RU2303090C2 - Polyester fibers with modified section - Google Patents

Abstract

FIELD: polymer fibers.

SUBSTANCE: invention relates to technology of producing high-quality polyester fibers with modified section characterized by satisfactory color tone and excellent moldability and suitable for textile industry. Polyester fibers characterized by deformed section are prepared from polyester polymer. Polymer is prepared via polycondensation of aromatic dicarboxylic acid ester in presence of catalyst comprising mixture of titanium compound-based component and phosphorus compound-based component. The former includes at least one titanium alkoxide or product of reaction between this alkoxide and specific carboxylic acid or its anhydride. The latter is compound of general formula III and/or product of reaction between titanium compound-based component and phosphorus compound-based component depicted by general formula IV.

EFFECT: improved color tone and quality without napping manifestations.

15 cl, 9 dwg, 11 tbl, 52 ex

Description

FIELD OF THE INVENTION

The present invention relates to polyester fibers with a modified cross section. More specifically, it relates to polyester fibers with a modified cross section obtained using a polyester polymer with a satisfactory color tone and excellent formability.

State of the art

Polyester polymers, in particular polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate, exhibit excellent mechanical, physical and chemical performance properties and are therefore widely used for the manufacture of fibers, films and other molded products.

Such polyester polymers, for example polyethylene terephthalate, are usually prepared by first synthesizing an ethylene glycol ester of terephthalic acid and / or its lower polymer, and then heating it under reduced pressure in the presence of a polymerization catalyst to undergo a reaction to achieve the desired degree of polymerization. Other polyesters are prepared in similar ways.

It is known that the type of polycondensation catalyst used has a decisive influence on the quality of the resulting polyester, and antimony compounds are most widely used as polycondensation catalysts for producing polyethylene terephthalate.

However, the problem associated with the use of antimony compounds is that the continuous continuous spinning of fibers from a melt of polyesters results in the accumulation of foreign materials sticking in the vicinity of the spinning hole (hereinafter referred to simply as “sticking to the die”), and to a change in the direction of flow of the molten polymer (bending), which, ultimately, causes napping and rupture of the threads or the formation of inhomogeneous physical properties an elementary filaments during fiber spinning and drawing stages.

In particular, when attempting to obtain filaments with modified cross-sections using melt spinning, the complex shape of the spinning hole causes foreign material on the die to have an even greater effect on the release state of the molten polymer, while the fibers will also problems such as teasing and tearing can occur.

As a means of solving these problems, the use of reaction products as the catalysts for polyesters between titanium compounds and trimellitic acid was described (for example, see the Japanese expert examination patent publication SHO No. 59-46258) and the use of reaction products as compounds for polyesters titanium and phosphorous esters (for example, see Japanese pending patent publication SHO No. 58-38722). Despite the fact that these methods do to some extent improve the heat resistance of the melt of the polyesters, the effect of the improvement is insufficient, and for the obtained polyester polymers an improvement in the color tone is required.

As catalysts for the preparation of polyesters, titanium compound / phosphorus compound complexes have also been proposed (for example, see HEI Japanese Patent Publication No. 7-138354). However, despite the fact that this method to some extent provides an improvement in the heat resistance of the melt, this effect is insufficient, and an improvement in color tone is required for the obtained polyesters.

Disclosure of invention

The first objective of the invention is to solve the above-mentioned problems of the prior art by providing polyester fibers with a modified cross section that are characterized by a satisfactory color tone, lack of napping and high quality. This goal is achieved by the following polyester fibers with a modified cross section.

Polyester fibers with a modified cross section, containing as a main component a polyester polymer and characterized by the presence of a modified cross section, where

this complex polyester polymer is obtained by polycondensation involving an ester of an aromatic dibasic carboxylic acid in the presence of a catalyst,

this catalyst contains at least one ingredient selected from the following mixture (1) and reaction product (2),

the mixture (1) is a mixture of the following components (A) and (B):

(A) a component based on a titanium compound, comprising at least one compound selected from the group consisting of

(a) titanium alkoxides described by the following general formula (I):

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one group selected from among alkyl groups containing from 1 to 20 carbon atoms and phenyl groups, m is an integer in the range of 1-4, and if m is an integer equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ can be the same or different, and

(b) reaction products between titanium alkoxides described by the above general formula (I) and aromatic polyvalent carboxylic acids described by the following general formula (II):

where n is an integer in the range of 2-4,

either their anhydrides, and

(B) a component based on a phosphorus compound containing at least one compound described by the following general formula (III):

where each of R ⁵ , R ⁶ and R ⁷ independently represents alkyl groups containing from 1 to 4 carbon atoms, and X represents at least one group selected from the group —CH ₂ - and the group —CH ₂ ( Y), where Y represents a phenyl group,

the mixture (1) of the catalyst is used at a ratio of the concentrations of the components in the mixture such that the ratio (%) M _Ti between millimoles of the titanium element in the component based on the titanium compound (A) and the number of moles of aromatic dibasic carboxylic acid ester and the ratio (%) M _p between millimoles of the phosphorus element in the component based on the phosphorus compound (B) and the number of moles of aromatic dibasic carboxylic acid ester, the following expressions (i) and (ii) are satisfied:

and the reaction product (2) is the reaction product between the following components (C) and (D):

(C) a component based on a titanium compound containing at least one compound selected from the group consisting of

(c) titanium alkoxides described by the above formula (I), and

(d) reaction products between titanium alkoxides described by the above general formula (I) and aromatic polyvalent carboxylic acids described by the above general formula (II) or their anhydrides, and

(D) a component based on a phosphorus compound containing at least one phosphorus compound described by the following general formula (IV):

where R ⁸ represents alkyl groups containing from 1 to 20 carbon atoms, or aryl groups containing from 6 to 20 carbon atoms, and p represents an integer equal to 1 or 2.

Component (A) of the mixture (1) for the catalyst and component (C) of the reaction product (2) for the catalyst for the polyester fibers with a modified cross-section of the invention preferably contain the corresponding titanium alkoxide (a) and titanium alkoxide (c), each with a molar the ratio in the reaction with respect to the aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride in the range from 2: 1 to 2: 5.

In the reaction product of reaction (2) for the polyester fiber catalyst with a modified cross section of the invention, the ratio in the reaction between component (D) and component (C) is preferably in the range from 1: 1 to 3: 1 based on the ratio between moles of atoms phosphorus in component (D) and moles of titanium atoms in component (C) (P / Ti).

The phosphorus compound described by the general formula (IV) used in the reaction product (2) for the polyester fiber catalyst with a modified cross section of the invention is preferably selected from monoalkyl phosphates.

The aromatic dibasic carboxylic acid ester in the case of polyester fibers with a modified cross-section of the invention is preferably a diester obtained by transesterification between a dialkyl ester of an aromatic dibasic carboxylic acid and an alkylene glycol ester in the presence of a catalyst containing a titanium compound.

The aromatic dibasic carboxylic acid in the case of polyester fibers with a modified cross-section of the invention is preferably selected from terephthalic acid, 1,2-naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, diphenyldicarboxylic acid and diphenoxyethane dicarboxylic acid, and alkylene glycol, triethylene glycol, ethylene glycol, and trialkylene glycol are preferred. , propylene glycol, neopentyl glycol, hexanemethylene glycol and dodecanmethylene glycol.

The second objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross section, which allows to obtain fabrics that do not cause adhesion and are characterized by excellent softness, impermeability, low air permeability, hygroscopicity and wear resistance. This goal is achieved by using the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as the main component a polyester polymer obtained by polycondensation in the presence of the above specific catalyst, where the cross-sectional shape of each individual fiber is flat and flat represents a form, including 3-6 forms with a circular cross section connected in the longitudinal direction.

The polyester fibers with a modified cross section preferably contain inorganic particles in an amount in the range of 0.2-10% (wt.).

In the cross section of the polyester fibers with the modified cross section, the flatness represented by the A / B ratio between the length A of the long axis and the maximum length B of the short axis perpendicular to the long axis A is preferably in the range of 3-6.

In the cross section of polyester fibers with a modified cross section, the irregularity represented by the B / C ratio between the maximum length of the short axis and the minimum length of C (minimum length at the junction points of the forms with a circular cross section) preferably exceeds 1 and less than 5 .

A third objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross-section), characterized by excellent hygroscopicity and quick drying ability. This goal is achieved by the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as a main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where in the cross section of each individual fiber from the core of the cross section the fibers go out 3-8 ribs, and the protrusion coefficient, determined in accordance with the following formula (iii), is in the range from 0.3 to 0.7 .

Here a ₁ represents the distance from the center of the circle inscribed in the inner walls of the fiber cross-section to the tip of the rib, ab ₁ represents the radius of the circle inscribed in the inner walls of the fiber cross-section.

The degree of crystallinity of the fiber in the case of polyester fibers with a modified cross section is preferably not more than 30%.

The degree of shrinkage of the fiber in boiling water in the case of polyester fibers with a modified cross section is preferably 15-70%.

The fourth objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross-section, which allows to obtain fabrics that are characterized by the presence of bulk and soft neck. This goal is achieved by using the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as the main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where the cross section of each individual fiber includes a core and several ribs extending from cores in the radial direction along the length of the core, and polyester fibers satisfying all of the following, respectively solutions (iv) to (vi) are subjected to alkaline hydrolysis to separate at least some of the ribs from the cores.

Here, S _A is the cross-sectional area of the core, D _A is the core diameter if the cross-section is a circle, or the diameter of the circumscribed circle if the cross-section is not a circle, a S _B , L _B and W _B are the cross-sectional area sections, maximum length and maximum width of ribs, respectively.

In the case of the modified cross-sectional polyester fibers described above, the polyester fibers preferably include a compound characterized by the compatibility parameter χ described by the following relation (vii) in the range 0.1-2.0, in an amount of, before alkali treatment in the range of 0.5-5.0% (mass.) based on the weight of the fibers of the complex polyester.

Here, V _a is the molar volume (cm ³ / mol) of the polyester, R is the gas constant (J / mol · K), T is the absolute temperature (K), and δa and δb are the solubility parameters (J ^{1 / 2} / cm ^3/2 ) for polyester and compound, respectively.

The fifth objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross-section, which allow you to get a silky fabric that causes a rough creaking sensation, an excellent feeling of swelling, a sense of flexibility and lightness, in the absence of spots from uneven dyeing. This goal is achieved by the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as a main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where the cross-sectional shape of an individual fiber is a shape comprising a triangular section shape and protrusion extending from one vertex of the triangle, where both the following relations (viii) and (ix) are satisfied, and a hollow region in the section of a triangular shape, comprising 3-15% of it.

Here, L1 is the distance from the connection point of the triangular shape section and the protrusion to the tip of the protrusion, L2 is the distance from the connection point of the triangular shape section and the protrusion to the side of the triangular shape section opposite the connection point, h1 is the width of the protrusion, and h2 is the length the sides of the triangular shape section opposite the junction of the triangular shape section and the protrusion.

Modified cross-sectional polyester fibers preferably include an organic sulfonic acid-metal salt of the metal described by the following general formula (V) in an amount in the range of 0.5-2.5% (wt.) Based on the weight of the fibers of the complex polyester.

Here, R ⁹ represents alkyl groups containing from 3 to 30 carbon atoms, or an aryl or alkylaryl group containing from 7 to 40 carbon atoms, and M represents an alkali metal or alkaline earth metal.

Brief Description of the Drawings

Figure 1 is a set of schematic illustrations showing examples of cross-sectional shapes for polyester fibers with modified cross-section, which achieve the second objective of the invention.

Figure 2 is a schematic illustration, for the purpose of explaining the dimensions, showing one example of a cross-sectional shape for polyester fibers with modified cross-section, which achieve the second objective of the invention.

FIG. 3 is a schematic illustration showing one example of a cross-sectional shape for polyester fibers with modified cross-sections that achieve the third object of the invention.

FIG. 4 is a schematic illustration showing one example of a nozzle outlet used to form modified cross-sectional polyester fibers that achieve the third objective of the invention.

5 is a schematic illustration showing one example of a cross-sectional shape for polyester fibers with a modified cross-section before processing under alkaline hydrolysis conditions that achieve the fourth objective of the invention.

6 is a schematic illustration showing examples of nozzle outlets used to form modified cross-section polyester fibers that achieve the fourth objective of the invention.

Fig. 7 is a schematic illustration showing a side view of polyester fibers with a modified cross section (after processing under alkaline hydrolysis conditions) that achieve the fourth objective of the invention.

FIG. 8 is a schematic illustration for illustrating dimensions, showing one example of a cross-sectional shape for polyester fibers with modified cross-sections that achieve the fifth objective of the invention.

FIG. 9 is a schematic illustration showing one example of a nozzle outlet used to form modified cross-sectional polyester fibers that achieve the fifth objective of the invention.

The best way to implement the invention

An essential feature of the polyester fibers with a modified cross section of the invention is that they are polyester fibers containing the polyester polymer as a main component and having a modified cross section, and that the polyester polymer is obtained as a result polycondensation involving an ester of an aromatic dibasic acid in the presence of a specific talizator. This makes it possible to obtain fibers from a complex polyester with a modified cross section, characterized by a satisfactory color tone, as well as the absence of napping and high quality, despite the formation of fibers from a die with a complex outlet. In addition to this, since stable production from the polymer can be carried out even when polyester fibers with a modified cross section are characterized by a high degree of irregularity, the fibers can exhibit satisfactory functions due to their irregularity (hygroscopicity, anti-fouling, impermeability) and bar (quality to the touch, change in color tone, gloss and the like). “Modified cross-section” means a cross-sectional shape that is not circular, such as in the case of an elliptical, flat, triangular, square, cross-shaped, star-shaped, C-shaped, H-shaped, I-shaped, L-shaped, S- shaped, T-shaped, U-shaped, V-shaped, W-shaped, X-shaped, Y-shaped or Z-shaped cross section. The effect of the invention is more pronounced in the case of complex cross-sectional shapes and modified cross-sections with strictly defined angles and sizes in each cross-sectional area.

The polycondensation catalyst consists of at least one representative selected from (1) mixtures of a component based on a titanium compound (A) and a component based on a phosphorus compound (B) described below, and (2) reaction products between the component based a titanium compound (C) and a component based on a phosphorus compound (D) as described below.

The titanium compound (A) in the mixture (1) for the polycondensation catalyst consists of at least one compound selected from the group consisting of

(a) titanium alkoxides described by the following general formula (I):

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one group selected from among alkyl groups containing from 1 to 20 carbon atoms, preferably from 1 to 6 atoms, and phenyl groups, m is an integer in the range of 1-4, and preferably 2-4, and if m is an integer equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ can be the same or different, and

(b) reaction products between titanium alkoxides described by the above general formula (I) and aromatic polyvalent carboxylic acids described by the following general formula (II):

where n is an integer in the range of 2-4, and preferably 3-4,

or their anhydrides.

The phosphorus compound (B) in the mixture (1) for the polycondensation catalyst consists of at least one compound described by the following general formula (III):

where each of R ⁵ , R ⁶ and R ⁷ independently represents alkyl groups containing from 1 to 4 carbon atoms, and X represents at least one group selected from the group —CH ₂ - and the group —CH ₂ ( Y) (where Y represents a phenyl group).

The product of reaction (2) for the polycondensation catalyst is a reaction product between a component based on a titanium compound (C) and a component based on a phosphorus compound (D).

A component based on a titanium compound (C) consists of at least one compound selected from the group consisting of

(c) titanium alkoxides described by the above formula (I), and

(d) reaction products between titanium alkoxides described by the above general formula (I) and aromatic polyvalent carboxylic acids described by the above general formula (II) or their anhydrides.

A component based on a phosphorus compound (D) consists of at least one phosphorus compound described by the following general formula (IV):

where R ⁸ represents alkyl groups containing from 1 to 20 carbon atoms, or aryl groups containing from 6 to 20 carbon atoms, and p represents an integer equal to 1 or 2.

If a mixture of (1) a component based on a titanium compound (A) and a component based on a phosphorus compound (B) is used as a polycondensation catalyst, then titanium alkoxide (a) described by general formula (I) or the reaction product (b) between titanium alkoxide (a) and aromatic carboxylic acid described by the general formula (II), or its anhydride, used as a component based on titanium compound (A), will be characterized by high solubility and compatibility with polyester polymers, and therefore, evenif the remainder of the component based on the titanium compound (A) remains in the polyester formed by polycondensation, no foreign material will accumulate around the die during spinning of the fibers from the melt, so that satisfactory quality polyester fibers can be obtained with high molding efficiency.

As described by the general formula (I), titanium alkoxides (a) used in the component based on the titanium compound (A) or (C) of the polycondensation catalyst, tetraisopropoxy titanium, tetrapropoxy titanium, tetra-n-butoxy titanium, tetra ethoxy titanium, tetraphenoxy titanium, titanium hexaalkyl titanate.

The aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride, which is reacted with titanium alkoxide (a) or (c), is preferably selected from phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their anhydrides. In particular, using trimellitic anhydride, a reaction product will be obtained that demonstrates a high affinity for the polyester polymer, which will effectively prevent the accumulation of foreign material.

If titanium alkoxide (a) or (c) of a component based on a titanium compound (A) or (C) is reacted with an aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride, then, for example, an aromatic polyvalent carboxylic the acid or its anhydride is preferably dissolved in a solvent, titanium alkoxide (a) or (c) is added dropwise to the solution and the mixture is heated for at least 30 minutes at a temperature of 0-200 ° C. The solvent used in this case is preferably selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene and xylene as appropriate.

The molar ratio in the reaction between titanium alkoxide (a) or (c) and aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride does not impose any particular restrictions, but if the proportion of titanium alkoxide is excessively high, then the color tone the resulting polyester may be deteriorated, or the softening temperature may be lowered, while if the proportion of titanium alkoxide is excessively low, then there may be difficulties in the reaction condensation. Therefore, the molar ratio in the reaction between titanium alkoxide (a) or (c) and the aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride is preferably in the range from 2 :) to 2: 5.

The reaction product (b) or (d) resulting from the reaction can be used directly or it can be used after purification by recrystallization using acetone, methyl alcohol and / or ethyl acetate.

The phosphorus compound (phosphonate derivative) described by the general formula (III) used in the component based on the phosphorus compound (B) of the mixture (1) for the polycondensation catalyst of the invention is preferably selected from dimethyl esters, diethyl esters, dipropyl esters and dibutyl esters of phosphonic acid derivatives such as carbomethoxymethanephosphonic acid, carboethoxymethanephosphonic acid, carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic I acid, carbomethoxyphenylmethanphosphonic acid, carbethoxyphenylmethanphosphonic acid, carbopropoxyphenylmethanphosphonic acid, carbobutoxyphenylmethanphosphonic acid and the like.

If for the polycondensation reaction involving an ester of an aromatic dibasic carboxylic acid, a component based on a phosphorus compound (B) consisting of a phosphorus compound (phosphonate derivative) described by the general formula (III) is used, then a reaction with a component based on a titanium compound (A) will proceed more moderately in comparison with the reaction using phosphorus compounds used as reaction stabilizers usually, and therefore the operational life as a catalyst for the component based on the titanium compound (A) in the method of carrying out the polycondensation reaction will be longer, and as a result, a smaller proportion of the component based on the titanium compound (A) with respect to the amount of aromatic dibasic carboxylic acid ester in the polycondensation reaction system can be used. In addition, even if a large amount of stabilizer is added to the polycondensation reaction system containing a component based on a phosphorus compound (B) consisting of a phosphorus compound described by the general formula (III), then the resulting polyester polymer will not suffer any heat resistance deterioration, and its color tone will also be satisfactory.

If mixture (1) is used as the polycondensation catalyst corresponding to the invention, then mixture (1) is used at such a ratio of the concentrations of the components in the mixture that the ratio (%) M _Ti between millimoles of the titanium element in the component based on the titanium compound (A) and the number of moles of the aromatic dibasic carboxylic acid ester and the ratio (%) M _p between millimoles of the phosphorus element in the component based on the phosphorus compound (B) and the number of moles of the aromatic dibasic carboxylic ester acids will satisfy the following ratios (i) and (ii):

The ratio of M _p / M _ti is in the range from 1 to 15, and preferably from 2 to 10. If the ratio of M _p / M _Ti is less than 1, then the color tone of the obtained complex polyester polymer may be yellowish, while if if it is more than 15, then the polycondensation reactivity of the polycondensation catalyst with such a composition will be insufficient, which will make obtaining the target complex polyester polymer difficult. The range for the M _p / M _Ti ratio of the invention is relatively narrow compared to the range used for conventional Ti-P catalysts, but maintaining this range provides an excellent result that was not obtained with commonly used Ti-P catalysts.

The value of the sum (M _p + M _Ti ) is in the range from 10 to 100, and preferably from 20 to 70. If the value (M _p + M _Ti ) is less than 10, then the fiber-forming properties of the obtained complex polyester polymer, the productivity of the molding method fibers from the melt and the performance of the resulting fibers will be unsatisfactory. If the value (M _p + M _Ti ) is greater than 100, then when using the obtained complex polyester polymer for forming fibers from the melt around the die, accumulation of foreign material will be observed to a small but significant degree. The value of M _ti in the General case, it is preferable to have in the range of 2-15, and more preferably 3-10.

If the reaction product (2) is used as the polycondensation catalyst of the invention, then the phosphorus compound described by the general formula (IV) used as the phosphorus compound (D) can be, for example, monoalkyl phosphate, such as mono-n- butyl phosphate, monohexyl phosphate, monododecyl phosphate, monolauryl phosphate or monooleyl phosphate; monoaryl phosphate such as monophenyl phosphate, monobenzyl phosphate, mono (4-ethyl phenyl) phosphate, monobiphenyl phosphate, mononaphthyl phosphate or monoantryl phosphate; dialkyl phosphate, such as diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dilauryl phosphate or dioleyl phosphate, or diaryl phosphate, such as diphenyl phosphate. Of these, monoalkyl phosphates or monoaryl phosphates are preferred, where p in formula (IV) is 1.

A component based on a phosphorus compound (D) used in the invention may be a mixture of two or more than two phosphorus compounds described by the general formula (IV), and mixtures of monoalkyl phosphates and dialkyl phosphates or a mixture of monophenyl phosphates and diphenyl phosphates may be mentioned as examples of preferred combinations . Particularly preferred are compositions wherein the monoalkyl phosphate is at least 50%, and in particular at least 90%, of the mixture based on the total weight of the mixture.

A method of obtaining a reaction product between a component based on a titanium compound (C) and a component based on a phosphorus compound (D) may include, for example, combining components (C) and (D) and heating them in glycol. Specifically, heating a glycol solution containing a component based on a titanium compound (C) and a component based on a phosphorus compound (D) will cloud the glycol solution with the precipitation of components (C) and (D) as reaction products. The precipitate can be collected for use as a catalyst to obtain a complex polyester polymer.

The glycol used in this case is preferably the same glycol component as that used in the preparation of the polyester using the obtained catalyst. For example, ethylene glycol is preferred if the polyester is polyethylene terephthalate, 1,3-propanediol is preferred if the polyester is polytrimethylene terephthalate, and tetramethylene glycol is preferred if the polyester is polytetramethylene terephthalate.

The product of the polycondensation reaction (2), corresponding to the invention, can be obtained by the method while combining the component in the form of a compound of titanium (C) and a compound of phosphorus (D) and glycol and heating them. However, since heating causes a reaction to occur between the component based on the titanium compound (C) and the component based on the phosphorus compound (D) to produce a precipitated reaction product that is insoluble in glycol, it is preferable that the reaction proceeds homogeneously. Therefore, in order to efficiently obtain a precipitate in the reaction, a preferred preparation method is a method in which separate solutions in the glycol of a component based on a titanium compound (C) and a component based on a phosphorus compound (D) are preliminarily prepared, and then the solutions are combined and heated .

The reaction temperature between components (C) and (D) is preferably in the range of 50 to 200 ° C., and the reaction time is preferably in the range of 1 minute to 4 hours. If the reaction temperature is excessively low, then the reaction may not take place sufficiently, or it may be necessary to have an excess reaction time, which will make it impossible to effectively obtain a precipitate of reaction products during a homogeneous reaction.

The ratio of the concentrations of the components in the mixture of the component based on the titanium compound (C) and the component based on the phosphorus compound (D), heated to the reaction in glycol, is preferably in the range from 1.0 to 3.0, and more preferably from 1.5 up to 2.5 based on the molar ratio between phosphorus atoms and titanium atoms. Within this range, a component based on a phosphorus compound (D) and a component based on a titanium compound (C) will react almost completely, which will avoid the presence of an incomplete reaction product, and therefore the reaction product can be used directly to obtain a polyester polymer with a satisfactory color tone. In addition, the practical absence of an excess of the unreacted phosphorus (V) compound results in achieving high performance without compromising the polymerization reactivity to produce a polyester.

The reaction product (2) for the polycondensation catalyst used in the invention preferably contains a compound described by the following general formula (VI):

where each of R ¹⁰ and R ¹¹ independently represents at least one group selected from among C _6-12 aryl groups derived from R ¹ , R ² , R ³ and R ⁴ in the General formula (I) describing titanium alkoxide of a component based on a titanium compound (C), and R ⁸ in the general formula (IV) describing a phosphorus compound of a component based on a phosphorus compound (D).

Since the reaction product between the titanium compound and the phosphorus compound (III) or (IV) described by formula (VI) has high catalytic activity, the polyester polymers obtained using it are characterized by a satisfactory color tone (low b value) and demonstrate satisfactory practical polymer performance at a level of acetaldehyde, residual metals and cyclic trimers is low enough for practical use. The reaction product described by formula (VI) is preferably present at a content level of 50% (wt.) Or more, and more preferably 70% (wt.) Or more.

If an ester of an aromatic dibasic carboxylic acid is subjected to polycondensation in the presence of a reaction product (2), then the latter can be used as a catalyst for producing the polyester directly, without separation of glycol and precipitated reaction product (2) obtained by the above method. In addition, after separating the precipitate from the solution in glycol containing the precipitated reaction product (2), using methods such as centrifugal precipitation or filtration, the precipitated reaction product (2) for purification can be recrystallized using, for example , acetone, methyl alcohol and / or water, and a purified product can be used as a catalyst. The structure of the catalyst can be confirmed using the solid-state NMR method and the method of quantitative analysis of the content of metal PMA.

The polyester polymer used in the invention is obtained by polycondensation involving an ester of an aromatic dibasic carboxylic acid in the presence of a catalyst containing the above mixture (1) of a component based on a titanium compound (A) and a phosphorus compound (phosphonate derivative) (B) and / or a reaction product (2) between a component based on a titanium compound (C) and a component based on a phosphorus compound (D). According to the invention, the aromatic dibasic carboxylic acid ester is preferably a diester formed from an aromatic dibasic carboxylic acid component and an aliphatic glycol component.

The aromatic dibasic carboxylic acid preferably mainly consists of terephthalic acid. More specifically, terephthalic acid is preferably at least 70 mole percent based on the total amount of the aromatic dibasic carboxylic acid component. As examples of preferred aromatic dibasic carboxylic acids other than terephthalic acid, mention may be made of phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethane dicarboxylic acid.

The aliphatic glycol component is preferably alkylene glycol, among which, for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexane methylene glycol and dodecamethylene glycol can be used, with ethylene glycol being particularly preferred.

In accordance with the invention, the polymeric polyester is preferably a polyester containing ethylene terephthalate formed from terephthalic acid and ethylene glycol as its main repeating unit. “Basic” means that the ethylene terephthalate repeating unit is at least 70 mole percent, based on the total number of repeating units in the polyester.

The polyester polymer used in the invention can also be a mixed polyester, obtained by copolymerization between the components that form the polyester, such as an acid component or a diol component.

As for the mixed components in the form of carboxylic acids, it is of course possible to use the above-mentioned aromatic dibasic carboxylic acids as well as components in the form of bifunctional carboxylic acids, including aliphatic dibasic carboxylic acids, such as adipic acid, sebacic acid acid, azelaic acid and decanedicarboxylic acid, and alicyclic dibasic carboxylic acids, such as cyclohexanedicarboxylic acid, or derivatives thereof Forming esters. As for the mixed diol components, the use of the above-mentioned aliphatic diols, as well as alicyclic glycols, such as cyclohexanedimethanol, and aromatic diols, such as bisphenol, hydroquinone and 2,2-bis, is possible as starting materials. β-hydroxyethoxyphenyl) propane.

In addition to this, it is also possible to use mixed polyester polymers obtained as mixed components by copolymerizing polyfunctional compounds such as trimesic acid, trimethylol ethane, trimethylol propane, trimethylol methane and pentaerythritol.

Such polyester polymers and mixed polyester polymers can be used individually or in combination of two or more than two polymers.

In accordance with the invention, the polyester polymer used is preferably a polycondensation product involving an aromatic dibasic carboxylic acid ester formed from aromatic dibasic carboxylic acid and aliphatic glycol as previously described. An aromatic dibasic carboxylic acid ester can also be obtained by conducting a diesterification reaction between an aromatic dibasic carboxylic acid and an aliphatic glycol, or it can be obtained by carrying out a transesterification between an aromatic dibasic carboxylic acid dialkyl ester and an aliphatic glycol. However, methods involving transesterification using aromatic dibasic carboxylic acids as dialkyl esters as starting materials are more preferable compared to diesterification methods using aromatic dibasic carboxylic acids as starting materials, as the former result in less debris of the phosphorus compound added to polycondensation reaction time as a phosphorus-containing stabilizer.

In addition, it is preferable to add all or part of the component based on the titanium compound (A) or (C) before initiating the transesterification reaction in order to use it as a catalyst for two reactions, i.e., a transesterification reaction catalyst and a polycondensation reaction catalyst. This will make it possible to reduce the level of titanium compound in the final polyester. More specifically, in the case of polyethylene terephthalate, for example, the transesterification reaction between a dialkyl ester of an aromatic dibasic carboxylic acid (formed mainly from terephthalic acid) and ethylene glycol is preferably carried out in the presence of a component based on titanium compound (A) containing (a), according to at least one compound selected from the group consisting of titanium alkoxides described by the above general formula (I), and (b) reaction products between titanium alkoxides described by the general formula (I), and aromatic polyvalent carboxylic acids described by the above general formula (II), or their anhydrides. Preferably, a phosphorus compound (phosphonate derivative) described by the above general formula (III) or a reaction product between a component based on a titanium compound is preferably added to the reaction mixture containing a diester obtained from aromatic dibasic carboxylic acid and ethylene glycol as a result of the transesterification reaction. (C) and the aforementioned component based on the phosphorus compound (D), and the polycondensation reaction is carried out in their presence.

The transesterification reaction is usually carried out at normal pressure, but carrying it out at a pressure in the range of 0.05-0.20 MPa will further stimulate the passage of the reaction catalyzed by the action of the component based on the titanium compound (A), while at the same time preventing the formation of large amounts of side diethylene glycol product, so that it will be possible to obtain more favorable heat resistance and other properties. The temperature is preferably in the range 160-260 ° C.

If the aromatic dibasic carboxylic acid used in the invention is terephthalic acid, then the starting materials used to make the polyester are terephthalic acid and dimethyl terephthalate. In this case, it is possible to use recovered dimethyl terephthalate obtained as a result of depolymerization of polyalkylene terephthalate, or recovered terephthalic acid obtained as a result of its hydrolysis. From the point of view of efficient use of resources, it is preferable to use recycled polyesters from recyclable PET bottles, fiber products, polyester film products and the like.

The polycondensation reaction can be carried out in one tank or in several separate tanks. The resulting product is a polyester according to the invention, and the polyester obtained by the polycondensation process is usually extruded in a molten state and cooled to obtain particles (granules).

The polyester used in the invention, which is obtained by the polycondensation method described above, can optionally be subjected to solid phase polycondensation.

Solid-state polycondensation consists of one or several stages, and it is carried out at a temperature in the range of 190-230 ° C and a pressure in the range of 1 to 200 kPa in an inert gas atmosphere such as nitrogen, argon or gaseous carbon dioxide.

The polyester particles obtained by the solid-state polycondensation process are then subjected to water treatment as needed by contacting with water, water vapor, an inert gas enriched in water vapor, or air enriched in water vapor to deactivate the catalyst remaining in granules.

The method for producing a polyester described above, including the steps of esterification and polycondensation, can be implemented in a batch, semi-continuous or continuous system.

The polyester polymer used in the invention is preferably selected from polyethylene terephthalate, polytrimethylene terephthalate and polytetramethylene terephthalate.

The polyester polymer used in the invention is preferably also characterized by an L ^* value in the range of 77-85 and a b ^* value in the range of 2-5, based on the L ^* a ^* b ^* colorimetric system (JIS Z8729).

The intrinsic viscosity of the polyester used in the invention and obtained by the method described above is preferably in the range of 0.40-0.80, more preferably 0.45-0.75, and even more preferably 0.50-0.70. The intrinsic viscosity is preferably not inferior to 0.40, because the strength of the fibers may be insufficient. On the other hand, an intrinsic viscosity in excess of 0.80 is irrational from an economic point of view because it requires an excess increase in the intrinsic viscosity of the starting polymer.

The polyester used in the invention, if necessary, may contain small amounts of additives, such as antioxidants, ultraviolet absorbers, flame retardants, fluorescent brighteners, matting agents, color correctors, antifoam agents, antistatic agents, antimicrobial agents, light stabilizers, heat stabilizers, light and the like, and preferably titanium dioxide as a matting agent and antioxidants as stabilizers are added.

The titanium dioxide used is preferably characterized by an average particle size in the range of 0.01-2 μm, and is preferably included in the polyester polymer in an amount in the range of 0.01-10% (wt.).

Incidentally, the level of titanium contained in the catalyst in the polyester polymer does not include titanium contained in any type of titanium dioxide added as a matting agent.

If the complex polyester polymer contains titanium dioxide as a matting agent, then the titanium dioxide of the matting agent can be removed from the sample of the complex polyester polymer by dissolving the complex polyester polymer in hexafluoroisopropanol, applying a solution for centrifugation to separate and precipitate the particles of dioxide titanium from the solution, separation and collection of the liquid supernatant according to the gradient method and evaporation of the solvent from the collected fraction for Sample exercises for the tests.

Antioxidants based on spatially hindered phenols are preferably used as antioxidants. The antioxidant is preferably added in an amount not exceeding 1% (wt.), And more preferably in the range of 0.005-0.5% (wt.). Adding in an amount exceeding 1% (wt.), As a result, will lead to the occurrence of a saturation effect and can cause slag formation during the formation of fibers from the melt. Antioxidants based on spatially hindered phenols can also be used in combination with secondary antioxidants based on simple thioethers.

There are no particular restrictions on the method of adding such antioxidants to the polyester, and they can be added at any desired stage, from the initiation of the transesterification reaction to the completion of the polycondensation reaction.

The second objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross-section, which allows to obtain fabrics that do not cause adhesion and are characterized by excellent softness, impermeability, low air permeability, hygroscopicity and wear resistance, and this goal is achieved when using the polyester fibers described below with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as the main component a polyester polymer obtained by polycondensation in the presence of the above specific catalyst, where the cross sections of the fibers are flat and the flat shape is a shape comprising 3-6 forms with a circular cross section connected in the longitudinal direction.

In this case, “connected” does not mean the actual connection at the level of spinning the fibers from the melt, but rather means that the result is a “connected” form. In addition, “round cross-sectional shapes” do not necessarily correspond to a flawless circle, but may also apply to an ellipse.

The cross-sectional shapes of the fibers will now be explained with reference to FIG. Figures 1 (a) to (c) are schematic illustrations of cross-sectional shapes for fibers, wherein (a) shows 3, (b) shows 4, and (c) shows 5 connected shapes with a circular cross-section.

That is, the fiber cross-sectional shapes are structures with circular cross-sectional shapes connected in the longitudinal direction (long axis direction), where the comb / comb pairs and the trough / trough pairs are symmetrically located on both sides of the long axis, and the number of these shapes with the circular cross section is preferably in the range from 3 to 6. If the number of shapes with a circular cross section is 2, then the softness will approach the softness of a fabric with fibers with a circular cross section, but the impermeability, low air permeability and hygroscopicity will tend to deteriorate. On the other hand, if the number of shapes with a circular cross section exceeds 7, then the fibers will be more susceptible to tearing and will tend to have poor wear resistance.

Polyester fibers with a modified cross section to improve impermeability preferably contain inorganic particles in an amount in the range of 0.2-10 wt.%.

Turning further to FIG. 2, it can be said that the flatness represented by the A / B ratio between the length A of the long axis of the cross section of the polyester fibers with the modified cross section and the maximum length B of the short axis perpendicular to the long axis A is preferably in the range 3-6. If it is inferior in size to 3, then the softness will be deteriorated, while if it exceeds 6, then there will be a tendency to a sensation of adhesion.

From the point of view of eliminating the sticking sensation and improving the hygroscopicity of polyester fibers with a modified cross section, the irregularity represented by the B / C ratio between the maximum length In the short axis of the flat cross section and the minimum length C (the minimum length at the junction points of the shapes with a circular cross section) is preferably such that 1 <B / C <5. Specifically, since water diffuses due to the capillary action in the hollows of the fibers with a flat cross-section of the invention, in comparison with fibers with a circular cross-section, excellent hygroscopic properties are obtained, while a degree of irregularity of only 1 allows simple flat fiber, which as a result leads to a sensation of adhesion and loss of hygroscopicity characteristics. If the B / C exceeds 5, then it will be possible to prevent the sensation of sticking while giving hygroscopicity characteristics, but other disadvantages may appear, that is, the joints of the molds with a round cross section will become excessively short, and the strength of the fibers with a flat cross section will be deteriorated with the formation of a tendency to obtain as a result of rupture of the thread, and therefore, the ratio B / C is preferably such that 1 <B / C <5, and more preferably 1.1 ≤ B / C 2 2.

The mass number of an individual fiber in the case of polyester fibers with a modified cross section or the mass number of a single fiber formed from individual fibers, in the case of polyester fibers with a modified cross section, does not impose any special restrictions, but when used for making clothes the mass number of an individual fiber is preferably in the range of 0.3-3.0 decitex, and the mass number of a single fiber in the case of fibers of a complex The modified cross-sectional polyester is preferably in the range of 30-200 dtex.

A third objective of the invention is to provide, in addition to the first objective, polyester fibers with a modified cross section, characterized by excellent hygroscopicity and quick drying ability. This goal is achieved by using the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as a main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where 3 cross out from the core of the cross section of the fiber to the outside -8 ribs, and the protrusion coefficient, determined in accordance with the following formula (iii), is in the range from 0.3 to 0.7.

Here a ₁ represents the distance from the center of the circle inscribed in the inner walls of the fiber cross-section to the tip of the rib, ab ₁ represents the radius of the circle inscribed in the inner walls of the fiber cross-section.

Polyester fibers characterized by such cross-sectional shapes have operational characteristics that provide resistance to exposure during the stretch - false twist stages and satisfactory hygroscopicity and the ability to quickly dry in fabrics even after the stretch - false twist stages.

In the case of such polyester fibers, there is also a small degree of formation of strand breaks (technological breaks) and teasing during the stretching - false twisting stages even when the false twisting stages are carried out under ordinary conditions. The obtained fibers, subjected to stretching - false twist, are also characterized by the presence of moderate dispersion in degrees of flatness for the fiber cross sections in the directions of the fiber axes, which allows one to have fiber cross sections that are not uniform in the directions of the fiber axes, thus forming fiber aggregates with large the gaps between the fibers. Such large gaps between the fibers lead to the characteristics of increased hygroscopicity and ability to dry quickly and to improved durability of the washing performance. Fiber aggregates characterized by moderate dispersion in degrees of flatness for fiber cross-sections in the directions of the fiber axes also demonstrate operational characteristics that give the tissues a feeling of natural dryness.

Ribs with a protrusion coefficient less than 0.3 do not form the proper capillary gaps in the cross sections of the fibers after drawing - false twisting, and therefore they cannot demonstrate hygroscopicity or the ability to quickly dry. Such short ribs also exhibit low fixability when the fabric is treated under conditions of absorption in an aqueous medium, so that the washing durability for the treatment agent will tend to decrease. The neck of the fabric also becomes flatter and paper-like. On the other hand, the ribs, characterized by a protrusion coefficient exceeding 0.7, to a greater extent undergo a concentration of the operating voltage on the ribs during the drawing - false twist, and therefore, partial destruction of the fiber cross sections will occur, which will make it impossible to ensure the proper formation of capillaries, and thus, the hygroscopicity characteristics will be degraded.

Even in the case of ribs characterized by a protrusion coefficient in the range of 0.3-0.7, it can be noted that if the number of such ribs in the cross section of the fiber is 1 or 2, then at most only one internally closed region will be formed the cross section of the fiber, and therefore the phenomenon of capillary action will not easily manifest itself, and the absorbency will be impaired. The neck of the fabric will also tend to become flatter and paper-like. On the other hand, if there are more than 8 ribs during the stretching - false twist operation voltage will tend to concentrate on the ribs, resulting in partial destruction of the cross sections of the fibers and making it impossible to ensure the proper formation of capillaries, thereby degrading the hygroscopicity characteristics.

The degree of crystallinity of the fibers in the case of polyester fibers with a modified cross section is preferably not more than 30%, and the degree of shrinkage in boiling water is preferably at least 15%. This limits the increase in the crystalline region of the fibers, in the case of fibers subjected to stretching - false twisting under ordinary conditions of stretching - false twisting, preventing the formation of an excessively rigid structure of the fibers and, thus, facilitating the formation of moderate dispersion in degrees of flatness for cross sections in the directions of the axes of the fibers. The results will be improved hygroscopicity and quick drying ability and increased durability of washing performance, as well as a feeling of natural dryness for fabrics. On the other hand, a stable fiber structure can be obtained by limiting the degree of drawing in boiling water to a value not exceeding 70%.

To obtain the modified cross-sectional polyester fibers described above, any widely known melt spinning method can be used. For example, you can use the method of drying the polyester under ordinary conditions, melting it using a machine for extruding a melt, such as a screw extruder, the release of the melt from the die (figure 4), having from 3 to 8, and preferably from 4 to 6, forming outlet ribs consisting of connected small circular holes (5 in FIG. 4) and slotted holes (4 in FIG. 4) located at regular intervals around a core-forming circular outlet (3 in FIG. 4), such as write, for example, in Japanese Patent Application №3076372, and thereafter cooling, curing and winding in accordance with methods known in the art. In order to obtain fibers characterized by the above degree of crystallinity and degree of shrinkage in boiling water, the winding speed will preferably be in the range of 2000-4000 m / min, and more preferably 2500-3500 m / min.

In this case, the radius of the core forming the circular outlet (b ₂ in FIG. 4) and the distance to the extremities of the forming ribs of the outlet from the center of the circular outlet (a ₂ in FIG. 4) can be varied by freely setting the protrusion coefficient for the fiber cross-sections in area 0.3-0.7. In order to achieve a certain degree of regulation of the protrusion coefficient for the fiber cross-sections, it is also possible to vary the temperature of the spinning block and / or the volumetric flow rate of the cooling air stream. The cooling air is preferably supplied from a transverse flow type spinning shaft with a length in the range of 50-100 cm and with its tip positioned 5-15 cm below the die.

The fourth objective of the invention is to provide, in addition to the first objective, polyester fibers with modified cross-section, which allows to obtain fabrics that are characterized by the presence of bulk and soft neck. This goal is achieved by using the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as a main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where the cross section of the fibers includes a core and several ribs extending from the core into the radial direction along the length of the core, and polyester fibers satisfying all of the following relations from (iv) to (vi), They are processed under alkaline hydrolysis in order to separate at least some of the ribs from the cores.

Here, S _A is the cross-sectional area of the core, D _A is the core diameter if the cross-section is a circle, or the diameter of the circumscribed circle if the cross-section is not a circle, and S _B , L _b and W _B are the cross-sectional area sections, maximum length and maximum width of ribs, respectively.

5 shows S _A , D _A , S _B , L _B and W _B for an example of a cross-section of fibers.

If S _B / S _A <1/20 or S _B / S _A > 1/3, that is, if there are ribs characterized by a cross-sectional area of less than 1/20, or greater than 1/3 of the core cross-sectional area then the bulk of the fibers will be degraded.

In addition, if L _B / D _A <0.6, that is, if there are ribs characterized by a maximum length of less than 0.6 times the core diameter, then the bulk of the fibers will be deteriorated, while, on the other hand, if L _B / D _A > 3.0, that is, if there are ribs characterized by a maximum length greater than 3.0 times the diameter of the core, then the ribs will tend to bend, resulting in a rough neck.

In addition, if W _B / D _A > 1/4, that is, if there are ribs characterized by a maximum width greater than 1/4 of the core diameter, then it will be difficult to divide the ribs under the action of treatment under alkaline hydrolysis conditions.

A smaller maximum width of the ribs will facilitate the separation of the ribs under the action of treatment under conditions of alkaline hydrolysis, but if it is excessively small, then the ribs will tend to bend, and therefore the minimum value for W _B / D _{A is} preferably approximately 1/8.

For a more detailed explanation of the dimensions for the core and the ribs of the fibers, it can be said that the mass number of the ribs preferably does not exceed 0.9 dtex, and more preferably does not exceed 0.7 dtex. If the mass number of the ribs is excessively large, then obtaining excellent quality to the touch as a result of the presence of separated ribs will not be possible, and when the ribs are separated, an increased area of the ribs will result in poor fabric drape. The mass number of the core is preferably in the range of 1 to 5 dtex. If the mass number of the core will exceed 5 dtex, then obtaining the appropriate softness will be impossible, even if the ribs and core are separated, and the neck of the tissues will tend to become coarser. If the mass number is inferior in size to 1 dtex, then the effect of the mutual filling will increase, even if the multi-leaf cross sections will have sharp shapes, and thus there will be a tendency for the effective obtaining of large gaps.

In the case of polyester fibers, prior to treatment under alkaline hydrolysis in the polyester fibers, it is preferable to have a compound characterized by the compatibility parameter χ described by the following ratio (vii) in the range 0.1-2.0, in an amount in the range 0 , 5-5.0 wt.% When calculating the total weight of the fibers. This will facilitate the separation of the ribs and the core with the effect of increased volume and improved neck.

Here, V _a is the molar volume (cm ³ / mol) of the polyester, R is the gas constant (J / mol · K), T is the absolute temperature (K), and δa and δb are the solubility parameters (J ^{1 / 2} / cm ^3/2 ) for polyester and compound, respectively.

If χ is less than 0.1, then the polyester and the compound will become compatible, which will make it difficult to separate the ribs by alkaline hydrolysis, while if χ will be more than 2.0, then the polyester and the compound will become completely phase separated, and the polymer becomes thickened, thereby forming a tendency to deterioration of the spinnability.

If the level of content of the compound in the polyester is less than 0.5 wt.%, Then obtaining the effect of increased bulk will be difficult, while if the level of content exceeds 5.0 wt.%, Then the compound will tend to aggregate , thereby complicating the manifestation of the same effect.

As specific examples of the compound may be mentioned polymers such as polyethylene, polypropylene, polyisobutylene, polystyrene, polytetrafluoroethylene, polihlortetraetilen, polychlorotrifluoroethylene, polivinilpropionat, poligeptaftorbutilakrilat, polybutadiene, polyisoprene, polychloroprene, polyethylene glycol, polytetramethylene glycol, politrietilenglikol, polymethyl acrylate, polipropilakrilat, polybutyl acrylate, poliizobutilakrilat, polymethylmethacrylate , polyethyl methacrylate, polybenzyl methacrylate, polyethoxyethyl methacrylate, polyformal egid, polietilensulfid and polistirolsulfid and polysiloxanes and modified forms thereof. These compounds can also be used in combination of two or more than two components.

If the average molecular weight of the compound is excessively low, then thermal decomposition will occur while in the extruder or die kit, while if it is excessively high, melt miscibility with the polyester will deteriorate, and therefore the preferred range is 3000 -25000.

When adding the compound to the polyester and mixing with it, any desired widely known method can be used, such as, for example, a method for kneading a polyester in a melt and a compound and granulating the melt, an injection molding method with introducing the compound into the molten polyester during the steps of forming the fiber from the melt or a mixing method using a static mixer.

Polyester fibers can be prepared prior to treatment under alkaline hydrolysis using, for example, the following method.

Namely, the polyester can be melted and discharged through the core-forming outlet, while the melt of the same polyester, discharged through several forming ribs of slit-like outlet, located in the radial direction at certain intervals around the outlet, while remaining a melt, combines with the first melt, and both are cooled to cure.

More specifically, the polyester is melted and discharged through such a nozzle as shown in FIG. 6A, for example, having a core-forming round outlet 5 and several (four in FIG. 6A) forming ribs of slot-shaped outlet openings located radially through certain the gaps around the core-forming round outlet 5, and then the polyester discharged from the outlet 5 and the polyester discharged from the outlet 6 in a molten state SRI combined and cooled to solidification.

If necessary, the filament obtained during molding can also be subjected to drawing and heat treatment.

If the number of ribs is equal to 1 or greater than 7, then the gaps between the filaments formed as a result of processing under conditions of alkaline hydrolysis will be small, and thus, giving the appropriate bulk will be difficult. The preferred number of slit-shaped outlet openings forming ribs located around the individual core-forming outlet is in the range of 3 to 6, and more preferably 4. The cross-sectional area, maximum length and maximum width of the ribs need not be the same, and they can be different for different ribs. The ribs preferably protrude outward in the radial direction, evenly spaced in the vicinity of the central core, but this condition is not restrictive.

In accordance with the invention, there are no particular restrictions on the dimensions of the core-forming round outlet 5 and the forming ribs of the slit-like outlet 6, but in order for the area and diameter of the cross section of the core and the cross-sectional area, the maximum length and maximum width of the ribs to fall into the ranges defined by three above relations (iv), (v) and _{(vi), D 'A,} L' B, W 'B and L' _AB will preferably satisfy all the following conditions (x) - (xii), wherein D ' _A Represent It wishes to set up a diameter forming the core of the round outlet nozzle 5 (or if the cross sectional shape of the outlet opening 5 is not circular, then D _'A is the diameter of the circumscribed circle to the outlet 5), L' _B, and W _'B represent the maximum length and the maximum width of the forming ribs of the slit-like outlet 6, respectively, a L ' _AB represents the shortest distance between the outlet 5 and 6 on the outlet plane.

If D _{A A} , L _{B B} , W _{B B} and L _{AB AB} will fall outside these indicated ranges, then the spinnability may be degraded and the wear of the die may be accelerated.

The slit-shaped outlet openings forming the ribs need not necessarily be uniform rectangles, and, as shown in FIG. 6B, they can have arched swollen sections, and their width can also be continuously changed.

On the other hand, if a filament including a core and ribs is obtained by discharging a polyester from an individual outlet instead of two different types of outlet openings 5, 6 (or 6 '), then the core and ribs will be integrated with approximately the same orientation core and ribs, and therefore the separation of the ribs as a result of subsequent processing under alkaline hydrolysis will tend to be associated with more significant difficulties.

In the fiber spinning process described above, the polymer discharged from the rib-forming slit-shaped outlet is drawn to a greater extent than the polymer discharged from the core-forming outlet, so that the ribs have a higher degree of orientation than the core. Therefore, the resulting filament has a slight confusion of molecules at the junction points of the core and ribs, and, accordingly, the strength of interfacial binding at the junction points will be small, so that treatment under alkaline hydrolysis conditions will preferably lead to the separation of the ribs from the core. In addition to this, the core and ribs are characterized by different degrees of shrinkage due to their differences in orientation, which makes it possible to obtain filaments characterized by the desired bulk and soft neck.

In accordance with the invention, the obtained filaments are subjected to treatment under conditions of alkaline hydrolysis in order to separate at least some of the ribs from the cores, since this separation method is effective in minimizing the formation of freely sticking fiber ends (teasing) as a result of cleavage of the ribs or cores. If the filaments are separated using physical means involving a large energy transfer, such as when processing using spray nozzles using a high pressure air stream, such as existing in the prior art, then a large volume of freely sticking fiber ends will form while the ribs will also be separated with the transition to a fibrillar form, thus, a woven or knitted material, characterized by an external idom similar appearance material made of yarn, and the symmetry of the woven or knitted material is deteriorated.

Processing under conditions of alkaline hydrolysis can be carried out in relation to filaments or yarn from them, or woven or knitted material. However, it is preferably carried out in relation to a woven or knitted material. The alkaline treatment conditions used may be alkaline treatment conditions for common polyester filaments. Specifically, it is possible to use an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, while in a suitable case, the concentration is brought to a range of 10-100 g / liter, the temperature to a range of 40-180 ° C, and time processing - up to a range of 2 minutes to 2 hours.

The degree of separation of the ribs S as a result of processing under conditions of alkaline hydrolysis is preferably at least 30%, and the degree of separation of the ribs S in the case of filaments located in the surface layer of the multifilament yarn preferably exceeds the degree of separation of the ribs S in the case of filaments, located in the middle of the complex thread. The degree of separation of the ribs S is a value determined by the following formula:

S (%) = (number of separated ribs / total number of ribs) × 100.

The filaments located in the surface layer of the multifilament yarn are defined as those filaments from the total number of multilobe filament yarns that are located at a small distance from the imaginary circumscribed circle for a multifilament yarn in the range of up to 30% of the cross sections of the multifilament yarns. Similarly, the filaments located in the middle of the complex filaments are those filaments that are located at a small distance from the center of an imaginary circumscribed circle.

Such alkaline hydrolysis leads to the production of individual fibers, where the ribs are separated from the cores as shown in Fig.7. Fig. 7 is an enlarged side view fragment for modified polyester fibers with a modified cross section, where 4 is an individual fiber, 1 is a core, and 2, 3 are ribs extending from the core in a radial direction and mostly separated from the core.

In the polyester fibers with modified cross section 4 shown in FIG. 7, as a result of processing under alkaline hydrolysis conditions, ribs 2, 3 are attached from the core 1, attached to the core 1 along the longitudinal direction of the core 1 and extending from the core 1 in a radial direction, getting independent fibers.

It is preferred that the ribs be continuously separated from the core 1 along the entire length of the individual fiber, like rib 2 in FIG. 7, which will enable the ribs to act as independent fibers. However, the separation of all the ribs along the entire length of the filament is not an essential point, and their parts can be connected to the core, as shown in the case of rib 3.

If the ribs are separated from the core 1, for example, in a woven or knitted material, then corresponding gaps will form between adjacent cores, and therefore the woven or knitted material will have a satisfactory volume (the example of fibers shown in Fig. 5 includes four ribs with one core, but in Fig. 7, one core has only two ribs 2, 3).

Polyester fibers with a modified cross section are preferably combined and mixed with the same or different fibers to form a multifilament yarn from which a woven or knitted material is made, and then subjected to alkaline hydrolysis. The filaments can be combined and mixed up to form a multifilament yarn using any widely known method, such as winding in parallel, twisting, twisting, and the like.

The fifth objective of the invention is to propose, in addition to the first objective, polyester fibers with modified cross-section, which allow you to get a silky fabric that causes a feeling of rough creaking, an excellent feeling of swelling, a sense of flexibility and lightness, in the absence of spots from uneven dyeing. This goal is achieved by using the following polyester fibers with a modified cross section.

Specifically, they are polyester fibers with a modified cross section, containing as the main component a polyester polymer obtained by polycondensation in the presence of the above-mentioned specific catalyst, where the cross-sectional shape is a shape including a triangular shape section and a protrusion extending from one vertex of the triangle contour, where both the following relations (viii) and (ix) are satisfied, and having a hollow region in golnoy section constituting 3-15% of it.

Here, L1 is the distance from the connection point of the triangular shape section and the protrusion to the tip of the protrusion, L2 is the distance from the connection point of the triangular shape section and the protrusion to the side of the triangular shape section opposite the connection point, h1 is the width of the protrusion, and h2 is the length the sides of the triangular shape section opposite the junction of the triangular shape section and the protrusion.

If the location of the protrusion will differ from the top of the triangle contour, for example, if it moves away from the middle of the side of the triangle contour, then the spinnability will tend to deteriorate, while if the protrusion moves away from several vertices, then it will not only be deteriorated spinnability, but also the neck of the resulting fabric will tend to lose its silk-like quality. In addition, if the shape of the protrusion is not flat, for example, if it has a shape with a circular cross section, then the creaking sensation for the fabric will be less pronounced. In this case, the flat shape does not necessarily represent a uniform flat shape throughout the thickness, and individual sections may be more thickened than others. In other words, the ratio (L1 / h1) between the length (L1) and the width (h1) of the protrusion, described later, may be 2 or more, and in particular 5 or more. If the ratio is less than 2, then the form cannot be called “flat,” and the resulting fabric will not create a feeling of creaking and flexibility.

The direction of departure of the protrusion from the triangular section is preferably oriented at an angle falling into the region covered by extrapolated lines extending the two sides of the triangle contour on both sides of the vertex, and most preferably it is the direction of the bisector for the vertex.

The present invention will now be explained in more detail with reference to the accompanying drawings. 8 is a schematic illustration showing a cross-sectional shape for polyester fibers with a modified cross-section. In Fig. 8, the connection point of the triangular-shaped section and the flat protrusion is the midpoint O between two points where the outer perimeter of the triangular-shaped section (A) intersects the outer perimeter of the flat protrusion (shown as a small white circle in the drawing for convenience). The length of the protrusion L1 is the distance from the connection point to the tip of the protrusion, and L2 is the distance from the connection point to the side of the section of a triangular shape (A). If the opposite side protrudes outward or extends inward, then L2 will be the distance to the line parallel to the line connecting the two vertices of the triangle outline, different from the connection point, and tangent to the opposite side.

The width h1 of the protrusion (B) is the maximum width of the flat protrusion in the direction perpendicular to the direction of departure of the protrusion (B), while the length h2 of the opposite side is the distance between two lines perpendicular to the opposite side and touching the triangular shape section (A).

The above relative expression (viii) defines the relationship between the size of the section with the contour of the triangle (A) and the length of the flat protrusion (B), and L1 / L2 is most preferably in the range of 1.5-2.5, since this is important in ensuring that tissue sensations of general creaking, flexibility and a feeling of swelling. If the value is less than 0.7, then a feeling of general creaking and flexibility will be difficult to achieve, while if it exceeds 3.0, then it will be difficult to organize stable production of yarn, and the resulting fabric will lack a feeling of swelling.

The relative expression (ix) defines the relationship between the size of the triangular section section (A) and the width of the flat protrusion (B), and h1 / h2 is most preferably in the range of 4.0-7.0, since this is important in ensuring that the resulting tissues feel puffiness. If the value is less than 3.0, then the resulting fabric will not cause a sensation of swelling, while if it exceeds 10.0, then the stability of the release during the spinning of the fibers will be degraded, which will make it difficult to organize stable production of yarn .

In order to give the tissues a feeling of lightness and a feeling of puffiness, a hollow region should be present in the triangular section (A) with a fraction of the hollow region of at least 3%. However, if the proportion of the hollow region is excessively large, then the possibility of organizing stable production of yarn will be worsened, and therefore the proportion of the hollow region when calculating per section of a triangular shape (A) is limited to a value not exceeding 15%. The proportion of the hollow region is more preferably in the range of 3-10%.

In accordance with the invention, a metal-containing salt of organic sulfonic acid, preferably described by the following general formula (V), is preferably present in the polyester in an amount in the range of 0.5-2.5 wt.% Based on the weight of the polyester, so that the processing under conditions alkaline hydrolysis can lead to the formation of small pores oriented in the direction of the fiber axes on the surfaces of the fibers with a modified cross section, and to provide tissue that causes a feeling of increased dryness and sensation creaking and characterized by a quality very close to the quality of silk obtained using the Indian silkworm.

[Chemical formula 9]

where R ⁹ represents an alkyl group containing from 3 to 30 carbon atoms, or an aryl or alkylaryl group containing from 7 to 40 carbon atoms, and M represents an alkali metal or alkaline earth metal.

If R ⁹ in this formula is an alkyl or alkylaryl group, then the alkyl group may be a linear or branched side group. From the point of view of compatibility with polyesters, R in the metal-containing salt of alkylsulfonic acid is most preferably an alkyl group. M is preferably an alkali metal, such as sodium, potassium or lithium, or an alkaline earth metal, such as calcium or magnesium, of which sodium and potassium are preferred. As such metal-containing salts of organic sulfonic acids, sodium stearyl sulfonate, sodium octyl sulfonate and sodium lauryl sulfonate can be specifically mentioned.

Modified polyester fibers with a modified cross-section can be obtained, for example, using the following method.

FIG. 9 is a schematic illustration showing one example of the shape of a die outlet used in the manufacture of the modified cross-sectional polyester fibers described above.

Specifically, the melt of the polyester at 280-300 ° C is released from the die, characterized by the shape of the outlet described above, a sizing is applied to the cooled and cured spun filaments and, if necessary, when using apparatus forming weaves, weaving is obtained, after which the machine is carried out winding not subjected to drawing yarn when using a pair of receiving rollers, maintained at room temperature. After that, the obtained non-drawn yarn is passed through a preheating roller heated to 80-100 ° C, and a contactless heater maintained at 170-240 ° C, at a drawing speed in the range of 600-1400 m / min in order to achieve the degree of drawing in the range of 1.5-3.0, and then, if necessary, form additional weaves.

From the point of view of stable spinning of the fibers, the temperature of spinning the fibers from the melt is preferably in the range of 275-300 ° C. The reception speed during the spinning of fibers and the degree of drawing are suitably set in order to obtain the strength of conjugated polyester fibers in the range of 2.0-5.0 cN / dtex and elongation in the range of 30-50%.

Polyester fibers with a modified cross-section are preferably characterized by a mass number of an individual fiber in the range of 1.5-5.0 dtex and a mass number for a complete single strand in the range of 50-170 dtex, and the degree of shrinkage in boiling water is suitably in the range 5.0-12.0%.

When fabric is prepared using the polyester fibers described above with a modified cross-section, a suitable twist can be made and knitting or weaving operations to obtain the desired structure as needed. The resulting fabric, if necessary, can be processed under conditions of alkaline hydrolysis to obtain excellent sensations of creaking, swelling, flexibility and lightness that could not be obtained in the case of woven or knitted materials of the prior art.

Since the goal is to obtain a feeling of lightness and creaking, weaving and knitting to obtain complex structures are not preferred, but instead weaving and knitting to obtain a filament or its modifications, simple twill weave or its modifications, satin weave and the like are preferable. In addition, the proportion of polyester fibers with a modified cross-section of the invention in the fabric does not have to be 100%, but preferably it is a large proportion in order to provide an excellent sensation of creaking, swelling, flexibility and lightness.

Examples

Further, the present invention will be explained in detail using the following examples, which are by no means limiting for the invention. The parameters in the examples were measured using the following methods.

(1) Intrinsic viscosity

It was measured at 35 ° C using ortho-chlorophenol as a solvent.

(2) Softness

When touched, an organoleptic assessment was made using marks 3: mild and extremely satisfactory, 2: satisfactory or 1: rough / hard and unsatisfactory.

(3) Impermeability

The L value was measured and ΔL was calculated as the L value when using a white sheet minus the L value when using a black sheet. A lower value was regarded as an excellent impermeability.

(4) Permeability to air

It was measured by the method of determining the permeability to air in accordance with JIS L-1096-79-6.27 when using the device for testing permeability to air of type Frazil.

(5) Hygroscopicity

It was measured using the Birek method in accordance with JIS1096.

(6) Wear resistance

After the fabrics were abraded 3000 times using a Martindale abrasion tester, those that showed no wear were considered good, and those that showed wear were considered bad.

(7) Titanium element content, phosphorus element content

A sample in the form of particles of a complex polyester was heated to melting on an aluminum plate, and then it was fed to a direct compression press and molded to obtain uniform shaped samples for testing and to measure the level of the content of the titanium element and the level of the content of the phosphorus element, the sample was sent to a fluorescence x-ray analyzer Model 3270E from Rigaku Corp.

(8) Value (L ^* -b ^* )

A 30 cm long knitted material was made from polyester fibers using a class 12 circular knitting machine, after which the Macbeth COLOR EYE color measuring device was used to measure the L ^* value and the b ^* value and the difference (L ^* -b ^* ) was determined.

(9) Teething number (/ 10 ⁶ m)

After passing 250 polyester fibers wound onto packages (or wound onto spools) through a warp machine equipped with a nap detector, the yarn was warped and drawn for 42 hours at a speed of 400 m / min. The warp machine was periodically stopped and the presence of teasing was visually confirmed, the total confirmed tee number was calculated on 10 ⁶ m of the length of a single thread and recorded as the tee number.

Example 1

Preparation of Titanium Compound

A 2-liter three-necked flask was prepared that has the function of mixing and mixing the contents, 919 g of ethylene glycol and 10 g of acetic acid were placed in it, and after mixing and stirring, 71 g of titanium tetrabutoxide was slowly added and a (clear) solution of the titanium compound in ethylene glycol was obtained. This solution hereinafter in this document will be abbreviated as "TV solution". The concentration of titanium atoms in the solution was 1.02%.

Preparation of phosphorus compound

A three-necked flask of 2 L volume was prepared having a function that allows heating, mixing and stirring of the contents, and 656 g of ethylene glycol was placed and heated to 100 ° C with stirring. After reaching 100 ° C, 34.5 g of monolauryl phosphate was added, the mixture was heated, mixed and stirred until dissolved, and a clear solution was obtained. This solution hereinafter in this document will be abbreviated as "solution P1".

Catalyst Preparation

After this, 310 g of the resulting TB solution were slowly added to the P1 solution (approximately 690 g) with the heating controller set to 100 ° C and stirring, and after adding the full amount, stirring was continued for 1 hour at 100 ° C until the reaction between the titanium compound and phosphorus compound. The ratio of the concentrations of the components in the mixture for the TB solution and the P1 solution was 2.0, representing a molar ratio between phosphorus atoms and titanium atoms. The product resulting from the reaction was insoluble in ethylene glycol and therefore was present as a cloudy, finely divided precipitate. This solution hereinafter in this document will be abbreviated as “TP1-2.0 catalyst”.

In order to analyze the precipitate obtained in the reaction, a part of the solution of the reaction mixture was filtered using a filter with a 5 μm pore and a precipitated reaction product was obtained in the form of a solid phase, which was then washed using water and dried. The concentration of elements in the resulting precipitated reaction product was analyzed using PMA, resulting in 12.0% of titanium, 16.4% of phosphorus and a molar ratio between phosphorus atoms and titanium atoms of 2.1. Solid-phase NMR analysis yielded the following results. Measurements made using the C-13 CP / MAS method (NMR with cross-polarization and rotation at a magic angle) (frequency 75.5 Hz) revealed the disappearance of chemical shift peaks due to the presence of butoxide in the regions of 14 ppm, 20 ppm . and 36 ppm available on titanium tetrabutoxide, while measurements using the P-31 DD / MAS method (NMR with dipole decoupling and rotation at a magic angle) (frequency 121.5 Hz) confirmed the presence of a new peak in the chemical shift in the region of 22 ppm not found in ordinary monolauryl phosphate. These data clearly indicate that the precipitate obtained under these conditions was a new compound resulting from the reaction between the titanium compound and the phosphorus compound.

Independently, a suspension obtained by mixing 179 mass parts of high-purity terephthalic acid and 95 mass parts of ethylene glycol and an esterification reaction were fed into a reactor that already contained 225 mass parts of the oligomer, while stirring in a nitrogen atmosphere while maintaining 255 ° C and normal pressure at a constant speed. carried out for 4 hours until completion when removing water and ethylene glycol formed during the reaction from the system. The degree of esterification was> 98%, and the degree of polymerization of the obtained oligomer was approximately 5-7.

After transferring 225 mass parts of the oligomer obtained as a result of the esterification reaction, the previously obtained 3.34 mass parts of “TP1-2.0 catalyst” were loaded into the polycondensation reactor as a polycondensation catalyst. To undergo the polycondensation reaction, the reaction temperature in the system was increased from 255 to 280 ° C, and the pressure in the reaction was gradually reduced from atmospheric pressure to 60 Pa when water and ethylene glycol formed during the reaction were removed from the system.

The degree of completion of the polycondensation reaction was confirmed by monitoring the load on the mixing paddle in the system, and when the desired degree of polymerization was reached, the reaction was stopped. During the reaction, titanium dioxide was added as a matting agent in an amount of 2.5% (wt.) Based on the total weight of the polyester. After this, the reaction product in the system was continuously extruded from the outlet to obtain a single strand, and then cooled and cut to obtain granular particles with a size of approximately 3 mm The intrinsic viscosity of the obtained polyethylene terephthalate was 0.62.

Fibers were formed from polyethylene terephthalate granules using a spinneret having 36 outlet openings, where each of them, at a fiber spinning temperature of 290 ° C, made it possible to obtain an individual filament with the cross-sectional shape shown in FIG. 1, and after applying a sizing and receiving fiber at at a speed of 3000 m / min, extraction was carried out without winding at a preheating temperature of 85 ° C, a heat setting temperature of 120 ° C and a drawing ratio of 1.67, and for filaments Contents at a speed of 5000 m / min to give multifilament yarns comprising filaments with flat cross-sections according to the invention, the mass number of individual filament was 2.4 dtex and the total denier of a single filament was equal to 86 dtex. The obtained multifilament yarns were used for weaving without twisting the warp or weft and received a filament weave at a weave density of 110 single yarns / 2.54 cm, and then dyeing was carried out according to the generally accepted method and the fabric was evaluated using the methods described above. The results are shown in table 1.

Examples 2-3, comparative example 1

The same methodology was used as in Example 1, except that the die was replaced with another with outlet openings that made it possible to obtain the shapes shown in FIGS. 1 (b) and (c) and the circular cross-sectional shape of an individual filament . The results are shown in table 1.

Reference Example 2

The same procedure was carried out as in Example 1, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the loading amount was 4.83 mass parts, and 0.121 was additionally charged as a stabilizer mass parts of a solution of trimethylphosphate in ethylene glycol with a concentration of 25%. The results are shown in table 1.

Reference Example 3

The same procedure was used as in Example 1, except that only the TB solution obtained in Example 1 was used as the polycondensation catalyst, and the loading amount was 1.03 mass parts. The results are shown in table 1.

Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Reference Example 2 Reference Example 3 Cross sectional shape (but) (b) (from) Round (b) (b) Flatness 3 3,7 4,5 - 3,7 3,7 Irregularity 2 2 2 - 2 2 Softness 2 3 3 one 2 2 Sticking sensation Absent Absent Absent Absent Absent Absent Impermeability (ΔL) 13.5 12.0 11.0 15.0 12.0 11.0 Permeability to air 2.0 1,2 1,1 6.8 1,2 1,5 Hygroscopicity fifty 55 fifty twenty 55 fifty Wear resistance Good Good Good Good Good Bad L * -b * 76 77 73 70 59 fifty Teasing (/ 10 ⁶ m) 0.04 0.05 0.05 0.05 2.70 0.80

Example 4

After loading 0.009 mass parts of tetra-n-butyl titanate (TBT) into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol, a pressure of 0.07 MPa was created in a stainless steel reactor suitable for carrying out the transesterification reaction with a temperature increase from 140 to 240 ° C, and after that, 0.035 mass parts of triethylphosphonoacetate (TEFA) was added to complete the transesterification reaction.

Then the reaction product was transferred to a polymerization reactor, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, a polycondensation reaction was carried out to obtain polyethylene terephthalate. During the reaction, titanium dioxide was added as a matting agent in an amount of 2.5% (wt.) Based on the total weight of the polyester. The intrinsic viscosity of polyethylene terephthalate was 0.62, and the diethylene glycol content was 1.5%. The resulting polyethylene terephthalate was also granulated in accordance with a conventional method.

Fibers were formed from polyethylene terephthalate granules using a spinneret having 36 outlet openings, where each of them, at a fiber spinning temperature of 290 ° C, made it possible to obtain an individual filament with the cross-sectional shape shown in FIG. 1, and after applying a sizing and receiving fiber at at a speed of 3000 m / min, extraction was carried out without winding at a preheating temperature of 85 ° C, a heat setting temperature of 120 ° C and a drawing ratio of 1.67, and for filaments Contents at a speed of 5000 m / min to give multifilament yarns comprising filaments with flat cross-sections according to the invention, the mass number of individual filament was 2.4 dtex and the total denier of a single filament was equal to 86 dtex. The obtained multifilament yarns were used for weaving without twisting the warp or weft and received a filament weave at a weave density of 110 single yarns / 2.54 cm, and then dyeing was carried out according to the generally accepted method and the fabric was evaluated using the methods described above. The results are shown in table 2.

Examples 5-6, comparative example 4

The same methodology was used as in Example 4, except that the die was replaced with another with outlet openings that made it possible to obtain the shapes shown in FIGS. 1 (b) and (c) and the circular cross-sectional shape of an individual filament . The results are shown in table 2.

Reference Example 5

After loading 0.064 mass parts of calcium acetate monohydrate into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol in a stainless steel reactor suitable for pressure reaction, a pressure of 0.07 MPa was created for the transesterification reaction with an increase in temperature from 140 to 240 ° C. and after that, 0.044 mass parts of an aqueous solution of phosphoric acid with a concentration of 56% (wt.) was added to complete the transesterification reaction.

Then the reaction product was transferred to the polymerization reactor in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain polyethylene terephthalate. In a manner analogous to that of Example 4, titanium dioxide was added during the reaction. Polyethylene terephthalate was also granulated in accordance with a conventional method.

Implemented the same methodology as in example 4, except for the use of these granules of polyethylene terephthalate. The results are shown in table 2.

table 2 Example 4 Example 5 Example 6 Reference Example 4 Reference Example 5 Ti compound Content Level (mmol.%) 5 5 5 5 - Compound P Type of TEFA TEFA TEFA TEFA - Content Level (mmol.%) thirty thirty thirty thirty - Sb compound Type of - - - - Sb ₂ About ₃ Content Level (mmol.%) - - - - 31 P / ti 6 6 6 6 - P + Ti 35 35 35 35 - Cross sectional shape (but) (b) (from) Round (b) Flatness 3 3,7 4,5 - 3,7 Irregularity 2 2 2 - 2 Softness 2 3 3 one 2 Sticking sensation Absent Absent Absent Absent Absent Impermeability (ΔL) 13.0 12.3 11.2 16.5 12.0 Permeability to air 2.1 1.4 1,2 7.0 1,2 Hygroscopicity 52 57 52 16 55 Wear resistance Good Good Good Good Good L * -b * 78 78 74 71 58 Teasing (/ 10 ⁶ m) 0,03 0.04 0.02 0.04 3.10

Further, the present invention will be further explained using examples 7-12 and comparative examples 6-7. The parameters in these examples and comparative examples were measured using the following methods.

(1) Crystallinity

It was determined using a wide-angle X-ray diffraction method. To measure the scattering intensity of Cu-Kα rays monochromatized using a nickel filter, an X-ray source (Rotorflex RU-200) from Rigaku Corp. was used. and the degree of crystallinity was calculated using the following formula:

Degree of crystallinity = scattering intensity in the crystalline region / total scattering intensity × 100 (%).

(2) The degree of shrinkage in boiling water

When using a sizing drum with a frame perimeter of 1.125 m, skeins with 20 turns were obtained and after applying a load of 0.022 cN / dtex, skeins were suspended on a panel with a scale applied and the initial skein length L _{0 was} measured. After that, for 30 minutes, the skein was processed in a hot water bath with a temperature of 65 ° C, and then it was cooled and hung again on a panel with a scale applied, after which the length L after shrinkage was measured, and the degree of shrinkage in boiling water was calculated at using the following formula:

The degree of shrinkage in boiling water = (L ₀ -L) / L ₀ × 100 (%).

(3) Performance coefficient

A micrograph of the cross section of a complex yarn of complex polyester was obtained, the distance (a ₁ ) from the center of the circle inscribed in the inner walls of the cross section of the individual fiber to the tip of the rib and the radius (b ₁ ) of the circle inscribed in the inner walls of the cross section of the fiber were measured, and at Using the following formula, the coefficient of protrusion was calculated

The coefficient of protrusion = (a ₁ -b ₁ ) / a ₁ .

(4) Titanium element content, phosphorus element content

A sample in the form of particles of a complex polyester was heated to melting on an aluminum plate, and then it was fed to a direct compression press and molded to obtain uniform shaped samples for testing and to measure the level of the content of the titanium element and the level of the content of the phosphorus element, the sample was sent to a fluorescence x-ray analyzer Model 3270E from Rigaku Corp.

(5) Height of accumulations on the die

After spinning the fibers from the melt using the method and conditions described in each example, a release agent was blown onto the surface of the die, the die was disconnected to prevent adhesion of the produced polymer, and using a microscope, the height of accumulations on the die was measured, which adhered and accumulated in the vicinity of the outlet holes. The height of accumulations on the die was measured for all outlet openings and the average value for them was recorded.

(6) Number of yarn breaks during spinning (%)

The number of yarn breaks during spinning was recorded during operation of the spinning machine, excluding yarn breaks due to artificial or mechanical factors, and the number of yarn breaks during spinning was calculated using the following formula:

The number of breaks in the threads during spinning (%) = [the number of breaks in threads / (the number of working winding machines × the number of removal)] × 100.

In this case, the amount of removal is the number of times that a package of non-drawn yarn was wound until a predetermined mass (10 kg) was reached.

(7) Number of yarn breaks during processing

A package of a complex polyester yarn wound up to a mass of 10 kg was subjected to a stretch - false twist when using the SDS-8 false twist machine from Scragg Co. and received two packs of polyester yarn subjected to false twisting, wound to a mass of 5 kg, the number of yarn breaks during the operation was recorded, and using the following formula, the number of yarn breaks during processing was calculated:

The number of strand breaks during processing = the number of strand breaks / (number of working spindles × 2) × 100.

(8) Teasing during processing

A teething counter DT-104 from Toray Co., Ltd. was used to determine the teasing number observed for the yarn twisted yarn at 20 minutes of continuous measurement at a speed of 50 m / min.

(9) Vulture fabric

Subjected to a hood - false twist, the thread was twisted at 600 turns / m and used as the warp and weft yarn to produce twill fabric. After that, the fabric was subjected to washing and relaxation treatment at 100 ° C, dry heat treatment for pre-shrinkage at 180 ° C for 45 seconds, processing under conditions of 15% alkaline hydrolysis and dyeing at 130 ° C for 30 minutes with natural drying, after which the final shrinkage was carried out at 170 ° C for 45 seconds and received a woven material. The sensation caused by the material was assessed by an expert by setting the grades on the following scale:

level 1: a feeling of natural dryness;

level 2: the feeling of dryness is somewhat incomplete;

level 3: a sensation similar to that of a flat paper.

(10) Hygroscopicity / ability to dry quickly (absorption number)

The indicator used in the case of hygroscopicity and the ability to quickly dry, was the number of seconds elapsed until the drops of dripping water will no longer reflect from the surface of the test fabric made from a false twisted yarn of polyester (absorption number), based on Section 5.1.1. Moisture absorption rate (drip method) in the test method for determining the hygroscopicity of fibrous products in accordance with JIS L1907. L ₁₀ represents the absorption number (s) after 10 times washing according to the method in accordance with JIS L0844-A-2.

(11) Value (L ^* -b ^* )

30 cm long circular knitted material was obtained from polyester fibers using a class 12 circular knitting machine, after which a Hunter-type differential colorimeter CR-200 from Minolta was used to measure the L ^* value and the b ^* value and the difference was determined (L ^* -b ^* ) .

Examples 7-9

The preparation of the titanium compound, the phosphorus compound and the catalyst and the preparation of the oligomer were carried out in exactly the same way as in Example 1.

After transferring 225 mass parts of the obtained oligomer into the polycondensation reactor as a polycondensation catalyst, the previously obtained 3.34 mass parts of the “TP1-2.0 catalyst” were loaded. After that, in order to undergo a polycondensation reaction, the reaction temperature in the system was increased from 255 to 280 ° C, and the pressure in the reaction was gradually reduced from atmospheric pressure to 60 Pa when water and ethylene glycol formed during the reaction were removed from the system.

The degree of completion of the polycondensation reaction was confirmed by monitoring the load on the mixing paddle in the system, and when the desired degree of polymerization was reached, the reaction was stopped. After this, the reaction product in the system was continuously extruded from the outlet to obtain a single strand, and then cooled and cut to obtain granular particles with a size of approximately 3 mm The intrinsic viscosity of the obtained polyethylene terephthalate was 0.630.

Independently pre-fabricated die based on the type of outlet, characterized by the shape of the outlet shown in figure 4, having 24 groups of outlet holes, each of which consisted of a core-forming round outlet (b ₂ in figure 4) with a radius of 0, 15 mm and forming ribs of the outlet with a slit width of 0.10 mm and a length of 0.88 mm, measured from the center of the circular outlet to the tip (a ₂ in FIG. 4) in the quantity shown in table 1, and it was inserted into the spinneret to Set and installed in the spinning unit. The aforementioned polyethylene terephthalate granules were dried at 150 ° C for 5 hours and then melted using a melt spinner equipped with a worm-type extruder, introduced into a spinning unit at 295 ° C and extruded from a die at a discharge speed of 40 g / min . After that, with a flow rate of 5 nm ³ / min, cooling air was injected into the polymer stream at 25 ° C from a spinning shaft of the transverse flow type with a length of 60 cm and with its tip located 10 cm below the die discharge plane, cooling to curing, after which a sizing was applied for spinning and at a speed of 3000 m / min the winding of the filament was carried out, obtaining filaments of polyethylene terephthalate, each of which was characterized by the degree of crystallinity, the degree of shrinkage in boiling water, the number of ribs and protrusion coefficient shown on Table 3. This procedure was melt spinning implemented continuously for 7 days.

The obtained filaments of polyethylene terephthalate were fed to an SDS-8 false twist machine from Scragg Co. (triaxial disk module of false twist, 216 spindles) for drawing - false twisting at a degree of drawing 1.65, heater temperature 175 ° C, the number of turns 3300 / m and the speed of drawing - false twisting 600 m / min, getting subjected to a false - false twist yarn from polyethylene terephthalate with a mass number of 84 dtex. The absorption numbers (L ₀ and L ₁₀ ), the neck of the fabric, the number of yarn breaks during processing and the number of teething during processing for examples 1-3 and comparative example 1 are summarized in table 3.

Reference Example 6

The same procedure was used as in Example 8, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the loading amount was 4.83 mass parts, and 0.121 was additionally charged as a stabilizer mass parts of a solution of trimethylphosphate in ethylene glycol with a concentration of 25%. The results are shown in table 3.

Table 3 Example 7 Example 8 Example 9 Reference Example 6 Polymerization catalyst The reaction product between titanium tetrabutoxide and monolauryl phosphate The reaction product between titanium tetrabutoxide and monolauryl phosphate The reaction product between titanium tetrabutoxide and monolauryl phosphate Sb ₂ O ₃ The ratio of components in a mixture of titanium compounds and phosphorus compounds in the polymerization catalyst ^* 2.0 2.0 2.0 - Number of ribs 3 four 6 four Coefficient of performance 0.51 0.48 0.48 0.48 The degree of crystallinity (%) 21 22 22 twenty The degree of shrinkage in boiling water (%) 59 56 55 57 Absorption Number L ₀ (sec) 0 0 0 0 L ₁₀ (sec) 10 3 7 eleven The height of accumulations on the die after 7 days of fiber formation (μm) 3.0 2,5 3,7 89 The number of breaks in the threads when spinning for 7 days (%) 0.3 0.5 1,0 5,4 The number of teasing (/ 10 ⁴ m) 2 3 one 31 The number of breaks in the threads when drawing - false twist (%) 3.2 3.4 4.2 25,4 (L * -b *) 88 97 95 92 Fabric bar certification Level 1 Level 1 Level 1 Level 1 * The molar ratio between phosphorus atoms and titanium atoms.

Examples 10-11

After loading 0.009 mass parts of tetra-n-butyl titanate (TBT) into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol, a pressure of 0.07 MPa was created in a stainless steel reactor suitable for carrying out the transesterification reaction with a temperature increase from 140 to 240 ° C, and after that, 0.035 mass parts of triethylphosphonoacetate (TEFA) was added to complete the transesterification reaction.

Then the reaction product was transferred to a polymerization reactor, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, a polycondensation reaction was carried out to obtain polyethylene terephthalate having a characteristic viscosity of 0.630 and a diethylene glycol content of 1, 5%. After that, the obtained polyethylene terephthalate was granulated in accordance with the usual method.

Independently pre-fabricated die based on the type of outlet, characterized by the shape of the outlet shown in figure 4, having 24 groups of outlet holes, each of which consisted of a core-forming round outlet (b ₂ in figure 4) with a radius of 0, 15 mm and forming ribs of the outlet with a slit width of 0.10 mm and a length of 0.88 mm, measured from the center of the round outlet to the tip (a ₂ in FIG. 4), in the amount shown in table 1, and it was inserted into spunbond to mplekt and installed in the spinning unit. The aforementioned polyethylene terephthalate granules were dried at 150 ° C for 5 hours and then melted using a melt spinner equipped with a worm-type extruder, introduced into a spinning unit at 295 ° C and extruded from a die at a discharge speed of 40 g / min . After that, with a flow rate of 5 nm ³ / min, cooling air was injected into the polymer stream at 25 ° C from a spinning shaft of the transverse flow type with a length of 60 cm and with its tip located 10 cm below the die discharge plane, cooling to curing, after which a sizing was applied for spinning and at a speed of 3000 m / min the winding of the filament was carried out, obtaining filaments of polyethylene terephthalate, each of which was characterized by the degree of crystallinity, the degree of shrinkage in boiling water, the number of ribs and protrusion coefficient shown in Table 4. This procedure was melt spinning implemented continuously for 7 days.

The obtained filaments of polyethylene terephthalate were fed to an SDS-8 false twist machine from Scragg Co. (triaxial disk module of false twist, 216 spindles) for drawing - false twisting at a degree of drawing 1.65, heater temperature 175 ° C, the number of turns 3300 / m and the speed of drawing - false twisting 600 m / min, getting subjected to a false - false twist yarn from polyethylene terephthalate with a mass number of 84 dtex. The absorption numbers (L ₀ and L ₁₀ ), the neck of the fabric, the number of yarn breaks during processing and the number of teething during processing for examples 1-3 and comparative example 1 are summarized in table 4.

Reference Example 7

After loading 0.064 mass parts of calcium acetate monohydrate into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol, a pressure of 0.07 MPa was created for the transesterification reaction under pressure from a stainless steel reactor with an increase in temperature from 140 to 240 ° C. and after that, 0.044 mass parts of an aqueous solution of phosphoric acid with a concentration of 56% (wt.) was added to complete the transesterification reaction.

Then, the reaction product was transferred to the polymerization reactor in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain polyethylene terephthalate having a characteristic viscosity equal to 0.630. After that, the polyethylene terephthalate was granulated in accordance with the usual method.

Implemented the same methodology as in example 2, except for the use of these granules of polyethylene terephthalate. The results are shown in table 4.

Table 4 Example 10 Example 11 Example 12 Reference Example 7 Ti compound Type of TBT TBT TBT - Content Level (mmol.%) 5 5 5 - Compound P Type of TEFA TEFA TEFA - Content Level (mmol.%) thirty thirty thirty - Sb compound Type of - - - Sb ₂ O ₃ Content Level (mmol.%) - - - 31 P / ti 6 6 6 - P + Ti (mol%) 35 35 35 - Number of ribs 3 four 6 four Coefficient of performance 0.51 0.48 0.48 0.48 The degree of crystallinity (%) 24 25 25 twenty The degree of shrinkage in boiling water (%) 53 52 52 57 Absorption Number L ₀ (sec) 0 0 0 0 L ₁₀ (sec) 8 four 6 eleven The height of accumulations on the die after 7 days of fiber formation (μm) 5,4 3.6 8.1 89 The number of breaks in the threads when spinning for 7 days (%) 1.4 0.3 2,5 5,4 The number of teasing (/ 10 ⁴ m) one one 0 31 The number of breaks in the threads when drawing - false twist (%) 3,5 3.9 4.0 25,4 (L ^* -b ^* ) 90 96 91 88 Fabric bar certification Level 1 Level 1 Level 1 Level 1

Further, the present invention will be further explained using examples 13-34 and comparative examples 8-11. The parameters in these examples and comparative examples were measured using the following methods.

(1) Cross-sectional shape of filaments

The cross-sectional area (S _A ) and the diameter (D _A ) of the core and the cross-sectional area (S _B ) and the maximum length and maximum width (W _B ) of the ribs were determined using a 3000x magnification photograph taken for the cross-section of the filament before alkaline hydrolysis.

(2) Spinning

The fiber was formed continuously for 8 hours, assigning a grade of “A” if absolutely no breaks in the threads occurred, “B” if there was a break in the individual filaments (napping), and “C” if the break in the yarn occurred.

(3) Separation of ribs (S)

The number of separated ribs was determined using a photograph with a magnification of 1000 × taken for the filament after processing under conditions of alkaline hydrolysis, and the degree of separation S (%) of the ribs in the surface layer and the middle region of the multifilament was calculated using the following formula:

S (%) = (number of separated ribs / total number of ribs) × 100.

(4) Neck of woven / knitted fabric

Three-dimensionality, a feeling of softness and drape for a woven or knitted material were assigned to a scale based on a general organoleptic assessment, ranging from A (very good) to E (bad).

(5) Compatibility parameter χ

The solubility parameters δa and δb for the polyester and the compound in the state of microphase separation with the polyester were determined from their solubilities in various solvents, and χ was determined using the following formula:

χ = (V _a / RT) (δa-δb) ² ,

where V _a is the molar volume (cm ³ / mol) of the polyester, R is the gas constant (J / mol · K), T is the absolute temperature (K), and δa and δb are the solubility parameters (J ^{1 / 2} / cm ^3/2 ) for polyester and compound, respectively.

(6) The height of accumulations on the die

After spinning the fibers from the melt using the method and conditions described in each example, a release agent was blown onto the surface of the die, the die was disconnected to prevent adhesion of the produced polymer, and using a microscope, the height of accumulations on the die was measured, which adhered and accumulated in the vicinity of the outlet holes. The height of accumulations on the die was measured for all outlet openings and the average value for them was recorded.

Examples 13-21

To a stirred mixture of 919 g of ethylene glycol and 10 g of acetic acid, 71 g of titanium tetrabutoxide was added and a (clear) solution of the titanium compound in ethylene glycol was obtained. Then, after adding 34.5 g of monolauryl phosphate to 656 g of ethylene glycol heated to 100 ° C and stirred, heating and stirring were continued until dissolved and a clear solution was obtained.

After that, both solutions were mixed while stirring at 100 ° C, and after the addition of full amounts, stirring of the resulting mixture was continued for 1 hour at 100 ° C to obtain a turbid solution. The ratio of the concentrations of the components in the mixture for the two solutions was regulated, bringing the molar ratio between phosphorus atoms and titanium atoms to 2.0. The resulting white precipitate was filtered off, and then washed with water and dried as a polymerization catalyst.

A suspension obtained by mixing 179 mass parts of high-purity terephthalic acid and 95 mass parts of ethylene glycol and an esterification reaction were fed into a reactor capable of containing 225 mass parts of an oligomer, with stirring in a nitrogen atmosphere and at a constant pressure of 255 ° C. carried out until the completion of the reaction by distillation from the system of water and ethylene glycol formed during the reaction. The degree of esterification was ≥98%, and the polymerization degree of the obtained oligomer was approximately 5-7.

After transferring 225 mass parts of the oligomer obtained by carrying out the esterification reaction into the polycondensation reactor, the previously obtained 3.34 mass parts of the catalyst were loaded as a polycondensation catalyst, and a compound intended for microphase separation with polyester was added with stirring, followed by pressure additionally reduced to 1 mm Hg for carrying out polymerization in accordance with the generally accepted method described below, and the granules were cut to obtain particles of polyethylene terephthalate, characterized by an intrinsic viscosity of 0.63 (hereinafter referred to as "polyethylene terephthalate granules"). Added and mixed compounds, χ values for compounds and their added amounts are shown in table 5.

The granules of polyethylene terephthalate were melted and released from a die having 24 sets of outlet openings having the shape shown in Fig. 6 B at 275 ° C, and cooling was carried out in the transverse flow spinning shaft while the cores and ribs were combined, followed by winding at a speed of 1000 m / min

The wound multifilament yarn was subjected to heat treatment with a hood at a stretch ratio of 2.55 using a hood machine equipped with a hot roller with a temperature of 90 ° C and a slot heater with a temperature of 150 ° C, and yarn with a characteristic of 60 dtex / 24 filaments was obtained.

A circular knitted material of class 20 was made from the obtained multifilament yarn, the circular knitted material was boiled for 20 minutes in an aqueous solution of sodium hydroxide at a concentration of 40 g / liter in order to conduct processing under conditions of alkaline hydrolysis.

Spinning, height of accumulation on the die, neck of the fabric and the like for each example are shown in table 5.

Comparative Examples 8, 9

Polyethylene terephthalate granules were obtained by the same method as in examples 15 and 18, except for the use of antimony trioxide as a polymerization catalyst, and they were used to obtain a multifilament yarn for comparative examples 8 and 9. Spinning, height of accumulation on a spinneret, neck of fabric and the like for each example are shown in table 5.

Examples 22, 23

In the case of example 22, the complex thread A obtained in example 15 and the complex thread B with a characteristic of 40 dtex / 18 filaments obtained by melting granules of polyethylene terephthalate with the release from the spinneret having 18 sets of flat outlet openings (L / D = 5) , winding at 1500 m / min, and after this drawing at a preheating temperature of 90 ° C and a drawing ratio of 2.7 was weaved using a spinning dies at an air pressure of 1.5 kg / cm ² and a feed rate of 1 5% getting rid annuyu multifilament yarn.

This blended multifilament yarn was twisted in an S300T / M unit and used as warp and weft yarns for weaving to form the woven fabric “Habutae”. After relaxation treatment, the fabric was subjected to heat shrinkage, and then processed under conditions of 20% alkaline hydrolysis. Table 6 shows the degree of shrinkage and mixing ratio for the complex thread A and complex thread B, as well as the separation of the ribs in the woven material and the neck of the fabric.

In the case of example 23, granules of polyethylene terephthalate, characterized by an intrinsic viscosity of 0.64, containing titanium oxide in the amount of 0.05% by weight as a matting agent, were melted to release at 275 ° C from a die having 24 sets of outlet openings, each of which has the shape shown in FIG. 6B, and cooling was carried out in the transverse flow spinning shaft while releasing the cores and ribs, followed by winding at a speed of 2500 m / min, and after buckle at preheating temperature of 90 ° C and a draw ratio of 1.8 was carried out a relaxation heat treatment using a non-contact heater to a temperature of 150 ° C at a degree of flow ahead of 2% to obtain a multifilament yarn A characteristic of 60 dtex / 24 filaments.

Independently, the polyethylene terephthalate granules were melted with an outlet from a die having 18 round outlet openings, wound at 1,500 m / min and stretched at a preheating temperature of 90 ° C and a drawing degree of 3.0, yielding complex B with a characteristic of 40 dtex / 18 filaments.

The multifilament yarn A and the multifilament yarn B were blended and used in weaving and processing under alkaline hydrolysis using the same methods as in Example 23.

Table 6 shows the degree of shrinkage and mixing ratio for the complex yarn A and complex yarn B obtained in examples 22 and 23, as well as the separation of the ribs in the resulting woven material and neck of the fabric. The mixing ratio is the proportion of the complex yarn A in the blended yarn when calculating the entire mixed multifilament yarn (mass of the yarn A + mass of the yarn B).

Table 6 Elementary thread A Elementary thread B Ribs Vulture Cloth The degree of shrinkage in boiling water (%) The degree of shrinkage during dry heat treatment (%) Mixing ratio (%) The degree of shrinkage in boiling water (%) The area of the surface layer (%) Mid region (%) Example 22 8 0.5 60 8 53 38 AT Example 23 6 -5 54 6 52 37 BUT

Examples 24-32

After loading 0.009 mass parts of tetra-n-butyl titanate (TBT) into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol, a pressure of 0.07 MPa was created in a stainless steel reactor suitable for carrying out the transesterification reaction with a temperature increase from 140 to 240 ° C, and after that, 0.035 mass parts of triethylphosphonoacetate (TEFA) was added to complete the transesterification reaction. In this case, M _p / M _Ti = 3, M _p + M _ti = 35.

Then the reaction product was transferred to a polymerization reactor, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, a polycondensation reaction was carried out to obtain polyethylene terephthalate having a characteristic viscosity of 0.63 and a level of diethylene glycol equal to 1.5%. After that, the obtained polyethylene terephthalate was granulated in accordance with the usual method.

The granules of polyethylene terephthalate were melted and released from a die having 24 sets of outlet openings having the shape shown in Fig. 6 B at 275 ° C, and cooling was carried out in the transverse flow spinning shaft while the cores and ribs were combined, followed by winding at a speed of 1000 m / min

The wound multifilament yarn was heat-treated with a hood at a stretch ratio of 2.55 using a hood machine equipped with a hot roller at a temperature of 90 ° C and a slot heater with a temperature of 150 ° C, and a yarn with a characteristic of 60 dtex / 24 filaments was obtained.

A circular knitted material of class 20 was made from the obtained multifilament yarn and the circular knitted material was boiled for 20 minutes in an aqueous solution of sodium hydroxide with a concentration of 40 g / l in order to conduct processing under conditions of alkaline hydrolysis.

Spinning, height of accumulation on the die, neck of the fabric and the like for each example are shown in table 7.

Comparative Examples 10, 11

After loading 0.064 mass parts of calcium acetate monohydrate into a mixture of 100 mass parts of dimethyl terephthalate and 70 mass parts of ethylene glycol, a pressure of 0.07 MPa was created for the transesterification reaction under pressure from a stainless steel reactor with an increase in temperature from 140 to 240 ° C. and after that, 0.044 mass parts of an aqueous solution of phosphoric acid with a concentration of 56% (wt.) was added to complete the transesterification reaction.

Then the reaction product was transferred to the polymerization reactor in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain polyethylene terephthalate. The resulting polyethylene terephthalate was granulated in accordance with a conventional method.

The multifilament yarn was obtained by the same method as in examples 26 and 29, except for the use of the polyethylene terephthalate granules mentioned above, and they were used for comparative examples 10 and 11. Spinning, height of accumulation on the die, fabric bar and the like for each example shown in table 7.

Examples 33, 34

In the case of Example 33, the multifilament yarn A obtained in Example 26 and the multifilament B with a characteristic of 40 dtex / 18 filaments obtained by melting granules of polyethylene terephthalate with a release from a spinneret having 18 sets of flat outlets (L / D = 5) , winding at 1500 m / min, and then drawing at a preheating temperature of 90 ° C and a drawing degree of 2.7, weaving was performed using a spinning dies at an air pressure of 1.5 kg / cm ² and a feed rate ahead of 1.5% getting rid shannu complex thread.

This blended multifilament yarn was twisted in an S300T / M unit and used as warp and weft yarns for weaving to form the woven fabric “Habutae”. After relaxation treatment, the fabric was subjected to heat shrinkage, and then processed under conditions of 20% alkaline hydrolysis. Table 8 shows the degree of shrinkage and mixing ratio for the complex thread A and complex thread B, as well as the separation of the ribs in the woven material and the neck of the fabric.

In the case of example 34, granules of polyethylene terephthalate, characterized by an intrinsic viscosity of 0.64, containing titanium oxide in the amount of 0.05% by weight as a matting agent, were melted to release at 275 ° C from a die having 24 sets of outlet openings, each of which has the shape shown in FIG. 6B, and cooling was carried out in the transverse flow spinning shaft while releasing the cores and ribs at the same time, followed by winding at a speed of 2500 m / min and after Pulls at a preheating temperature of 90 ° C and a draw ratio of 1.8 carried out relaxation heat treatment using a non-contact heater at a temperature of 150 ° C with a feed rate ahead of 2%, yielding complex filament A with a characteristic of 60 dtex / 24 filaments.

Independently, the polyethylene terephthalate granules were melted with an outlet from a die having 18 round outlet openings, wound at 1,500 m / min and stretched at a preheating temperature of 90 ° C and a drawing degree of 3.0, yielding complex B with a characteristic of 40 dtex / 18 filaments.

The multifilament yarn A and the multifilament yarn B were blended and used in weaving and processing under alkaline hydrolysis using the same methods as in Example 33.

Table 8 shows the degree of shrinkage and mixing ratio for the complex yarn A and complex yarn B obtained in examples 33 and 34, as well as the separation of the ribs in the resulting woven material and neck of the fabric.

Table 8 Complex thread A Complex thread B Ribs Vulture Cloth The degree of shrinkage in boiling water (%) The degree of shrinkage during dry heat treatment (%) Mixing ratio (%) The degree of shrinkage in boiling water (%) The area of the surface layer (%) Mid region (%) Example 33 8.3 0.6 60 15.6 fifty 35 AT Example 34 6.1 -4.0 54 16.1 56 39 BUT

Further, the present invention will be further explained using examples 35-40 and comparative examples 12-13. The parameters in these examples were measured using the following methods.

(1) Intrinsic viscosity

It was measured at 35 ° C using ortho-chlorophenol as a solvent.

(2) The release state of the polymer

The release state of the polymer was observed during the spinning of the fibers upon release of the polymer from the die, and the release state was evaluated on the following scale. The observation was carried out starting from the 1st hour, the 3rd day and the 7th day after the start of the formation of conjugate fibers.

Level 1: the produced elementary thread drew a consistent line of incidence with a stable course.

Level 2: slight bending, twisting or twisting of the produced elementary thread.

Level 3: large bending, twisting or twisting of the produced elementary thread. Partial contact of the polymer with the surface of the die, which as a result leads to frequent ruptures of filaments.

(3) Hollowness (%)

The area of the hollow region (A) in the cross section of each individual fiber and the area (B) bordering the cross section were measured by micrographs of the cross sections of polyester fibers and the average value for all cross sections of individual fibers was calculated as hollow (%) when calculating with using the following formula:

Hollowness (%) = A / B × 100.

(4) Irregular sizes (U,%)

It was measured using a USTER TESTER-4 device from Zellweger Uster at a feed speed of 400 m / min.

(5) Teething number (/ 10 ⁶ m)

After passing 250 polyester fibers wound onto packages (or wound onto spools) through a warp machine equipped with a nap detector, the yarn was warped and drawn for 42 hours at a speed of 400 m / min. The warp machine was periodically stopped and the presence of teasing was visually confirmed, the total confirmed tee number was calculated on 10 ⁶ m of the length of a single thread and recorded as the tee number.

(6) Stains from uneven staining

30 cm long circular knitted material was obtained from polyester fibers using a class 12 circular knitting machine, dye (Terasil Blue GFL) was used for dyeing at 100 ° C for 40 minutes, and the uniformity of dyeing was certified using the following scale based on visual inspection an expert.

Level 1: uniform staining, virtually no stains from uneven staining.

Level 2: a certain number of stripes or spots due to uneven staining.

Level 3: a significant number of stripes or spots due to uneven staining on one side.

(7) Strength and elongation

They were measured in accordance with JIS-L1013.

(8) Vulture

A creaking sensation, a feeling of bulkiness, flexibility and lightness, a group of 5 experts certified in accordance with a three-level scale with very good (excellent), good (satisfactory) or poor (unacceptable) levels with the calculation of average values.

Example 35

The preparation of the titanium compound, the phosphorus compound and the catalyst and the preparation of the oligomer were carried out in exactly the same way as in Example 1.

After transferring 225 mass parts of the oligomer obtained as a result of the esterification reaction, the previously obtained 3.34 mass parts of “TP1-2.0 catalyst” were loaded into the polycondensation reactor as a polycondensation catalyst. To undergo a polycondensation reaction, the reaction temperature in the system was increased from 255 to 280 ° C, and the pressure in the reaction was gradually reduced from atmospheric pressure to 60 Pa when water and ethylene glycol formed during the reaction were removed from the system, and then 0.6% (wt. .) C8-20 (average value = 14) of sodium alkyl sulfonate, and after completion of the reaction from the outlet, the reaction product was continuously extruded in a single strand system, which was cooled and cut to obtain granular particles with a size of approximately equal to 3 mm. The intrinsic viscosity of the obtained polyethylene terephthalate was 0.63.

After drying the obtained polyester granules in accordance with the usual method, they were introduced into a spinning machine equipped with a melt extruder (screw extruder) and melted, after which they were introduced into a spinneret kit located in a spinning block maintained at 290 ° C, and after of this, the melt was discharged, and the produced filaments were cooled to cure, after which a sizing was applied to them before weaving and subsequent winding at a receiving speed of 1400 m / min. The obtained non-drawn filament was subjected to drawing at a temperature of the preheating roller of 90 ° C, a temperature of the heat shrink heater (non-contact type) of 200 ° C, a degree of drawing 23 and a drawing speed of 800 m / min, and finally weaving was formed to form fibers from a complex polyester with a modified cross-section with a characteristic of 83 dtex / 24 filaments with a hollow core equal to 15%. During the spinning of the fibers, no accumulation of foreign material was recorded in the vicinity of the outlet openings of the die, and the release state of the polymer remained stable for a long period of time.

The obtained filaments were used as warp and weft yarns for weaving to obtain the woven material “Habutae”, and then, in accordance with conventional methods, washing, heat shrinkage, alkaline hydrolysis (hydrolysis degree of 15%) and dyeing were obtained to obtain a dyed woven material with calico weave. The evaluation results for the obtained fibers and woven material are shown in table 9.

Reference Example 12

The same procedure was used as in Example 35, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the charge amount was 4.83 mass parts, and 0.121 was additionally charged as stabilizer mass parts of a solution of trimethylphosphate in ethylene glycol with a concentration of 25%, obtaining a complex polyester having a characteristic viscosity of 0.63. The polyester was spun and drawn using the same method and conditions as in Example 1, and polyester fibers with a modified cross-section with a characteristic of 83 dtex / 24 filament were obtained. During the formation of the fibers around the outlet openings of the die, the formation of accumulations of material was noted, while the appearance of bending, twisting or twisting was also observed among the produced filaments. By the exact same method as in Example 1, a dyed woven fabric was also obtained. The results for the obtained fibers and fabrics are shown in table 9.

Table 9 Example 35 Reference Example 12 Polycondensation Catalyst TP1-2.0 Sb ₂ O ₃ The release state of the polymer (level) After 1 hour of spinning one 2 After 3 days of spinning one 3 After 7 days of fiber spinning one 3 Irregularity of sizes (U,%) After 1 hour of spinning 0.6 0.8 After 3 days of spinning 0.5 1,2 After 7 days of fiber spinning 0.5 1.8 The number of teasing (/ 10 ⁶ m) After 1 hour of spinning 0.06 1,1 After 3 days of spinning 0,07 2,5 After 7 days of fiber spinning 0,07 3.2 Spots from uneven staining (level) After 1 hour of spinning one 2 After 3 days of spinning one 3 After 7 days of fiber spinning one 3 Vulture Excellent Excellent Strength (cN / dtex) 2.2 2.1 Relative extension (%) 33 32

Examples 36-37

The molding and drawing of the fibers was carried out in accordance with the same method and conditions as in Example 35, except that the cross-sectional shapes of the individual fibers were characterized by the values shown in Table 10 to obtain polyester fibers with a modified cross-section. By the exact same method as in Example 35, dyed woven materials were also obtained. Vultures for the resulting woven materials are shown in table 10.

Reference Example 13

The molding and drawing of the fibers was carried out in accordance with the same method and conditions as in Example 35, except that the cross-sectional shape of the individual fibers corresponded to a circular cross-section to obtain polyester fibers. By the exact same method as in Example 35, a dyed woven fabric was also obtained. The neck for the obtained woven material is shown in table 10 (there was absolutely no sensation of creaking).

Table 10 Example 36 Example 37 Reference Example 13 L1 / L2 2.0 0.8 - h2 / h1 5.3 5.3 - Vulture Excellent Excellent poorly

Examples 38-40

The molding and drawing of the fibers was carried out in accordance with the same method and conditions as in example 35, except that the hollow values for the fibers were as shown in table 11, to obtain fibers from a complex polyester with a modified cross section . By the exact same method as in Example 35, dyed woven materials were also obtained. The evaluation results for the obtained fibers and woven materials are shown in table 11.

Table 11 Example 38 Example 39 Example 40 Hollowness (%) 3 8 13 The release state of the polymer (level) After 1 hour of spinning one one one After 3 days of spinning one one one After 7 days of fiber spinning one one one Irregularity of sizes (U,%) After 1 hour of spinning 0.5 0.4 0.4 After 3 days of spinning 0.5 0.3 0.4 After 7 days of fiber spinning 0.5 0.4 0.4 The number of teasing (/ 10 ⁶ m) After 1 hour of spinning 0.05 0.04 0.05 After 3 days of spinning 0.05 0,03 0.04 After 7 days of fiber spinning 0.04 0.04 0.05 Spots from uneven staining (level) After 1 hour of spinning one one one After 3 days of spinning one one one After 7 days of fiber spinning one one one Vulture Excellent Excellent Excellent Strength (cN / dtex) 2.6 2.2 1.8 Relative extension 39 33 24 (%)

Claims (15)

1. Polyester fibers with a modified cross-section, containing a polyester polymer as a main component and characterized by the presence of a modified cross-section, where this polyester polymer is obtained by polycondensation involving an aromatic dibasic carboxylic acid ester in the presence of a catalyst, this catalyst contains at least one ingredient selected from the following mixture (1) and the reaction product (2), mixture (1) pre It is a mixture of the following components (A) and (B): (A) a component based on a titanium compound, comprising at least one compound selected from the group consisting of reaction products between titanium alkoxides described by the following general formula (I):

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one group selected from among alkyl groups containing from 1 to 20 carbon atoms and phenyl groups, m is an integer in the range of 1-4, and if m is an integer equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ can be the same or different, with aromatic polyvalent carboxylic acids described by the following general formula (II):

where n is an integer in the range 2-4, or their anhydrides, and the molar ratio in the reaction of titanium alkoxides and aromatic polyvalent carboxylic acids or their anhydrides is in the range from 2: 1 to 2: 5; and (B) a phosphorus compound component comprising triethylphosphonoacetate described by the following general formula (III):

mixture (1) for the catalyst is used at a ratio of the concentrations of the components in the mixture such that the ratio (%) M _Ti between millimoles of the titanium element in the component based on the titanium compound (A) and the number of moles of aromatic dibasic carboxylic acid ester and the ratio (%) M _p between millimoles of the phosphorus element in the component based on the phosphorus compound (B) and the number of moles of aromatic dibasic carboxylic acid ester satisfy the following expressions (i) and (ii):

and the reaction product (2) is the reaction product between the following components (C) and (D): (C) a component based on a titanium compound containing at least one compound selected from the group consisting of titanium alkoxides described by the above formula (I), and (D) a component based on a phosphorus compound containing at least one phosphoric acid monoester described by the following general formula (IV):

where R ⁸ represents an alkyl group containing from 1 to 20 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and the molar ratio in the reaction between component (D) and component (C) is in the range from 1: 1 up to 3: 1 calculated on the atomic ratio (P / Ti) between the phosphorus atoms in component (D) and the titanium atoms in component (C). 2. Polyester fibers with a modified cross section according to claim 1, wherein the phosphorus compound described by the general formula (IV) used in the reaction product (2) for the catalyst is selected from monoalkyl phosphates. 3. Polyester fibers with a modified cross section according to any one of claims 1 or 2, wherein the aromatic dibasic carboxylic acid ester is a diester obtained by transesterification between a dialkyl ether of aromatic dibasic carboxylic acid and an alkylene glycol ester in the presence of a catalyst containing a titanium compound. 4. Polyester fibers with a modified cross section according to any one of claims 1 to 3, wherein the aromatic dibasic carboxylic acid is selected from terephthalic acid, 1,2-naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, diphenyldicarboxylic acid and diphenoxyethane dicarboxylic acid, and alkylene glycol selected from ethylene glycol, butylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol. 5. Polyester fibers with a modified cross section according to any one of claims 1 to 4, wherein the cross section of an individual fiber has a flat shape and the flat shape is a shape including 3-6 shapes with a circular cross section connected in the longitudinal direction. 6. Polyester fibers with a modified cross section according to claim 1, which contain particles of titanium dioxide in an amount of 0.2-10 wt.% Based on the weight of the fibers. 7. Polyester fibers with a modified cross section according to claim 5, where in the cross section of the fibers the flatness represented by the A / B ratio between the length A of the long axis and the maximum length B of the short axis perpendicular to the long axis A is preferably in the range of 3 -6. 8. Polyester fibers with a modified cross section according to any one of claims 5 or 7, wherein the irregularity in the cross section of individual fibers is represented through the B / C ratio between the maximum length of the short axis and the minimum length of C (minimum length at the junction points of the shapes with a circular cross-section) in size is preferably greater than 1 and less than 5. 9. Polyester fibers with a modified cross section according to any one of claims 1 to 4, wherein the cross section of an individual fiber includes a core and 3-8 ribs extending outward from the core and a protrusion coefficient determined in accordance with the following formula (iii ), is in the range from 0.3 to 0.7:

where a ₁ is the distance from the center of the circle inscribed in the inner walls of the cross section of the individual fiber to the tip of the rib, ab ₁ is the radius of the circle inscribed in the inner walls of the cross section of the fiber. 10. Polyester fibers with a modified cross section according to claim 9, where the degree of crystallinity of the fiber does not exceed 30%. 11. Polyester fibers with a modified cross section according to claims 9 or 10, wherein the degree of fiber shrinkage in boiling water is 15-70%. 12. The polyester fibers with a modified cross section according to any one of claims 1 to 4, where the individual polyester fiber includes a core and several ribs extending from the core in a radial direction along the length of the core, and individual fibers with cross-sectional shapes satisfying all of the following ratios (iv) to (vi), are subjected to alkaline hydrolysis in order to separate at least some of the ribs from the cores.

where S _A is the cross-sectional area of the core, D _A is the core diameter if the cross-section is a circle, or the diameter of the circumscribed circle if the cross-section is not a circle, a S _B , L _B and W _B are the cross-sectional area sections, maximum length and maximum width of ribs, respectively. 13. Polyester fibers with a modified cross-section according to claim 14, wherein a compound having a compatibility parameter χ described by relation (vii) below in the range 0.1-2.0 is included in the polyester fibers before alkaline treatment , in an amount in the range of 0.5-5.0 wt.% based on the weight of the polyester fibers.

where V _a represents the molar volume (cm ³ / mol) of the polyester; R represents a gas constant (J / mol · K); T represents the absolute temperature (K); δa and δb are solubility parameters (J ^1/2 / cm ^3/2 ) for the polyester and the compound, respectively. 14. Polyester fibers with a modified cross section according to any one of claims 1 to 4, where the cross section of an individual fiber has a shape that includes a triangular section and a protrusion extending from one vertex of the triangle contour, where both of the following relations are satisfied (viii) and (ix), and having a hollow region in the section of a triangular shape, comprising 3-15% of it:

where L1 is the distance from the connection point of the triangular section and the protrusion to the tip of the protrusion; L2 is the distance from the connection point of the triangular shape section and the protrusion to the side of the triangular shape section opposite the connection point; hi is the width of the protrusion; h2 is the length of the side of the triangular section section opposite the junction of the triangular section section and the protrusion. 15. Polyester fibers with a modified cross section according to 14, which includes a metal salt of organic sulfonic acid, described by the following General formula (V), in an amount in the range of 0.5-2.5 wt.% Based on mass of polyester fibers

where R ⁹ represents an alkyl group containing from 3 to 30 carbon atoms, or an aryl or alkylaryl group containing from 7 to 40 carbon atoms; M is an alkali metal or alkaline earth metal.

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