline. Therefore, the amount of the phosphorus compound added is 0.1 to 5 moles based on the bifunctional carboxylic acid component constituting the polyester.
should be within the range of In addition, the amount of metal compound added is
When the total number of metal equivalents of the metal compound and the phosphorus compound is less than 2.0 times the number of moles of the phosphorus compound, the resulting polyester fiber has a deep color.

The drapability and slipperiness of the film become insufficient, and the softening point of the polyester produced also decreases. On the other hand, if a metal compound is used in an amount exceeding 3.2 times this amount, coarse particles will be generated and the transparency of the fibers and films will decrease, and the ta, depth of the color of the fibers, drapability, and friction durability will decrease. K decreases. Therefore, the total number of equivalents of the metal compound and the metal of the phosphorus compound relative to the number of moles of the phosphorus compound needs to be in the range of 260 to 3.2 times.

It is necessary to add the phosphorus compound and the metal compound to the polyester reaction system without reacting them in advance, and by doing so, the insoluble particles can be easily produced in a uniform ultrafinely dispersed state in the polyester. It is necessary to react the above-mentioned phosphorus compound and metal compound externally to form insoluble particles before adding them to the polyester reaction system. By doing this, the insoluble particles can be easily dispersed in a uniform ultrafine state in the polyester. can be generated. If the above-mentioned phosphorus compound and metal compound are reacted externally in advance to form insoluble particles and then added to the polyester reaction system, the dispersibility of the insoluble particles in the polyester becomes poor and coarse agglomerated particles may be contained. This is not desirable.

The above-mentioned phosphorus compound and metal compound can be added in any order at any stage until the synthesis of the polyester is completed. However, if only the phosphorus compound is added before the first stage reaction is completed, the completion of the first stage reaction may be inhibited, and if only the metal compound is added in the first half of the first stage reaction. If added, if this reaction is an esterification reaction, coarse particles may be generated during this reaction, or if it is a Nissdell exchange reaction, the reaction may proceed abnormally quickly and cause bumping phenomenon. In this case, it is preferable that the amount used does not exceed the amount normally used as a catalyst.

The remaining amount of the metal compound and the timing of addition of the total amount of the phosphorus compound are determined in the latter half of the first stage reaction of polyester synthesis (reaction rate 50
It is preferable that the process be performed after the stage (I) or higher. In addition, if the phosphorus compound and metal compound are added at a stage when the second stage reaction has progressed too much, particle aggregation and coarsening are likely to occur, so the intrinsic viscosity of the reaction mixture that is added to the second stage reaction is Preferably, it is before reaching 0.3.

The above-mentioned phosphorus compound and metal compound may each be added at once, added in two or more divided portions, or added continuously.

In the present invention, any catalyst can be used for the first stage reaction, but some of the above metal compounds have the ability to catalyze the g1 stage reaction, particularly the transesterification reaction, and such compounds are used. In this case, it is not necessary to use a separate catalyst, and the metal compound can be added before or during the first stage reaction to serve as a catalyst. Therefore, it is preferable that the amount used is within a range that does not exceed the amount normally used as a catalyst.

In the present invention, the compound having an inorganic ammonium ion used as a dispersant for insoluble fine particles precipitated by the reaction between the phosphorus compound and the metal compound has the following general formula (m CNH,, l+A-...・(It is an ammonium compound represented by 10.

The formula is an anionic residue, including organic and inorganic 7-ionic residues, such as organic carboxyl groups such as acetate, sulfate, benzoate, phthalate, stearate, etc. 7-ion residues of acid salts, borates, sulfates.

Bisulfates monobisulfites, phosphates, carbonates.

7-ion residues of inorganic acid salts such as bicarbonate, thiocyanate, etc.; halides such as chloride;
Furkylbenzene sulfonate.

An example is a 7-ion residue of tosylate.

'1 Preferred examples of such ammonium compounds □■: On the body side, ammonium acetate, ammonium oxalate, ammonium carbonate, ammonium bicarbonate, ammonium hydroxide, ammonium chloride, ammonium ethosulfate, ammonium dotesylbenzenesulfonate,
Ammonium alkylsulfonesulfonate (ammonium tosylate) having an average carbon number of 14
, ammonium borate, ammonium chloride, ammonium chloride, ammonium 7 midosal 7 ate, ammonium tartrate, ammonium aminoformate (NH.C)
OONL), 8-7nilino-1-naphthalenesulfonate ammonium, cal/% miso51 hummonium,
Quen Shun Ammonium T Ammonium Phosphate Ammonium Hypophosphite, Ammonium Salicylate! Examples include ammonium sulfaminate, ammonium sulfaminate, and ammonium sulfanyl glycolate.

If the amount of the ammonium compound blended is too small, the effect of improving the dispersibility of internally precipitated particles in the polyester will be insufficient, and if this amount is increased, the particle dispersibility will improve, but if it is too large, the particles will no longer be dispersed. The properties of the difunctional carboxylic acid component do not show any significant improvement, and instead the polymer becomes yellowish.For this reason, the amount of ammonium compound to be added is 0.001 to 0.00% relative to the difunctional carboxylic acid component.
Should be in the range of 5 molt, especially 0.01 to 0.3
A range of molch is preferred.

The ammonium compound may be added at any stage until the synthesis of the polyester described above is completed; for example, it may be added and mixed into the polyester raw materials, it may be added during the first stage reaction, or it may be added during the first stage reaction. It may be added between the end of the reaction and the start of the second stage reaction, or it may be added during the second stage reaction.

The ammonium compound may be added in a mixture with the phosphorus compound and/or the metal compound, and this is preferable from the viewpoint of particle dispersibility. In particular, phosphorus compounds, metal compounds and ammonium compounds
Most preferably, the agents are added as a mixed clear solution.

As explained above, in the present invention, (a) a specific amount of the phosphorus compound, (bl) an alkaline earth metal compound and/or alkali metal compound in a quantitative ratio of "C% to the phosphorus compound, and (e) ) By adding an ammonium compound to the polyester reaction system and subsequently completing the production of the polyester, the dispersibility of the internal particles is particularly markedly improved. , has a high degree of polymerization, high softening point, high whiteness, and good passability through the spinning and spinning processes, and after being made into fibers, it is subjected to alkali weight loss treatment to achieve high alkali filter 1.
: Even under low temperature conditions, extremely precise and precise fiber surface irregularities are formed, making it possible to produce polyester fibers with outstanding drapability, dry texture, depth of color, clarity, gloss, and friction durability. It is possible to obtain a polyester that can be used to form a polyester film having extremely excellent slipperiness.

Furthermore, when the base polyester constituting the fiber is a modified polyester dyeable with cationic dyes, the pores formed by the alkali weight loss treatment tend to become particularly coarse. The effect of applying is particularly large. Examples of such modified polyesters that can be dyed with cationic dyes include polyesters in which an isophthalic acid component having 1 to 7 moles of alkali metal sulfonate groups is copolymerized with respect to the difunctional carboxylic acid component constituting the polyester. I can do it.

In addition, the polyester obtained by the method of the present invention includes:
Optional additives as necessary, such as catalyst 2 color inhibitor,
Heat resistant agent, flame retardant.

A fluorescent whitening agent, a matting agent, a coloring agent, etc. may also be included.

f. Examples The following examples will be further explained. In the examples, parts and q indicate parts by weight and weight %, and the depth of color and friction discoloration resistance when dyeing the obtained polyester fibers were measured by the following method.

(+) Deepness of color As a measure of the depth of color, bathochromicity (K/S') was used. In this study, I measured the spectral reflectance (■) of the sample fabric using a Takashi RC-330ffi self-recording spectrophotometer.
-Munk). The larger this value is, the greater the deep color effect is.

Note that K is an absorption coefficient and S is a scattering coefficient.

(11) Friction discoloration resistance Using a single-oscillation flat abrasion machine for friction fastness testing, a georgette made of 100 ml of ethylenethenephthalate was used as the friction cloth, and the failed fabric was
The surface was worn a predetermined number of times under a load of oog, and the degree of discoloration was determined using a gray scale for discoloration and fading. When the wear resistance was extremely low, it was rated as 1st grade, and when it was extremely high, it was rated as 5th grade.

For practical purposes, a level 4 or above is required.

Example 1 100 parts of dimethyl terephthalate, 6 parts of ethylene glyfur
0 parts and 0.06 s of calcium acetate monohydrate (0.066 mol relative to dimethyl terephthalate) were charged into a transesterification tank, and the mixture was heated to 140'O for 4 hours under a window element gas atmosphere.
The transesterification reaction was carried out while raising the temperature from 230' to 230'O and distilling the generated methanol out of the system. Subsequently, 0.5 parts of trimethyl phosphate (
0.693 mol% based on dimethyl terephthalate) and 0
．． Y4 was produced by reacting 31 parts of calcium acetate monohydrate (1 part, 2 times the mole relative to trimethyl phosphate) in 8.5 parts of ethylene glycol at a temperature of 120'O for 60 minutes under total reflux. To 9.31 parts of a clear solution of acid diester calcium salt, 0.57 parts of calcium acetate hydrate (0.9 times the mole relative to trimethyl phosphate) and 0.016 parts of 7-ammonicum acetate (terephthalate) were added at room temperature. Add 9.896 parts of a mixed clear solution of diester calcium phosphate, calcium acetate and ammonium acetate obtained by dissolving 0.04 mol % based on dimethyl acid, and then add 0.04 part of antimony trioxide. and transferred to a polymerization can. Then, after 1 hour, 760txddl to 1ml
Reduce the pressure to 111 and increase the pressure at the same time for 1 hour and 30 minutes to 230.
The temperature was raised from '0 to 285'0. Under reduced pressure of 1 tn*H1 or less, polymerization temperature 285'O''11'' for further 3 hours,
Polymerization was carried out for a total of 4 hours and 30 minutes to obtain a polymer having an intrinsic viscosity of 0.640 and a softening point of 258'O. After the reaction was completed, the polymer was made into chips according to a conventional method.

The chips were dried by a conventional method, melt-spun at 290°0 using a spinneret with 36 circular spinning holes with a hole diameter of 0.3, and then stretched at a draw ratio of 3.5 times by a conventional method. A raw yarn of 75 denier/36 filaments was obtained.

S twist 2500T/m and 2 twist 2500T/m on this yarn
The highly twisted yarn was then steamed at 80°C for 30 minutes to heat it up.

The high twist yarn has a warp density of 47 pieces/LM and a weft density of 32 pieces/LM.
0! A satin georgette fabric was woven with two S and Z twists arranged alternately.

The obtained gray fabric is heated to boiling temperature in a rotary washer for 2 hours.
After 0 minutes of relaxing treatment, 3.5 degrees of hydration after pre-7F using the usual method.)
The fabric was treated with an aqueous IJ cum solution at boiling temperature to obtain a fabric with a weight loss rate of 30-.

The fabric after this alkali treatment is Dianix Black.
HG-FS (Mitsubishi Chemical Industries Φυ product) 15% owf
After staining at 30°0 for 60 minutes, sodium hydroxide x Fl/
A black dyed cloth was obtained by photo-washing with an aqueous solution containing i and Hydol Sulfide 1971 at 70'O for 20 minutes. Table 1 shows the color depth and friction discoloration resistance of this black cloth after 200 wears.

This black dyed fabric had excellent drapability and stiffness, and had a very good rayon-like feel.

Example 2 Same as Example 1 except that 0.012 parts of ammonium carbonate monohydrate (0.02 molti based on dimethyl terephthalate) was used instead of ammonium acetate used as the ammonium compound in Example 1. I went to The results are shown in Table 1. The obtained woven fabric had excellent drapability similar to rayon.

Example 3 Same as Example 1 except that 0.016 part of ammonium bicarbonate (0.039 mol % based on dimethyl terephthalate) was used instead of ammonium acetate used as the ammonium compound in Example 1. A rayon-like fabric with high drapability was obtained. The results are shown in Table 1.

Example 4 0.072 parts of 25% NH,Q instead of ammonium acetate used as the ammonium compound in Example 1
H aqueous solution (0.1 mol% based on dimethyl terephthalate)
) was used in the same manner as in Example 1. The results were as shown in Table 1.

This fabric had excellent drapability and stiffness, and had a good feel.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the ammonium acetate used in Example 1 was not used.

The results were as shown in Table 1.

Example 5 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts, 0.06 parts of calcium acetate monohydrate (0.066 molti relative to dimethyl terephthalate), and 0.04 parts of antimony dioxide were placed in a transesterification tank, and heated under nitrogen gas atmosphere for 14 hours to 140'0 to 230'. The transesterification reaction was carried out while raising the temperature to 0° and distilling the generated methanol out of the system. Subsequently, the obtained reaction product was added in advance to 5.69 parts of a 10% ethylene glyfur solution of calcium acetate monohydrate (0.627 mol % as calcium acetate based on dimethyl terephthalate) and 0.0 parts of ammonium acetate at room temperature. Mixed solution 5.71 parts obtained by dissolving 0.024 parts (0.06 mol% based on dimethyl terephthalate)
After 5 minutes, 0.575 parts of isopropyl acid phosphate was added. Next, while expelling ethylene glycol from the system, the internal temperature was raised to 240°0, and the reaction mixture was transferred to a polymerization vessel.

After that, 3,5-
3 parts sodium (β-human p-xyethoxycarbonyl)benzenesulfonate (1 part per dimethyl terephthalate)
．． 7 mol%) and 0.112 parts of sodium acetate trihydrate (0.16 mol% relative to dimethyl terephthalate) as an ether formation inhibitor were added to the tt polymerization reactor. followed by 1
Over a period of time, the pressure was reduced from 760 mH, 9 to 1 smHJi', and at the same time, the internal temperature was raised to 280'O over 1 hour and 30 minutes. Under reduced pressure below 1 mHI, polymerization temperature 280
Polymerization was continued for an additional 2 hours and 30 minutes at zero temperature for a total of 4 hours to obtain a polymer with an intrinsic viscosity of 0.552 and a softening point of 252°0.

Using and repolymer, the following steps were carried out in the same manner as in Example 1: spinning, stretching, 9-strong twisting, twist stopping, weaving, and embossment.

A satin georgette fabric with a weight loss rate of 15% was obtained by presetting and alkali treatment.

The fabric after this alkali treatment is processed into Aizan Cathil.
onBlack CD-GLH (Hodogaya Chemical @Product) 8
After dyeing at 120° 0 for 60 minutes in a dye bath containing 21/l of Glauber's salt at % ovf, a black dyed fabric was obtained by nibbling according to a conventional method. The color depth and friction discoloration resistance of this black dyed fabric after 200 wears were as shown in Table 1. The resulting fabric was extremely tri-7 cetate-like, with a glossy deep black color and a dry touch texture.

Comparative Example 2 The same procedure as in Example 5 was carried out except that the ammonium acetate used in Example 5 was not used. The results are shown in Table 1.

Claims (1)

[Claims] (1) When producing a polyester by reacting a difunctional carboxylic acid, mainly terephthalic acid, or its ester-forming derivative with at least one alkylene glycol, at any stage until the production reaction is completed. , (a) 0.1 to 5 mol% of the difunctional carboxylic acid component of the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) However, R is H or a monovalent The organic group, X is OH, OR' or a monovalent organic group (wherein R' is a monovalent organic group), Q is a metal, H or a monovalent organic group, and n is 1 or 0. A phosphorus compound represented by (b) where the total number of equivalents of metals in (a) and (b) is (a)
an alkaline earth metal compound and/or alkali metal compound in an amount that is 2.0 to 3.2 times the number of moles of the phosphorus compound; and (c) 0.001 to 0.001 to the difunctional carboxylic acid component. 0.5 mol% of the following general formula (II) [NH_
4]＾+A＾−・・・・・・・・・(II) [However, A represents an anion residue] Insoluble fine particles characterized by adding and blending an ammonium compound represented by the following are uniformly dispersed. A method for producing polyester.