JPH039930B2 - - Google Patents

Description

[Detailed description of the invention]

a Field of Application The present invention relates to a method for producing polyester. More specifically, particle dispersibility is improved, when made into a film, it has excellent transparency and slipperiness, and when made into a fiber and subjected to alkali weight reduction, extremely fine irregularities are formed on the fiber surface, making it difficult to dye. This invention relates to a method for producing polyester suitable for obtaining a woven or knitted fabric that exhibits excellent color depth and clarity, as well as excellent drapability similar to rayon and excellent dry touch feel similar to triacetate. 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 lack the depth of color and are inferior in color development and clarity when colored. There is. 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, a method of forming a transparent thin film on the surface of polyester fibers and a method of applying plasma irradiation of 80 to 500 mA·sec/cm ³ to the surface of a woven or knitted fabric to form fine irregularities on the surface of the fibers have been proposed. 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. In the method of applying plasma irradiation, unevenness does not occur on the surface of the fiber in the part of the fiber that will be in the shadow of the irradiated surface, so the smooth fiber surface will not be formed on the surface due to the rolling of threads within the fiber structure that occurs during wearing. There is a drawback that color spots appear. On the other hand, as a method for imparting irregularities to the surface of polyester fibers, fibers made of polyoxyethylene glycol or polyester blended with polyoxyethylene glycol and a sulfonic acid compound 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 and blending fine particles of inert inorganic substances such as zinc oxide, calcium phosphate, etc. into a polyester reaction system are treated with an aqueous alkaline solution. A method for producing hygroscopic fibers has been proposed in which fine pores are formed by eluting inorganic fine particles. However, the fibers obtained by these methods do not have the effect of improving color depth, and instead show a decrease in visual density. That is, in these methods, if the treatment with the alkaline aqueous solution is not sufficient, no effect of improving the color depth is observed at all, and when the treatment with the alkaline aqueous solution is sufficient, the color depth is not improved, Perhaps due to the diffuse reflection of light by the micropores, the visual density decreases, making it look whitish even when colored in a dark color, and the strength of the resulting fibers decreases significantly.
It easily becomes fibrillated and cannot be put to practical use. In addition, fibers made of polyester containing inorganic fine particles such as silica with a particle size of 80 mμ or less are subjected to an alkali weight reduction treatment to give irregular irregularities of 0.2 to 0.7 μm on the fiber surface, and 50 to 50 μm in diameter 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 due to the extremely complicated shape of the unevenness, the unevenness is destroyed and destroyed by external physical effects such as friction. There are disadvantages in that the damaged portions are significantly discolored or have a difference in gloss compared to other undestructed portions, and furthermore, they easily become fibrillated. On the other hand, rayon-like texture is an unexplored field for polyester fiber, and especially in the women's wear field, there is a demand for rayon-like texture that has excellent drape and stiffness and can express a luxurious and romantic silhouette. There is. However, it has not been possible to obtain polyester fibers that have both the high drape properties and stiffness of rayon. On the other hand, triacetate-like vivid dyeability and gloss,
Furthermore, there is a demand for polyester fibers that have a dry touch feel and are rich in coolness, but conventionally such polyester fibers have not been available. c. Purpose of the Invention The present inventor has conducted intensive studies to provide polyester fibers that do not have the above drawbacks and have excellent color depth and clarity by adding micropores to polyester fibers. , a specific amount of a phosphorus compound and a specific ratio of an alkaline earth metal compound to the phosphorus compound are added to a polyester reaction system, insoluble fine particles are reacted and precipitated in the system, and the resulting polyester containing the insoluble fine particles is produced. By treating melt-spun 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, and this makes it possible to change the color when colored. It was discovered and proposed earlier that polyester fibers with excellent depth and definition, less discoloration due to friction, and excellent fibril resistance can be obtained. As a result of further investigation into the processing method and characteristics of the polyester fibers mentioned above, in addition to the above-mentioned color effects, especially under high alkali weight loss rates,
It has been found that the drape properties of woven and knitted fabrics are significantly improved. 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 the micropores significantly progresses, so a problem was observed in that it was difficult to obtain the above-mentioned color and texture effects. The inventor of the present invention has conducted intensive studies to solve this problem by further improving the fine dispersibility of precipitated particles in polyester, and has found that by using a compound containing an inorganic ammonium ion, polyester The dispersibility of the precipitated particles in the fiber has been significantly improved, and extremely fine particle dispersibility has been achieved, making it possible to achieve high alkali weight loss not only for regular polyester fibers but also for modified polyester fibers that can be dyed with cationic dyes. Extremely fine surface irregularities are formed, which not only improves color but also
It has been found that significant improvements in gloss, drapability, and dry texture can be achieved. Furthermore, since the polyester obtained in the present invention has improved particle dispersibility as described above, it can be made into a film with excellent transparency and slipperiness.
For magnetic tapes such as audio, video, and computers, for magnetic recording media such as floppy disks, for photographs, for graphic arts, for stamping wheels, for decorative threads such as gold and silver threads, and for electrical materials such as capacitors. It was found that it is also extremely useful as a raw material for films such as. The present invention was completed as a result of further studies based on these findings. d. Constitution of the Invention That is, the present invention involves producing a polyester by reacting a bifunctional carboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof with at least one kind of alkylene glycol. (a) from 0.1 to 5 with respect to the difunctional carboxylic acid component;
Mol% of the following general formula (I) [However, R is H or a monovalent organic group, and X is
OH, OR' or a monovalent organic group (where R' is a monovalent organic group), Q is a metal, H or a monovalent organic group,
n is 1 or 0. ] A phosphorus compound represented by (b) an alkaline earth metal in an amount such that the total number of equivalents of metals (a) and (b) is 2.0 to 3.2 times the number of moles of the phosphorus compound (a) compound and/or alkali metal compound and (c) 0.001 to the difunctional carboxylic acid component.
A polyester in which insoluble fine particles are uniformly dispersed, characterized in that 0.5 mol% of the following general formula () [NH ₄ ] ⁺ A ^- ... () [where A represents an anionic residue] is added and blended. This is a manufacturing method. The polyester in the present invention is a polyester having terephthalic acid as the main acid component and at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is It may also be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/or a part of the glycol component is replaced with the above-mentioned glycol other than the main component or other diol component. It may also be made of polyester. Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid,
Diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5-
Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sodium sulfoisophthalic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. In addition, examples of diol compounds other than the above-mentioned glycols include cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S.
Examples include aliphatic, alicyclic, and aromatic diol compounds such as, and polyoxyalkylene glycols. Particularly one of the difunctional carboxylic acid components.
A modified polyester in which ~7 mol % of the polyester is replaced with an isophthalic acid component containing an alkali metal sulfonate group such as 5-sodium sulfoisophthalic acid is a preferred polyester because the effects of the present invention are remarkable. Further, to the extent that the polyester is substantially linear, hot polycarboxylic acids such as trimellitic acid and pyromellitic acid, glycerin, trimethylolpropane,
Polyols such as pentaerythritol can be used. Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are transesterified. The first stage reaction is to react with terephthalic acid to produce a glycol ester and/or its low polymer, and the first stage reaction product is heated under reduced pressure until the desired degree of polymerization is achieved. It is produced by a second step of polycondensation reaction. The phosphorus compound used in the present invention has the following general formula (I) It is a phosphorus compound represented by the following formula, where R is H or a monovalent organic group, and a monovalent organic group is particularly preferable. Specifically, this monovalent organic group is an alkyl group, an aryl group, an aralkyl group, or [(CH ₂ )lO]kR″ (where R″ is H, an alkyl group,
An aryl group or an aralkyl group, l is an integer of 2 or more, k is an integer of 1 or more), etc. are preferable. X is
OH, OR' or a monovalent organic group, R' is the above R
Same as the definition of monovalent organic group in
R' and R may be the same or different, and the monovalent 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 monovalent organic group,
Among these, metal is preferred. The metal in Q is preferably an alkaline earth metal or an alkali metal;
More preferably Li, Na, K, Mg1/2, Ca1/2,
Sr1/2 and Ba1/2 can be raised, especially Ca
Particularly preferred is 1/2. The monovalent organic group in Q is
It is the same as the definition of the organic group in R and R' above, and may be the same or different from R and R'.
n is 1 or 0. Such phosphorus compounds include, for example, orthophosphoric acid,
phosphoric acid triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate; phosphoric acid mono- and diesters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate; Phosphite triesters such as phosphorous acid, trimethyl phosphite, triethyl phosphite, and tributyl phosphite; phosphorous acids such as methyl acid phosphite, ethyl acid phosphite, isopropyl acid phosphite, and butyl acid phosphite; Acid 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; One type selected from metal-containing phosphorus compounds obtained by reacting a compound with a predetermined amount of an alkali metal compound such as Li, Na, or K or an alkaline earth metal compound such as Mg, Ca, Sr, or Ba. The above phosphorus compounds can be used. In order to produce the above-mentioned metal-containing phosphorus compounds, orthophosphoric acid, phosphorous acid, phosphonic acid, orthophosphoric acid ester (mono, di, or tri), phosphite (mono, di, or tri), or phosphonic acid ester are usually used. and a predetermined amount of the corresponding metal compound 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 to be 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. , alkaline earth metals such as Ca, Sr, and Ba, acetates of alkali metals such as Li, Na, and K;
organic carboxylates such as oxalates, benzoates, phthalates, stearates; inorganic acid salts such as borates, sulfates, silicates, carbonates, bicarbonates;
Halides such as chloride, ethylenediamine4
Examples include chelate compounds such as acetic acid complexes, hydroxides, oxides, alcoholates such as methylates, ethylates, and glycolates, and phenolates. Particularly preferred are organic carboxylates, halides, chelate compounds, and alcoholates that are soluble in ethylene glycol, and among them, organic carboxylates are particularly preferred. Furthermore, Ca is particularly preferred as the alkaline earth metal. The above metal compounds may be used alone or in combination of two or more. When blending the above-mentioned phosphorus compounds and metal compounds, the resulting fibers are subjected to alkali weight loss treatment to give them excellent color depth, clarity, and drapability, and the resulting film has excellent transparency. In order to provide smoothness and slipperiness, it is necessary to specify the amount of the phosphorus compound to be used and the ratio of the amount of the metal compound to the amount of the phosphorus compound to be used. 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, whereas if it is too large, the transparency and abrasion resistance of the fibers and films will be insufficient. Sexuality begins to decline. Therefore, the amount of the phosphorus compound added should be in the range of 0.1 to 5 mol% based on the difunctional carboxylic acid component constituting the polyester. In addition, the amount of the metal compound added is such that the total amount of metal equivalents of the metal compound and the phosphorus compound is 2.0 with respect to the number of moles of the phosphorus compound.
If the amount is less than twice the amount, the resulting polyester fibers will have insufficient depth of color, drapability, and slipperiness of the film, and furthermore, the softening point of the polyester produced will be lowered. On the other hand, if a metal compound is used in an amount exceeding 3.2 times this amount, coarse particles will be generated, reducing the transparency of fibers and films, and
The depth of color, drapability and friction durability of the fibers are reduced. 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 2.0 to 3.2 times. It is necessary to add the above-mentioned phosphorus compound and metal compound to the polyester reaction system without reacting them in advance, and by doing so, it is possible to easily generate insoluble particles in a uniform ultrafinely dispersed state in the polyester. can. 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 uniformly and ultrafinely dispersed in the polyester. It can be easily 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 are contained. So I don't like it. 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, coarse particles may be generated during the esterification reaction, or the reaction may proceed abnormally quickly and cause bumping phenomena during the transesterification reaction. In this case, it is preferable that the amount used as a catalyst is not excessively exceeded. The timing of addition of the remaining amount of the metal compound and the total amount of the phosphorus compound is preferably after the second half of the reaction in the first stage of polyester synthesis (the stage at which the reaction rate is 50% or more). In addition, if the phosphorus compound and metal compound are added at a stage where the second stage reaction has progressed too much, agglomeration and coarsening of particles are likely to occur.
The intrinsic viscosity of the reaction mixture in the second stage reaction is
Preferably 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 metal compounds mentioned above have the ability to catalyze the first stage reaction, particularly the transesterification reaction, and such compounds can be used. When used, it is not necessary to use a separate catalyst; the metal compound can be added before or during the first-stage reaction to serve as a catalyst, but as mentioned above, it is possible to prevent the bumping phenomenon. Therefore, the amount used is preferably kept 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 is represented by the following general formula () [NH ₄ ] ⁺ A ^- ... (). It is an ammonium compound. A in the formula
is an anionic residue, including organic and inorganic anionic residues, such as acetate, oxalate,
Anionic residues of organic carboxylates such as benzoates, phthalates, stearates, etc., borates,
anionic residues of inorganic acid salts such as sulfates, bisulfates, bisulfites, phosphates, carbonates, bicarbonates, thiocyanates, etc., halides such as chlorides, etc.
Examples include anion residues of hydroxide, hydrosulfate, alkyl sulfate, alkyl ether sulfate, alkyl sulfonate, alkylbenzene sulfonate, and tosylate. Preferred specific examples of such ammonium compounds include ammonium acetate, ammonium oxalate, ammonium carbonate, ammonium bicarbonate, ammonium hydroxide, ammonium chloride, ammonium ethosulfate, ammonium dodecylbenzenesulfonate, and those having an average carbon number of 14. Ammonium alkylsulfonate, ammonium p-toluenesulfonate (ammonium tosylate),
Ammonium borate, ammonium chloride, ammonium formate, ammonium amidosulfate, ammonium tartrate, ammonium aminoformate ( _{NH2COONH4 )} , ammonium 8-anilino-1-naphthalenesulfonate, ammonium carbamate, ammonium citrate, phosphoric acid Examples include ammonium, ammonium hypophosphite, ammonium salicylate, ammonium succinate, ammonium sulfamate, ammonium sulfanilate, and ammonium thioglycolate. If the amount of the ammonium compound blended is too small, the effect of improving the dispersibility of internally precipitated particles in polyester will be insufficient.As the amount is increased, the particle dispersibility will improve, but if it is too large, the particles will no longer form. Dispersibility showed no significant improvement;
Instead, the polymer begins to turn yellow.
Therefore, the amount of ammonium compound added is 0.001 to 0.5 mol% based on the bifunctional carboxylic acid component.
It should be in the range of 0.01 to 0.3 mol%, particularly preferably 0.01 to 0.3 mol%. The ammonium compound may be added at any stage until the synthesis of the polyester is completed. For example, the ammonium compound may be added and mixed into the polyester raw materials, added during the first stage reaction, or added at the first stage.
It may be added between the end of the first stage 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, it is most preferable to add a phosphorus compound, a metal compound, and an ammonium compound as a mixed transparent solution. e Effects of the Invention As explained above, in the present invention, (a) a specific amount of the phosphorus compound, (b) a specific amount ratio of an alkaline earth metal compound and/or alkali metal to the phosphorus compound. By adding the compound and (c) the ammonium compound to the polyester reaction system and then completing the production of the polyester, the dispersibility of the internal particles is particularly significantly improved. By doing this, it contains extremely finely dispersed internal particles, has a high degree of polymerization, a high softening point, high whiteness, and good passability through the spinning and film forming processes, and after being made into fibers. By performing alkali weight loss treatment, extremely fine and dense fiber surface irregularities are formed even under high alkali weight loss rates, resulting in improved drapability, dry feel,
It is possible to obtain a polyester that can provide polyester fibers that are extremely excellent in color depth, clarity, gloss, and friction durability, and that can provide a polyester film that is extremely transparent and easily slippery when formed into a film. It can be done. 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 this method is particularly large. Such modified polyester dyeable with cationic dyes includes:
For example, there may be mentioned a polyester obtained by copolymerizing an isophthalic acid component having an alkali metal sulfonate group in an amount of 1 to 7 mol % based on the bifunctional carboxylic acid component constituting the polyester. Note that the polyester obtained by the method of the present invention may contain optional additives, such as catalysts, color inhibitors, heat resistant agents, flame retardants, fluorescent brighteners,
A dissipating agent, a coloring agent, etc. may be included. f Examples The following examples will be further explained. Parts and % in Examples indicate parts by weight and % by weight, and the depth of color and friction discoloration resistance when dyeing the obtained polyester fibers were measured by the following method. (i) Depth of color As a measure of depth of color, bathochromicity (K/
S) was used. This value was determined by measuring the spectral reflectance (R) of the sample fabric using a Shimadzu RC-330 self-recording spectrophotometer.
−Munk). The larger this value is, the greater the deep color effect is. K/S=(1-R) ² /2R (measurement wavelength 500 mμ) In addition, K shows an absorption coefficient and S shows a scattering coefficient. (ii) Resistance to friction discoloration Using a Gakushin type flat abrasion machine for friction fastness testing, the test cloth was abraded a specified number of times under a load of 500g using a dioset made of 100% polyethylene terephthalate as the friction cloth. hand,
The degree of discoloration was determined using a gray scale for discoloration. The case where the wear resistance was extremely low was rated as 1st grade, and the case where it was extremely high was rated as 5th grade. For practical purposes, level 4 or above is required. Example 1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, and 0.06 parts of calcium acetate monohydrate (0.066 mol% relative to dimethyl terephthalate) were charged into a transesterification tank, and heated from 140°C over 4 hours under a nitrogen gas atmosphere. The transesterification reaction was carried out while raising the temperature to 230°C and distilling the generated methanol out of the system. Subsequently, 0.5 part of trimethyl phosphate (relative to dimethyl terephthalate) is added to the resulting reaction product.
0.693 mol%) and 0.31 part of calcium acetate monohydrate (1/2 mole relative to trimethyl phosphate) at 8.5%
At room temperature, 9.31 parts of a clear solution of phosphoric acid diester calcium salt prepared by reacting in 100% ethylene glycol at a temperature of 120°C for 60 minutes under total reflux was added.
Diester calcium phosphate salt, calcium acetate, obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times the mole relative to trimethyl phosphate) and 0.016 parts ammonium acetate (0.04 mole% relative to dimethyl terephthalate). 9.896 parts of a mixed clear solution of ammonium acetate and ammonium acetate were added, followed by 0.04 part of antimony trioxide and transferred to a polymerization vessel. Next, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour.
At the same time, the temperature was raised from 230°C to 285°C over 1 hour and 30 minutes. Polymerize for an additional 3 hours at a polymerization temperature of 285℃ under a reduced pressure of 1 mmHg or less, for a total of 4 hours and 30 minutes, to reduce the intrinsic viscosity.
0.640 and a softening point of 258°C was obtained. After the reaction was completed, the polymer was made into chips according to a conventional method. This chip was dried using a conventional method, and a spinneret with 36 circular spinning holes with a hole diameter of 0.3 mm was used.
The mixture was melt-spun at 290°C and then drawn at a draw ratio of 3.5 times according to a conventional method to obtain a raw yarn of 75 denier/36 filaments. This yarn has S twist of 2500T/m and Z twist of 2500T/m.
The highly twisted yarn was then subjected to a steam treatment at 80° C. for 30 minutes to untwist it. The twisted yarn has a warp density of 47 threads/cm and a weft density of 32.
A satin jersey fabric was woven by alternately arranging two S and Z twists at a thread/cm ratio. The obtained gray fabric was relaxed with a rotary washer for 20 minutes at boiling temperature, jibbo-erected, and then brisseted using a conventional method, and then treated with a 3.5% aqueous sodium hydroxide solution at boiling temperature to achieve a weight loss rate of 30%. fabric was obtained. Dianix fabric after this alkali treatment
BlackHG-FS (Mitsubishi Chemical Industries, Ltd. product) at 15% owf
After staining at 130℃ for 60 minutes, add 1g of sodium hydroxide/
A black-dyed cloth was obtained by reduction washing at 70° C. for 20 minutes with an aqueous solution containing 1 g of hydrosulfite. Table 1 shows the depth and friction discoloration resistance of this black cloth after 200 wears. This black dyed cloth has excellent drape and stiffness,
It had a very good rayon-like texture. Example 2 The same procedure as in Example 1 was carried out except that 0.012 parts of ammonium carbonate monohydrate (0.02 mol % based on dimethyl terephthalate) was used in place of ammonium acetate used as the ammonium compound in Example 1. . The results are shown in Table 1. The obtained woven fabric had excellent drapability similar to rayon. Example 3 In place of the ammonium acetate used as the ammonium compound in Example 1, 0.016 parts of ammonium bicarbonate (based on dimethyl terephthalate) was added.
A rayon-like fabric with high drapability was obtained in the same manner as in Example 1 except that 0.039 mol %) was used. The results are shown in Table 1. Example 4 0.072 parts of 25% in place of ammonium acetate used as the ammonium compound in Example 1
NH ₄ OH aqueous solution (for dimethyl terephthalate)
The same procedure as in Example 1 was carried out except that 0.1 mol %) was used. 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, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% relative to dimethyl terephthalate) and 0.04 part of antimony trioxide were charged into a transesterification tank, and the mixture was heated under a nitrogen gas atmosphere for 4 hours. From 140℃ to 230℃ over time
The transesterification reaction was carried out while raising the temperature to 0.degree. C. and distilling the generated methanol out of the system. Subsequently, 5.69 parts of a 10% ethylene glycol solution of calcium acetate monohydrate (as calcium acetate, based on dimethyl terephthalate) was added to the reaction product obtained in advance.
5.714 parts of a mixed solution obtained by dissolving 0.024 parts of ammonium acetate (0.06 mol% relative to dimethyl terephthalate) in 0.627 mol%) at room temperature were added, and after another 5 minutes, isopropyl acid phosphate was added.
0.575 part was added. Next, while expelling ethylene glycol from the system, the internal temperature was raised to 240°C, and the reaction mixture was transferred to a polymerization vessel. After that, 3,5-(β-hydroxyethoxycarbonyl) is added as a cationic dye-dyeable copolymerization component.
3 parts of sodium benzenesulfonate (1.7 mole % based on dimethyl terephthalate) and 0.112 parts of sodium acetate trihydrate (0.16 mole % based on dimethyl terephthalate) as an ether formation inhibitor were added to the polymerization kettle. Then 760mmHg over 1 hour
The pressure was reduced from 1 mmHg to 1 mmHg, and at the same time, the internal temperature was raised to 280°C over 1 hour and 30 minutes. Polymerization was further carried out for 2 hours and 30 minutes at a polymerization temperature of 280°C under reduced pressure of 1 mmHg or less, for a total of 4 hours, to obtain a polymer having an intrinsic viscosity of 0.552 and a softening point of 252°C. Using this polymer, spinning, stretching, hard twisting, twist stopping, weaving, embossing, presetting, and alkali treatment were carried out in the same manner as in Example 1 to obtain a satin dioset fabric with a weight loss rate of 15%. Aizen Cathilon uses this alkali-treated fabric.
Black CD-GLH (Hodogaya Chemical Co., Ltd. product) 8% owf
After dyeing at 120° C. for 60 minutes in a dye bath containing 2 g of Glauber's salt, a black dyed cloth was obtained by soaping according to a conventional method. The color depth and friction discoloration resistance of this black dyed fabric after 200 abrasions were as shown in Table 1.
The resulting fabric was extremely triacetate-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.

【table】

【table】

Claims (1)

[Scope of Claims] 1. In producing a polyester by reacting a difunctional carboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof with at least one alkylene glycol, the process up to the completion of the production reaction (a) from 0.1 to 5 with respect to the difunctional carboxylic acid component;
Mol% of the following general formula (I) [However, R is H or a monovalent organic group, and X is
OH, OR' or a monovalent organic group (where R' is a monovalent organic group), Q is a metal, H or a monovalent organic group,
n is 1 or 0. ] A phosphorus compound represented by (b) an alkaline earth metal in an amount such that the total number of equivalents of metals (a) and (b) is 2.0 to 3.2 times the number of moles of the phosphorus compound (a) compound and/or alkali metal compound and (c) 0.001 to the difunctional carboxylic acid component.
Insoluble fine particles are uniformly produced by adding and blending 0.5 mol% of an ammonium compound represented by the following general formula () [NH ₄ ] ⁺ A ^- ... () [However, A represents an anion residue] A method for producing dispersed polyester.