RU2303091C2 - Mixed yarn with polyester fibers having different degrees of shrinkage - Google Patents

Abstract

FIELD: polymer fibers.

SUBSTANCE: invention relates to technology of producing high-quality mixed yarns constituted by polyester fibers having different degrees of shrinkage and characterized by good color tone and lack of napping, which allow the yarns to be applied in textile industry. Ester used to produce yarn is prepared by using catalyst comprising, in the first embodiment of invention, mixture consisting of (i) Ti compound component composed by one or several specimens selected from Ti alkoxides of general formula I and products of reaction between these alkoxides and carboxylic acids of general formula II or their anhydrides and (ii) phosphorus compound component consisting of a compound depicted by general formula III. According to second embodiment, catalyst comprises product prepared by reaction between Ti compound component composed by one or several specimens selected from Ti alkoxides of general formula I and products of reaction between these alkoxides and carboxylic acids of general formula II or their anhydrides and (ii) phosphorus compound component of general formula IV.

EFFECT: enlarged resource for polymer fibers.

10 cl, 4 tbl, 9 ex

Description

FIELD OF THE INVENTION

The present invention relates to blended yarn with filaments with different degrees of shrinkage from polyesters. More specifically, it relates to blended yarn with filaments with different degrees of shrinkage from polyesters obtained using polymeric polyesters characterized by a satisfactory color tone and excellent formability.

State of the art

Polyester filaments have excellent mechanical, physical and chemical characteristics and are therefore widely used in applications for filaments.

Attempts have been made using filament yarn made from polymeric polyesters to make bulk yarn, and, for example, filament yarns characterized by unequal degrees of shrinkage, which are arranged in the form of filaments of a core and filament sheaths (for example, the layout of a patent application in Japan) have been proposed HEI No. 5-209366).

Polymers constituting polyester filaments, for example polyethylene terephthalate, are usually prepared by first producing the 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 carry out the reaction to the desired degree polymerization. Other polyesters are prepared by similar methods.

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 use of antimony compounds involves a problem due to the fact that 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 a change in the direction of flow of the molten polymer (bending), which, ultimately, causes napping and rupture of filaments or the formation of inhomogeneous physical their properties filament fibers during spinning and drawing steps.

As a means of solving these problems, the use of reaction products between titanium compounds and trimellitic acid as catalysts for producing polyesters (for example, see Japanese Examined Patent Publication SHO No. 59-46258) and the use of reaction products between compounds as catalysts for polyesters were described. titanium and phosphorous acid esters (for example, see Japanese Patent Laid-Open Layout SHO No. 58-38722). Despite the fact that these methods, to some extent, improve the heat resistance of the melt of polyesters, the effect of the improvement is insufficient, and for the obtained polymeric polyesters, an improvement in color tone is required.

As catalysts for the production of polyesters, titanium compound / phosphorus compound complexes have also been proposed (for example, see Japanese Patent Laid-Open Layout No. 7-138354 in Japan). 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 for the obtained polyesters an improvement in the color tone is required.

Blended yarn with various strands of shrinkage is used especially for the manufacture of luxury clothing, and therefore it is necessary to demonstrate high quality and color tone.

Description of the invention

The first objective of the invention is to solve the above-mentioned problems of the prior art as a result of the offer of blended yarn with filaments with different degrees of shrinkage from polyesters, characterized by a satisfactory color tone, lack of teasing and high quality. This goal is achieved by using the following blended yarn with filaments with different degrees of shrinkage from polyesters.

Blended yarn with filaments with different degrees of shrinkage from the polyesters of the invention is a blended yarn comprising two different types of filaments characterized by different degrees of shrinkage in boiling water, individually comprising a polymeric polyester as the main component,

where the polymeric polyester is a polymer obtained by polycondensation with 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 in the form of a titanium compound containing 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 link 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 of 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 in the form of 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 unit selected from the group -CH ₂ and the group -CH ₂ (Y ), where Y represents a phenyl group,

the catalyst mixture (1) is used when the concentration ratio of the components in the mixture is such that the ratio (%) M _Ti between millimoles of the titanium element in the component in the form of a 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 in the form of a 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 in the form of 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 in the form of a phosphorus compound containing at least one phosphorus compound 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 p represents an integer equal to 1 or 2.

Component (A) of the mixture (1) of the catalyst and component (C) of the reaction product (2) of the catalyst in the case of blended yarn with filaments with different degrees of shrinkage from the polyesters of the invention preferably contain the corresponding titanium alkoxide (a) and titanium alkoxide (c), each with a molar 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 product of reaction (2) of the catalyst for producing blended yarn with filaments with different degrees of shrinkage from polyesters 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 when calculated using the ratio between moles of phosphorus atoms in component (D) and moles of titanium atoms in component (C) (P / Ti).

The phosphorus compound described by general formula (IV) used in the product of reaction (2) of the catalyst for producing blended yarn with filaments with different degrees of shrinkage from the polyesters of the invention is preferably selected from monoalkyl phosphates.

The aromatic dibasic carboxylic acid ester in blended yarn with filaments of varying degrees of shrinkage from the polyesters of the invention is preferably a diester obtained by transesterification between an aromatic dibasic carboxylic acid dialkyl ester and an alkylene glycol ester in the presence of a catalyst containing a titanium compound.

The aromatic dibasic carboxylic acid in blended yarn with filaments of varying degrees of shrinkage from the polyesters 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 is preferably selected ethylene glycol, butylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanemethylene glycol and dodecanomethylene glycol.

The second objective of the invention is to propose, in addition to the first objective, a blended yarn with filaments with different degrees of shrinkage from polyesters, characterized by excellent bulk and creating a feeling similar to the feeling of wool. This goal is achieved by using the following blended yarn with filaments with different degrees of shrinkage from polyesters.

Specifically, this is a mixed yarn with filaments with different degrees of shrinkage from polyesters, containing as the main component a polymeric polyester obtained by polycondensation in the presence of the above-mentioned specific catalyst, where two different types of filaments are yarn, partially formed oriented polyester fibers, characterized by a degree of shrinkage in boiling water of not more than 5%, and a polyester filament a, characterized by a degree of shrinkage in boiling water equal to 8% or more.

A third object of the invention is to propose, in addition to the first objective, a blended polyester yarn that allows the fabric to create a feeling of luxurious worsted wool and an excellent sensation of elasticity and gives a shine-free effect. This goal is achieved by using the following blended yarn with filaments with different degrees of shrinkage from polyesters.

Specifically, this is a blended yarn with filaments with different degrees of shrinkage from polyesters, containing as the main component a polymeric polyester obtained by polycondensation in the presence of the above-mentioned specific catalyst, where both filaments are conjugated filaments with a hidden ability to the formation of crimps formed from two different polyesters, conjugated according to the method with the location "side by side" or by the method with an eccentric By the arrangement in the core-shell structure, the degree of shrinkage for elementary threads with a low degree of shrinkage is in the range of 0.5-8.0%, and the degree of shrinkage in boiling water for elementary threads with a high degree of shrinkage is at least 10% .

In the case of blended yarn with filaments with different degrees of shrinkage from polyesters described above, the degree of tortuosity of filaments with a high degree of shrinkage after treatment in boiling water is preferably at least 1.5%.

In addition, in the case of the blended yarn with filaments with different degrees of shrinkage from polyesters described above, the filaments with a low degree of shrinkage are preferably filaments which are received at a reception speed in the range of 2000-4000 m / min when forming fibers from the melt and which are subjected to relaxation heat treatment.

In addition, in the case of the blended yarn with filaments with different degrees of shrinkage from polyesters described above, the mass number of a filament for a filament with a high degree of shrinkage preferably exceeds the corresponding characteristic of a filament with a low degree of shrinkage, while the mass numbers of the individual filament for a filament threads with a low degree of shrinkage and elementary threads with a high degree of shrinkage are in the ranges of 0.05-3.5 dtex and 0.55-15.0 dtex, respectively, and the difference in mass numbers between them is equal to 0.5 decitex or more.

The best way to implement the invention

The essential features of blended yarn with filaments with different degrees of shrinkage from polyesters of the invention are that it consists of two filaments with different degrees of shrinkage in boiling water, both of which contain polymeric polyester as their main component, and that polymeric a polyester is a polymer obtained by polycondensation with an ester of an aromatic dibasic carboxylic acid in the presence of a specific catalyst, the written herein below. This makes it possible to obtain blended yarn with filaments with different degrees of shrinkage, characterized by the presence of a satisfactory color tone, the absence of teasing and high quality. The degree of shrinkage in boiling water in two different filaments is preferably 2% or more, more preferably in the range of 5-50%, and even more preferably 5-30%. As explained hereinafter, in order to stably form the blended yarn of the invention as a main component containing a polyester polyester to produce a high-quality blended yarn that is not exposed to bristling and the like, thereby demonstrating a tangible effect, two different filaments, both of which can be conjugated filaments obtained from two different polymers.

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

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

(a) titanium alkoxides having the general formula (I):

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one link selected from among alkyl groups containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, and phenyl groups, m is a whole a number in the range of 1-4, and preferably 2-4, and if m is an integer of 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 polycondensation catalyst mixture (1) contains at least one compound described by the following general formula (III):

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

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

The component in the form of a titanium compound (C) contains 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 in the form of a phosphorus compound (D) contains at least one phosphorus compound having the 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 p is an integer equal to 1 or 2.

If a mixture of (1) a component in the form of a titanium compound (A) and a component in the form of a phosphorus compound (B) is used as a polycondensation catalyst, then titanium alkoxide (a) having the general formula (I) or the reaction product (b) between titanium alkoxide (a) and aromatic carboxylic acid having the general formula (II), or its anhydride, used as a component in the form of a titanium compound (A), will be characterized by high solubility and compatibility with polymeric polyesters, and therefore, even if the remainder is compone This in the form of a titanium compound (A) will remain in the polymeric polyester obtained by polycondensation, during the formation of fibers from the melt in the vicinity of the die, no accumulation of foreign material will occur, so that with a high efficiency of forming the fibers, an elementary thread can be obtained from polyester with satisfactory quality.

As described by the general formula (I), titanium alkoxides (a) used in the component according to the invention as a titanium compound (A) or (C) of a polycondensation catalyst, tetraisopropoxy titanium, tetrapropoxy titanium, tetra-n-butoxy titanium, tetra ethoxy titanium titanium octane titanium titanium, .

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 polymeric polyester, which will effectively prevent the accumulation of foreign material.

If titanium alkoxide (a) or (c) in a component in the form of 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 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 necessary.

The molar ratio in the reaction between titanium alkoxide (a) or (c) and an aromatic polyvalent carboxylic acid having 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 degraded, or the softening temperature may be lowered, while if the proportion of titanium alkoxide is excessively low, then it may be difficult to go through the polycon nsatsii. Therefore, the molar ratio in the reaction between titanium alkoxide (a) or (c) and an aromatic polyvalent carboxylic acid having the general formula (II) or its anhydride is preferably in the range from (2: 1) to (2: 5).

The product of reaction (b) or (d) obtained by the reaction can be used directly, or they can be used after purification by recrystallization with acetone, methyl alcohol and / or ethyl acetate.

A phosphorus compound (phosphonate derivative) having the general formula (III) used in the component as a phosphorus compound (B) of a mixture (1) of a polycondensation catalyst of the invention is preferably selected from dimethyl esters, diethyl esters, dipropyl esters and dibutyl esters esters of phosphonic acid derivatives such as carbomethoxymethanephosphonic acid, carboethoxymethanephosphonic acid, carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic acid, as rbomethoxyphenylmethanphosphonic acid, carboethoxyphenylmethanphosphonic acid, carbopropoxyphenylmethanphosphonic acid, carbobutoxyphenylmethanphosphonic acid and the like.

If for the polycondensation reaction involving an ester of an aromatic dibasic carboxylic acid, a component in the form of a phosphorus compound (B) consisting of a phosphorus compound (phosphonate derivative) described by the general formula (III) is used, then the reaction with the component in the form of a titanium compound (A) will proceed more moderately in comparison with the reaction using phosphorus compounds used as reaction stabilizers usually, and therefore, the service life as a catalyst for the component in the form the titanium compound (A) in the method of carrying out the polycondensation reaction will be longer, and as a result, a smaller fraction of the component in the form of the titanium compound (A) can be used with respect to the amount of aromatic dibasic carboxylic acid ester in the polycondensation reaction system. In addition, even if a large amount of stabilizer is added to the polycondensation reaction system containing a component in the form of 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) will be used at a ratio of component concentrations in the mixture such that the ratio (%) M _Ti between millimoles of the titanium element in the component in the form of a titanium compound ( a) and the number of moles of the ester of an aromatic dicarboxylic acid and the ratio (%) M _p between the millimoles of phosphorus element in the component in the form of phosphorus compound (B) and the number of moles of the aromatic diacid ester karbono oh acid satisfy the following description of correlative expressions (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 polymer complex polyester may be yellowish, while if if it is more than 15, then the reactivity in polycondensation of a polycondensation catalyst with such a composition will be insufficient, which will make obtaining the target polymer complex polyester difficult. The range for the M _p / M _Ti ratio according to 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 formation characteristics of the filaments of the obtained polymer complex polyester, productivity the method of forming fibers from the melt and the operational characteristics of the obtained filaments will be unsatisfactory. If the value (M _p + M _Ti ) is greater than 100, then when using the obtained polymer complex polyester for forming fibers from the melt in the vicinity of the die, accumulation of foreign material will be observed to a small but significant degree. The value of M _Ti is generally preferred 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.

The phosphorus compound component (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 in the form of a titanium compound (C) and a component in the form of a phosphorus compound (D) may include, for example, combining components (C) and (D) and heating them in glycol. Specifically, heating a solution in glycol containing a component in the form of a titanium compound (C) and a component in the form of a phosphorus compound (D) will lead to cloudiness of the solution in glycol with the precipitation of components (C) and (D) as reaction products . The precipitate can be collected for use as a catalyst to obtain a polymeric polyester.

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 with simultaneous combination of a 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 in the form of a titanium compound (C) and the component in the form of a phosphorus compound (D) to obtain a precipitated reaction product that is insoluble in glycol, it is preferable that the reaction proceed 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 in the form of a titanium compound (C) and a component in the form of a phosphorus compound (D) are preliminarily obtained, and then the solutions are combined and heated .

The reaction temperature between components (C) and (D) is preferably in the range of 50 ° C. 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 for the component in the form of a titanium compound (C) and the component in the form of a 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 to 2.5 when calculated as a molar ratio between phosphorus atoms and titanium atoms. Within this range, a component in the form of a phosphorus compound (D) and a component in the form of 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 polymer complex polyester with a satisfactory color tone. In addition, the practical absence of an excess unreacted phosphorus (V) compound results in achieving high performance without compromising the polymerization reactivity to produce a polyester.

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

where each of R ¹⁰ and R ¹¹ independently represents at least one unit selected from aryl groups containing from 6 to 12 carbon atoms derived from R ¹ , R ² , R ³ and R ⁴ in the General formula (I ), which describes the titanium alkoxide of the component as a titanium compound (C), and R ⁸ in the general formula (IV), which describes the phosphorus compound in the component as a phosphorus compound (D).

Since the reaction product between the titanium compound and the phosphorus compound (III) or (IV) described by the formula (V) has high catalytic activity, the polyester polyesters 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 (V) 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 it can be used as a catalyst for producing a 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 use the purified product as a catalyst. The structure of the catalyst can be confirmed using the method of solid-state NMR and the method of quantitative analysis of the content of metal PMA (X-ray microanalysis).

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

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 polymer polyester 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 polymeric polyesters obtained by copolymerization as mixed components of polyfunctional compounds such as trimesic acid, trimethylol ethane, trimethylol propane, trimethylol methane and pentaerythritol.

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

In accordance with the invention, the polymer polyester used is preferably a polycondensation product involving an aromatic dibasic carboxylic acid ester formed from the aromatic dibasic carboxylic acid and aliphatic glycol described above. 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, since the former result in fewer small particles of a phosphorus compound added during the polycondensation reaction as a phosphorus-containing stabilizer.

In addition, it is preferable to add all or part of the component in the form of a 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 reaction between the 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 in the form of a titanium compound (A) containing (a) at least one a 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 olivalent 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 the component in the form of 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 in the form of a phosphorus compound (D) and the polycondensation reaction are carried out in their presence.

The transesterification reaction will usually be 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 in the form of a titanium compound (A), while at the same time preventing the formation of large amounts of diethylene glycol by-product, so that more favorable heat resistance and other properties can be achieved. 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 recyclable polyesters from recycled 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 produce particles (chips).

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

Solid-phase 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 kPa 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, including contacting with water, water vapor, an inert gas enriched in water vapor, or air enriched in water vapor to deactivate the catalyst remaining in the crumb.

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

The polyester used in the invention, if necessary, may contain small amounts of additives, such as antioxidants, ultraviolet absorbers, flame retardants, fluorescent illuminants, matting agents, color correctors, antifoam agents, antistatic agents, antimicrobial agents, light stabilizers, heat stabilizers, light protection agents 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 microns, and it is preferably included in the polymer complex polyester in an amount in the range of 0.01-10% (wt.).

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

If the polymeric polyester contains titanium dioxide as a matting agent, then the titanium dioxide of the matting agent can be removed from the polymer polyester sample to measure as a result of dissolving the polymeric polyester in hexafluoroisopropanol, feeding the solution by centrifugation to isolate and precipitate particles of titanium dioxide from the solution , separating and collecting the liquid supernatant according to the gradient method and evaporating the solvent from the collected fraction to obtain a sample for and tests carried.

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 in excess of 1% (mass.), As a result, will lead to the occurrence of a saturation effect and may cause the formation of slag during the formation of fibers from the melt. Hindered phenol antioxidants can also be used in combination with secondary thioether antioxidants.

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 propose, in addition to the first objective, a blended yarn with filaments with different degrees of shrinkage from polyesters, which is characterized by excellent bulk and creates a feeling similar to the feeling of wool. This goal is achieved by using the following blended yarn with filaments with different degrees of shrinkage from polyesters.

Specifically, this is a mixed yarn with filaments with different degrees of shrinkage from polyesters, containing as the main component a polymeric polyester obtained by polycondensation in the presence of the above-mentioned specific catalyst, where the filaments with a low degree of shrinkage are yarn, formed by partially oriented polyester fibers, characterized by a degree of shrinkage in boiling water not exceeding 5%, and filaments with high Oka shrinkage yarns are of polyester, a degree of shrinkage in boiling water of 8% or more.

If the two different filaments mentioned above are combined and mixed yarn with filaments with different degrees of shrinkage, formed from these filaments, is used to obtain fabric, then the fabric can be subjected to conventional relaxation heat treatment to give the fabric an excellent bulk.

If the degree of shrinkage in boiling water for filaments with a low degree of shrinkage will exceed 5%, then the filaments with a low degree of shrinkage will tend to undergo excessive shrinkage during heat treatment after fabrication, thereby not achieving the desired volume. As filaments with a low degree of shrinkage, self-stretching yarn is most preferred.

On the other hand, the degree of shrinkage in boiling water for filaments with a high degree of shrinkage of less than 8% tends to result in a smaller difference for the ends of the filaments compared to filaments with a low degree of shrinkage, which makes it difficult to achieve high bulk . However, if the degree of shrinkage in boiling water is excessively high, then when used in a woven material, the recovery after stretching will be unsatisfactory, creating a tendency to produce warpage (“arcs”), and therefore 25% is a suitable upper limit. The preferred range for the degree of shrinkage in boiling water for filaments with a high degree of shrinkage is the range of 12-20%.

Blended yarn with filaments with different degrees of shrinkage from polyesters can be obtained, for example, by the method described below.

The filaments with a low degree of shrinkage of the invention, that is, the yarn yarn formed by partially oriented polyester fibers subjected to relaxation heat treatment, can be obtained, for example, by fixing the yarn formed by partially oriented polyester fibers obtained at a reception speed of 2200 -4500 m / min for 0.01-0.30 seconds when feeding ahead of 0.5-5.0% and the temperature of the contactless heater 160-210 ° C.

The polyester forming filaments with a high degree of shrinkage is preferably polyethylene terephthalate copolymerized with isophthalic acid (a degree of copolymerization of 5-30 mole percent based on the acid component is preferred). If such a complex polyester is used, then filaments with a high degree of shrinkage can be obtained, for example, by first winding undrawn filaments from complex polyester at a speed of forming fibers of 1000-1500 m / min, and then stretching and heat-setting at the degree of extraction of 2.5-3.5 and a fixation temperature of 150-180 ° C. In this case, the relative elongation of the filaments with a high degree of shrinkage is preferably in the range of 45-60%.

Blended yarn with filaments with different degrees of shrinkage from polyesters is preferably obtained by mixing up the aforementioned filaments with a low degree of shrinkage and a high degree of shrinkage. There are no particular restrictions on the entanglement method, but pneumatic entanglement is preferred. The proportion used in this case is preferably a yarn sheath formed by filaments with a high degree of shrinkage: filaments with a low degree of shrinkage = from 25:75 to 75:25 (wt.). The pneumo-entangling method may be weaving or processing using Taslan technology. The yarn obtained as a result of entanglement can also be subjected to additional processing, as necessary, including twisting or sizing - heat setting.

The blended yarn described above with filaments of varying degrees of shrinkage from polyesters can be used for weaving, for example, as warp and / or weft and subjected to relaxation heat treatment to produce woven fabric with excellent bulk. The woven material can also be subjected to alkaline hydrolysis either after or during relaxation heat treatment. The degree of alkaline hydrolysis in this case can be appropriately selected in the range of 5-30% (wt.) Depending on the target volume.

A third objective of the invention is to propose, in addition to the first objective, a blended polyester yarn that allows the fabric to create a feeling of luxurious worsted wool and an excellent sensation of elasticity and gives a shine-free effect. This goal is achieved by using the following blended yarn with filaments with different degrees of shrinkage from polyesters.

Specifically, this is a mixed yarn with filaments with different degrees of shrinkage from polyesters, including as the main component a polymeric polyester obtained by polycondensation in the presence of the above-mentioned specific catalyst, where both filaments with high shrinkage and elementary yarns with a low degree of shrinkage are conjugated elementary yarns with a hidden crimp ability, formed from two different complex fields esters conjugated according to the method with a side-by-side arrangement or by a method with an eccentric arrangement in the core-shell structure, the degree of shrinkage of elementary threads with a low degree of shrinkage is in the range of 0.5-8.0%, and the degree of shrinkage is boiling water for filaments with a high degree of shrinkage is at least 10%.

In the blended yarn described above with filaments with different degrees of shrinkage from polyesters, both filaments with a high degree of shrinkage and filaments with a low degree of shrinkage are conjugated filaments with latent crimpability, formed from two different polyesters from the number of the above-mentioned specific polymeric polyesters conjugated by the side-by-side method or by the method with an eccentric arrangement in the structure of the core points. In this case, the combination of polyesters in conjugated filaments may be a combination of unequal polyesters from among the polyesters mentioned below, or it may be a combination of the same polyesters with different characteristic viscosities.

Low shrink filaments are preferably conjugated filaments obtained by pairing polyethylene terephthalates with different characteristic viscosities. This type of conjugated filament will allow you to get a softer fabric with a more velvet-silky neck. From the point of view of facilitating the stable production of yarn and the latent ability to form crimps, the intrinsic viscosity of the polyester constituting the conjugate filament (when measured at a temperature of 30 ° C. using an ortho-chlorophenol solvent) is preferably in the range 0.50-1, 0 for a component with a low degree of shrinkage and in the range of 0.35-0.55 for a component with a high degree of shrinkage, with a difference between both of at least 0.15.

On the other hand, highly shrinkable filaments are preferably conjugated filaments obtained by pairing a polyethylene terephthalate copolymerized with isophthalic acid at a level of 8-15 mole percent based on the total amount of the acid component and a polyester substantially free of copolymerized component.

If the degree of shrinkage in boiling water for filaments with a low degree of shrinkage is less than 0.5%, then there will be a tendency for the feeling of luxurious worsted wool to be difficult. On the other hand, if the degree of shrinkage in boiling water exceeds 8.0%, then the difference in the degree of shrinkage will be less compared to the high shrinkage filaments described hereinafter, which tends to prevent the creation of an excellent feeling of elasticity or elasticity characteristics. The degree of shrinkage in boiling water for filaments with a low degree of shrinkage is preferably in the range of 2.0-6.0%.

A method for producing filaments with a low degree of shrinkage will be explained in detail below, but filaments with a low degree of shrinkage are preferably filaments, the reception of which when forming the fibers from the melt is carried out at a receiving speed of 2000-4000 m / min and which are subjected to relaxation heat treatment. The use of this type of conjugated filaments will allow you to get a softer fabric that creates an excellent feeling of luxurious worsted wool and is characterized by the presence of a velvet-silky neck.

On the other hand, if the degree of shrinkage in boiling water for filaments with a high degree of shrinkage is less than 10%, then the elasticity characteristics will tend to deteriorate. In addition to this, the difference in the degree of shrinkage from the corresponding parameter for filaments with a low degree of shrinkage will be insufficient and it will be difficult to create an excellent feeling of luxurious worsted wool. The degree of shrinkage in boiling water for filaments with a high degree of shrinkage is preferably in the range of 10-50%, and more preferably 10-40%.

The degree of tortuosity of filaments with a high degree of shrinkage after treatment in boiling water is preferably at least 1.5%. If the degree of crimp is less than 1.5%, then the characteristics of elasticity will not be very high, and it will be difficult to create a feeling of luxurious worsted wool.

In the blended yarn with filaments with different degrees of shrinkage from polyesters described above, the filaments with a low degree of shrinkage and a high degree of shrinkage are mixed and mixed up to obtain a mixed yarn, which is then subjected to heat treatment so that the filaments with a high degree of shrinkage would be located mainly in the core region, and filaments with a low degree of shrinkage would be located mainly in the shell region. The difference in degrees of shrinkage for filaments with a low degree of shrinkage and with a high degree of shrinkage in the regions of the core and shell will result in the formation of crimp with different orientations and periods of crimp, while different levels of crimp manifesting in the areas of the core and shell of mixed yarn, will form a two-level crimp structure. Such a two-level crimp structure will allow the fabrics to create a feeling of luxurious worsted wool while at the same time giving the corresponding elasticity characteristics. In addition, it was found that the location of the filaments with a low degree of shrinkage in the region of the shell provides a highly superior feeling of luxurious worsted wool, not found in the prior art.

The mass number of individual filaments for filaments with a low degree of shrinkage is preferably in the range of 0.05-3.5 dtex, while the mass number of individual filaments for filaments with a low degree of shrinkage is preferably in the range of 0.55-15 , 0 dtex. In addition, the mass number of individual filaments for filaments with a low degree of shrinkage is preferably less than the mass number of individual filaments for filaments with a high degree of shrinkage, the difference between them being preferably 0.5 dtex or more, and more preferably 1.0 dtex or more. Such a difference in mass numbers will make it possible to achieve crimp formation with unequal tortuosity values found in the core and shell regions, with a distinct two-level crimp structure, while at the same time giving the fabric a more velvet-silky neck and creating an excellent feeling of luxurious worsted wool.

The blended yarn described above with filaments of varying degrees of shrinkage from polyesters is a blended yarn obtained by mixing up with blending of filaments with a high degree of shrinkage and a low degree of shrinkage, but an excessively small number of weaves will result in insufficient entanglement between the filaments threads with a high degree of shrinkage and a low degree of shrinkage and will tend to give the surface of the fabric an unsightly appearance, while Remy, as an excessively large number of weaves, will lead to a decrease in the gaps between the filaments and to insufficient swelling of the fabric, which will make it difficult to create a feeling of luxurious worsted wool. The number of weaves is preferably in the range of 10-90 / m, and more preferably in the range of 15-50 / m.

Blended yarn with filaments with different degrees of shrinkage from polyesters, which is obtained by mixing with a blend of filaments with a high degree of shrinkage and a low degree of shrinkage, can be obtained without the commonly used stages of false twisting. Therefore, the blended yarn of the invention can make it possible to obtain a fabric characterized by the presence of a so-called gloss-free effect, not showing any gloss or gloss resulting from deformation of the cross-sections of the filaments as a result of a false twist.

Therefore, there are no special restrictions on the cross-sectional shape of individual filaments for filaments with a low degree of shrinkage and a high degree of shrinkage, but in order to obtain the effect of lack of gloss, compressed and deformed cross sections, such as those obtained in the case of yarn of false twists, disrespectful.

Blended yarn with filaments with different degrees of shrinkage from polyesters can be obtained, for example, by the following method.

Filaments with a low degree of shrinkage are obtained by drying two different polyesters in the form of granules using conventional methods, melting them using conventional melt fiber forming equipment equipped with a worm melter, and forming conjugated fibers according to the side-by-side method "either by a method with an eccentric arrangement in the structure of the core-shell, cooling, adding a suitable sizing and receiving at a reception speed of 2000-4000 m / min without Hooks with obtaining conjugated filaments with a hidden ability to form crimp. If the receiving speed exceeds 4000 m / min, then for the conjugated filament it will be difficult to bring the degree of shrinkage in boiling water to the level of 0.5-8.0% during the relaxation heat treatment described below, and there will be a tendency for fabrics that create the feel of luxurious worsted wool will be more difficult. On the other hand, if the receiving speed is less than 2000 m / min, then the resulting conjugated filament will tend to become brittle, which will result in a decrease in handling comfort when used in blended yarn.

In the case of conjugated filaments with a hidden ability to form crimps, characterized by the presence of such a difference in the degree of shrinkage, the heat treatment conditions of conjugated filaments subjected to stretching at a speed of forming fibers in the above range can be adjusted by adjusting the relaxation heat treatment to in order to obtain filaments with a low degree of shrinkage, characterized by a degree of shrinkage in boiling water in the range of 0.5-8.0%. For example, to obtain filaments with a low degree of shrinkage, characterized by a degree of shrinkage in boiling water in the range of 0.5-8.0%, after the first winding of the conjugated filaments subjected to drawing, they can be passed through heat treatment equipment equipped with a heater, located between at least two rotating rollers for relaxation heat treatment. The heater is preferably a non-contact type mounted on the supply side. The degree of relaxation in this case will be different depending on the spinning speed of the fibers and the like, but preferably it is in the range of 1-45%, and more preferably in the range of 1-10%. A degree of relaxation of less than 1% will tend to result in a degree of shrinkage greater than 8%. On the other hand, a degree of relaxation greater than 45% will result in more feeding filaments wound on the roller during the relaxation heat treatment.

The temperature of the heater is preferably in the range of 180-280 ° C, and more preferably 200-260 ° C. If the temperature of the heater is less than 180 ° C, then the degree of shrinkage in boiling water will tend to exceed 10%. If the temperature of the heater exceeds 280 ° C, then a tendency to break of the filament will be observed in the vicinity of the heater.

Filaments with a high degree of shrinkage can be obtained by the following method. For two different types of granules of polyesters, the fibers are molded from the melt with the help of the well-known spinning dies for forming conjugated fibers and coiled at 1000-4000 m / min, and after that the obtained non-stretched filament is subjected to stretching. The non-drawn filament can also be drawn directly immediately after forming the fibers, without first having to be wound.

The hood is preferably carried out with pre-heating in the temperature range of 30-100 ° C, and the temperature of the heat setting is in the range of 140-280 ° C. The preheating temperature below 30 ° C will tend to result in inhomogeneous drawing and the formation of filaments characterized by the presence of numerous heterogeneities in quality. On the other hand, a preheating temperature in excess of 100 ° C will tend to lead to instability in the formation of fibers, including a more significant movement of the filament on the rollers and to increased amounts of defects on the filament. A heat-setting temperature lower than 140 ° C will not allow the hood to be drawn stably, creating a tendency to irregularities in the hood and the formation of teasing or places with defects in coloring, while a heat-setting temperature exceeding 280 ° C will tend to lead to rupture of filaments during heat setting.

The degree of drawing will vary depending on the spinning speed of the fibers, but it is preferably set such that the elongation of the filaments with a high degree of shrinkage after drawing is equal to 25-65%. If the degree of stretching is set so that the elongation is less than 25%, then as a result of stretching, rupture of filaments and napping will occur to a greater extent. Conversely, if the degree of stretching is set such that the elongation exceeds 65%, then in the resulting filaments with a high degree of shrinkage, more complex strands not subjected to stretching will be observed.

Filaments with a low degree of shrinkage and filaments with a high degree of shrinkage, obtained by the method described above, can be arranged in parallel, and in the case of entanglement with mixing, in order to obtain mixed polyester yarn according to the invention, when fed ahead of schedule 1 -5% and when using the well-known dies forming weaves, the air pressure in the die can be adjusted to obtain 15-90 weaves / m.

In order to make textiles that create an excellent feeling of luxurious worsted wool, characterized by the elasticity and gloss effect, the blended yarn with filaments with different degrees of shrinkage from polyesters can be used for weaving or knitting and subjected to commonly used processing steps in the form washing, dyeing and finishing to obtain a hidden ability to form crimps.

Examples

The present invention will be further explained in detail using the following examples.

(1) Content of titanium metal element, phosphorus element content

The sample in the form of particles of a complex polyester was heated to melting on an aluminum plate, and then served in a press for direct compression and molded to obtain a flat molded sample for testing. The sample was fed to a Model 3270E fluorescence X-ray analyzer from Rigaku Corp. for measuring the content of a titanium metal element and the content of a phosphorus element.

(2) intrinsic viscosity

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

(3) Volumetric

Volume was determined by measuring the worsted wool quality (St) for each standard and graded on a scale with levels 1-5.

(4) Teasing of fabric

The degree of teasing was evaluated and graded on a scale with levels of 1-5, with 5 corresponding to the lowest degree of teasing.

(5) The property of deep staining

Staining was performed using black disperse dye under the same conditions, and grading was based on a scale with levels 1-5 based on visual inspection, while the deepest color corresponded to level 5.

Parameters were measured using the following methods, and intrinsic viscosity was measured using method (1) for examples 4-10 and comparative examples 4-5.

(6) The degree of shrinkage in boiling water (%)

It was measured in accordance with Method 8.18.1 B of JIS L1013.

(7) Degree of tortuosity

The yarn was wound on a bobbin with a tension of 1225/2500 mn × 9 (mass number in tex (50 mg (mass number in denier) and received a skein corresponding to approximately 3300 dtex (3000 de). After receiving skein, a load was applied to one end of the skein in the form 49/2500 mn × 9 × mass number in dtex + 49/25 mn × 9 × mass number in tex (2 mg × mass number in denier + 200 mg × mass number in denier) and after one minute the length L0 was measured (cm ). Then, after removal of the load, 49/25 mn × 9 × mass number in tex (200 mg × mass number in denier) was processed for 20 minutes in with boiling water at 100 ° C. After processing in boiling water, 49/2500 mn × 9 × mass number in tex (2 mg × mass number in denier) was removed, and the yarn in the free state was dried under natural conditions for 24 hours. the naturally dried sample was again loaded with 49/2500 mn × 9 × mass number in dtex + 49/25 mn × 9 × mass number in tex (2 mg × mass number in denier + 200 mg × mass number in denier) and after one minute, the length L1 (cm) was measured. After that, a load of 49/25 mn × 9 × mass number in tex (200 mg × mass number in denier) was removed and after one minute the length L2 was measured, and the total degree of tortuosity was calculated using the following formula. The measurements were carried out 10 times and the average value was determined.

The degree of tortuosity (%) = [(L1-L2) / L0] × 100

(8) Number of weaves (/ m)

It was measured in accordance with JIS L1013 8.15.

(9) Stretch Factor

A test sample of 5 cm × 20 cm was subjected to an initial load of 20 g when using a tensile testing machine equipped with an automatic recording device, and the test sample was clamped to withstand a distance between clamps of 10 cm, subjected to tension at a constant load of 1.5 kg and stretching speed of 30 cm / min, and then immediately restored to its original position at the same speed and plotted the load-elongation curve. The tensile coefficient was expressed using the following formula, where the tensile value (with an accuracy of 0.01 cm) after stretching under the influence of a constant load of 1.5 kg and immediately before the immediate restoration of the original position of the sample at the same speed was indicated as L (cm) .

ST = [L / 10] × 100 (%)

(10) Sensation of luxurious worsted wool and shine effect

Weaved from blended yarn to obtain a twill weave with a base in the form of 192 single strands / 3.79 cm and a weft in the form of 144 single strands / 3.79 cm, and then dyed blue, and 5 experts evaluated the feel of luxurious worsted wool (soft velvet-silky fingerboard, a feeling of puffiness) and the effect of lack of shine. The effect was indicated as good or bad.

(11) Polymer Release State

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 graduated on the following scale. Observation was carried out starting from the second day after the formation of conjugated fibers.

Level 1: Launched filament traced a consistent drop line with a stable feed.

Level 2: Slight bending, twisting or twisting for the produced filament.

Level 3: Large bends, twists or twists for the produced filament. Partial contact of the polymer with the surface of the die, which as a result leads to frequent ruptures of filaments.

(12) Teething number (/ 10 ⁶ m)

After passing 250 wrapped (or wound on spools) filaments of blended polyester yarns 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, and 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 atom in the solution was 1.02%.

Preparation of phosphorus compound:

A three-necked flask with a volume of 2 L was prepared, which has the function of heating, mixing and stirring the contents, and 656 g of ethylene glycodia were placed and heated to 100 ° C under stirring. After reaching 100 ° C., 34.5 g of monolauryl phosphate was added and the mixture was heated, mixed and stirred until dissolved to give a clear solution. This solution hereinafter in the present invention 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 the present invention will be abbreviated as “TP1-2.0 catalyst”.

In order to analyze the precipitate obtained in the reaction, part of the solution of the reaction mixture was filtered using a filter with 5 μm pores and a precipitated reaction product was obtained in the form of a solid phase, and then it was washed with 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, as in titanium tetrabutoxide, while P-31 DD / MAS measurement (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 region 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 a reaction were fed into a reactor that already contained 225 mass parts of the oligomer, while stirring in a nitrogen atmosphere under conditions of maintaining 255 ° C and normal pressure at a constant speed. The esterification was carried out for 4 hours before completion when water and ethylene glycol formed during the reaction were removed 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 parts by weight of the oligomer obtained by carrying out the esterification reaction, the previously obtained 3.34 parts by weight of the “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 ° C 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 achieved, the reaction mixture was suspended. 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.

The granules were used as starting material for spinning fibers at a fiber spinning speed of 3200 m / min and yarn yarn formed by partially oriented polyester fibers with a characteristic of 90 dtex / 24 filaments (mass number of an individual filament: 3.8 dtex) which were subjected to heat treatment for 0.05 seconds at a feed, with a lead of 1.5% and a fixation temperature of 185 ° C (plate heater) and received a filament of shell, characterized by the degree of shrinkage in boiling in ode equal to 0%.

Regardless, after the preparation of the catalyst by the same method as described above, polyester granules copolymerized with isophthalic acid at an introduction level of 10.0% were used as starting material for forming fibers at a fiber forming speed of 1300 m / min, ( intrinsic viscosity: 0.640) and after the first yarn was not drawn, it was drawn and thermofixed at a draw degree of 3.2 and a fixation temperature of 160 ° C, yarn yarn was obtained as filaments of those subjected to a hood, with a characteristic of 91 dtex / 15 filaments (mass number of an individual filament: 6 dtex) and a degree of shrinkage in boiling water of 15%.

After this, in accordance with the processing method using Taslan technology, a mixed yarn with a core-shell structure was subjected to pneumo-entangling when feeding ahead of elementary threads with a high degree of shrinkage (side of elementary threads of the core) 3% and feeding ahead of the elementary threads with a low degree of shrinkage (side filament yarn) 7%, air pressure 784 kPa and speed 400 m / min.

The obtained mixed-yarn mixed yarn was twisted at 1200 cr / m [15300 / (dtex / 1.11) ^1/2 ; dtex = 1.81] and received twisted yarn intended for use as a warp and weft, with a twill weave 2/2 with a density of unpainted fabric 42.2 single thread / cm for warp and 21.9 single thread / cm for weft. Unpainted fabric was subjected to preliminary relaxation for 20 seconds at 100 ° C, and then for relaxation for 40 minutes a disk relaxer was used at a limit temperature of 120 ° C and after proper shrinkage of the warp and weft, after preliminary fixation after air drying, the fabric was subjected to alkaline hydrolysis to a degree of 13% (wt.). For coloring at 135 ° C for 60 minutes, dispersed dye was used using a nozzle dyeing machine for finishing. The evaluation results for the obtained dyed fabric are shown in Table 1. The obtained woven material created a sensation similar to that of wool.

Comparative Example 1

The same procedure was used 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 charged amount was 4.83 mass parts, and an additional 0.121 was charged as stabilizer part of a solution of trimethylphosphate in ethylene glycol with a concentration of 25% and received polyethylene terephthalate with a characteristic viscosity of 0.630 and a polyester obtained by copolymerization with isophthalic acid at the level of its introduction 10.0 mole percent. The polymers were used to obtain blended yarn with filaments with different degrees of shrinkage in the same way as in example 1 and got dyed fabric. The evaluation results are shown in table 1.

Reference Example 2

The same procedure was carried out as in Example 1, except that in order to obtain polyethylene terephthalate with an intrinsic viscosity of 0.630 and a polyester obtained by copolymerizing it with isophthalic acid at a level of 10.0 mol%, As the polycondensation catalyst, only the TB solution obtained in Example 1 was used, and the loading amount was 1.03 mass parts. The polymers were used to make blended yarns with filaments with different degrees of shrinkage in the same manner as in Example 1, and dyed fabric was obtained. The evaluation results are shown in table 1.

Table 1 Example 1 Comparative Example 1 Reference Example 2 Polymerization catalyst TP1-2.0 Sb ₂ O ₃ TV solution Bulk 4-5 4-5 4-5 Napping 5 3-4 5 Deep staining property 4-5 four 2-3

Example 3

The same procedure was used as in Example 2, except that 0.016 parts of titanium trimellitate (TMT) synthesized by the method described below was used as the titanium compound. The evaluation results for the obtained dyed fabric are shown in table 2.

The method of synthesis of titanium trimellitate:

To a solution of trimellitic anhydride in ethylene glycol (0.2%) at a 1/2 molar ratio with trimellitic anhydride was added tetrabutoxytitanium and the reaction was carried out for 60 minutes in air at normal pressure, maintaining a temperature of 80 ° C, after which the system was cooled to normal temperature, and the resulting catalyst was recrystallized using 10 times the amount of acetone, and then the precipitate was filtered using filter paper and dried at 100 ° C for 2 hours to obtain the target compound.

After loading 0.016 parts of titanium trimelitate (TMT) into a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol in a stainless steel reactor suitable for pressure reaction, a pressure of 0.07 MPa was created to carry out the transesterification reaction with an increase in temperature from 140 ° C to 240 ° C, and then 0.035 parts by weight 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 a polyester with a maximum viscosity of 0.630 and a diethylene glycol content of 1.5% and the polymer was granulated in the usual way.

The granules were used as starting material for spinning fibers at a fiber spinning speed of 3200 m / min and yarn yarn formed by partially oriented polyester fibers with a characteristic of 90 dtex / 24 filaments (mass number of an individual filament: 3.8 dtex) which were subjected to heat treatment for 0.05 seconds with a feed ahead of 1.5% and a fixation temperature of 185 ° C (plate heater) and received filaments with a low degree of shrinkage, characterized by a degree of shrinkage subcontroller in boiling water of 0%.

Regardless, polyester granules copolymerized with isophthalic acid at a level of 10.0% addition (intrinsic viscosity: 0.640) after polycondensation using the same method as described above were used as starting material for forming the fibers. for the formation of fibers at a speed of 1300 m / min and after the first receipt of the yarn not subjected to stretching, it was subjected to stretching and heat setting at a drawing degree of 3.2 and a fixing temperature of 160 ° C to obtain elementary x yarns with a high degree of shrinkage of yarn yarn, independently subjected to drawing, with a characteristic of 91 dtex / 15 elementary yarns (mass number of an individual yarn: 6 dtex) and a degree of shrinkage in boiling water of 15%.

After this, in accordance with the processing method using Taslan technology, a mixed yarn with a core-shell structure was subjected to pneumo-entangling when feeding ahead of elementary threads with a high degree of shrinkage (side of elementary threads of the core) 3% and feeding ahead of the elementary threads with a low degree of shrinkage (side filament yarn) 7%, air pressure 784 kPa and speed 400 m / min.

The obtained mixed-yarn mixed yarn was twisted at 1200 cr / m [15300 / (dtex / 1.11) ^1/2 ; dtex = 1.81] and received twisted yarn intended for use as a warp and weft, with a twill weave 2/2 with a density of unpainted fabric 42.2 single thread / cm for warp and 21.9 single thread / cm for weft. Unpainted fabric was subjected to preliminary relaxation for 20 seconds at 100 ° C, and then for relaxation for 40 minutes a disk relaxer was used at a temperature limit of 120 ° C and after proper shrinkage of the warp and weft as a result of preliminary fixation after air drying, the fabric was subjected to alkaline hydrolysis to a degree of 13% (wt.). For coloring at 135 ° C for 60 minutes, dispersed dye was used using a nozzle dyeing machine for finishing. The evaluation results for the obtained dyed fabric are shown in Table 2. The obtained woven material created a sensation similar to that of wool.

table 2 Example 3 Reference Example 2 Ti compound Type of TMT - Content (% (mmol.)) 5 - Compound P Type of TEFA - Content (% (mmol.)) thirty - Sb compound Type of - Sb ₂ O ₃ Content (% (mmol.)) - 31 M _r / M _Ti 6 - M _p + M _Ti (% (mmol.)) 35 - Bulk 4-5 4-5 Napping 5 3-4 Deep staining property 4-5 four

Example 4

Obtaining a compound of titanium, a compound of phosphorus and a catalyst and obtaining an oligomer was carried out in the same manner as in example 1.

After transferring 225 mass parts of the obtained oligomer into a polycondensation reactor as a polycondensation catalyst, 3.34 mass parts of the previously prepared “TP1-2.0 catalyst” were loaded into it. After that, to carry out the polycondensation reaction, the reaction temperature in the system was increased from 255 ° C 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 mixture was suspended. 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 granules of polyethylene terephthalate with characteristic viscosities of 0.63, 0.55 and 0.43.

To obtain polyester granules based on polyethylene terephthalate with an intrinsic viscosity of 0.63 copolymerized with isophthalic acid at a level of 10 mol%, based on the total amount of the acid component, the previously obtained TP1-2.0 catalyst was used for transesterification and copolymerization with using 161 mass parts of high-purity terephthalic acid, 18 mass parts of high-purity isophthalic acid and 95 mass parts of ethylene glycol.

The copolymerized polyethylene terephthalate-based polyester and the aforementioned polyethylene terephthalate with a characteristic viscosity of 0.43 were used for melt spinning of filaments conjugated by the side-by-side arrangement with a mass ratio of conjugated filaments of 50/50 (melt spinning temperature: 280 ° C, the difference in the viscosity of the melts: 70 Pa · sec) and after winding at a winding speed of 1450 m / min, extraction and heat setting were carried out at a drawing degree of 2.4, a drawing speed of 600 m / min, erature hoods 90 ° C, and the fusing temperature of 230 ° C to obtain filaments of high shrinkage characteristics with 110 dtex / 24 filaments.

Regardless, polyethylene terephthalate with an intrinsic viscosity of 0.630 and polyethylene terephthalate with an intrinsic viscosity of 0.43 were used for melt spinning of filaments conjugated by the side-by-side arrangement with a mass ratio of conjugated filaments of 50/50 (melt spinning temperature: 285 ° C, the difference in the viscosity of the melts: 70 Pa · sec) followed by winding at a winding speed of 3000 m / min and received conjugated elementary threads with a characteristic of 70 dtex / 24 elementary threads. The resulting conjugated filaments were passed through a non-contact slit heater set at 230 ° C. (relaxation heat treatment temperature) and subjected to relaxation heat treatment at a relaxation rate of 3.5% and a travel speed of 400 m / min to obtain filaments with a low degree of shrinkage, and they were combined with filaments with a high degree of shrinkage, subjected to entanglement to obtain mixed yarn using air pressure in a spinneret forming dies, 0.2 MPa and smats Ali. The resulting blended yarn with a characteristic of 183 dtex / 48 filaments had 35 weaves / m.

In any of the cases of forming conjugated filaments, no accumulation of foreign material was found in the vicinity of the outlet of the die, while the release state of the polymer was stable for a long period, and the obtained mixed polyester yarn showed excellent quality with a low degree of teasing. The degree of shrinkage in boiling water for filaments with a low degree of shrinkage and the degree of shrinkage in boiling water and the degree of crimp for filaments with a high degree of shrinkage are shown in table 1.

This blended yarn was used in weaving, and an assessment of the quality of the fabric revealed a satisfactory color tone, excellent elasticity and shine effect, a velvet-silky neck and a suitable puffiness and an excellent feeling of luxurious worsted wool.

Example 5

Blended yarn was obtained by the same method as in example 4, except that the temperature of heat setting in the manufacture of filaments with a high degree of shrinkage was changed from 230 ° C to 250 ° C, and the degree of relaxation in the manufacture of filaments with a low degree shrinkage changed from 3.5% to 6%. The evaluation results are shown in table 3. The color tone of the obtained fabric was satisfactory.

Example 6

Blended yarn was obtained by the same method as in example 4, except that the temperature of heat setting in the manufacture of filaments with a high degree of shrinkage was changed from 230 ° C to 150 ° C, and the degree of relaxation in the manufacture of filaments with a low degree shrinkage changed from 3.5% to 8%. The evaluation results are shown in table 3. The color tone of the obtained fabric was satisfactory.

Reference Example 4

The same procedure was carried out as in Example 4, except that an antimony compound was used as the polymerization catalyst to obtain the polyester. During the spinning of the fibers, there was a significant accumulation of foreign material in the vicinity of the outlet of the die, the state of release of the polymer was characterized by the presence of a significant amount of twisting, twisting and sticking to the surface of the die, and the obtained mixed polyester yarn showed a high value of the napping value. The color tone of the fabric was worse compared to the color tone in Example 4.

Table 3 Example 4 Example 5 Example 6 Release Status High shrink filaments one one one Low shrink filaments one one one Low shrink filaments The degree of shrinkage (%) 5 four one High shrink filaments The degree of shrinkage (%) 16 eleven 26 The degree of tortuosity (%) 3.0 1,5 7.9 Teasing number for blended yarn (/ 10 ⁶ m) 0.1 0.2 0.2 Stretch ratio 23 19 thirty The feeling of luxurious worsted wool Good Good Good Gloss effect Good Good Good

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 to carry out the transesterification reaction with an increase in temperature from 140 ° C 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, disodium 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 at the end of the reaction at various points with the desired degrees of polymerization to obtain polyethylene terephthalates with ultimate viscosities of 0.63 and 0.43, each of which was granulated in the usual way.

After loading 0.064 parts by weight of calcium acetate monohydrate into a mixture of 90 parts by weight of dimethyl terephthalate, 10 parts by weight of dimethyl isophthalate and 70 parts by weight of ethylene glycol, the transesterification was carried out according to the method described above, and antimony trioxide was added to undergo the polymerization reaction to obtain a polyester based on polyethylene terephthalate with 0.63, copolymerized with isophthalic acid at the level of its introduction of 10 molar percent, calculated on the total amount of the acid component, p after which the polymer was granulated in the usual manner.

High shrinkage filaments were prepared using polyethylene terephthalate granules with an intrinsic viscosity of 0.63 and polyester granules based on polyethylene terephthalate copolymerized with isophthalic acid. Filaments with a low degree of shrinkage were also obtained using granules of polyethylene terephthalate with an intrinsic viscosity of 0.63 and granules of polyethylene terephthalate with an intrinsic viscosity of 0.43. These filaments were combined to produce blended yarn.

During the entire process of forming fibers, there was a significant accumulation of foreign material in the vicinity of the outlet of the die, the release state of the polymer was characterized by significant twisting, twisting and sticking to the surface of the die, and the obtained mixed polyester yarn had a high nibble value.

Table 4 Reference Example 5 Ti compound Type of - Content (% (mmol.)) - Compound P Type of - Content (% (mmol.)) - Sb compound Type of Sb ₂ About ₃ Content (% (mmol.)) 31 M _r / M _Ti 6 M _p + M _Ti (% (mmol.)) 35 Release Status High shrink filaments 3 Low shrink filaments 3 Low shrink filaments The degree of shrinkage (%) 6 High shrink filaments The degree of shrinkage (%) fifteen Degree of tortuosity 3.0 Teasing for blended yarn (/ 10 ⁶ m) 2.0 Stretch ratio 26 The feeling of luxurious worsted wool Good Gloss effect Good

Industrial Applicability

From blended yarn with filaments with different degrees of shrinkage from the polyesters of the present invention can be obtained fabrics characterized by bulk and excellent color tone. Fabrics are characterized not only by the presence of such an excellent color tone, but also by virtually no teasing and extremely excellent quality, and therefore they can be used for the manufacture of luxurious fabrics.

Claims (10)

1. Blended yarn with filaments with different degrees of shrinkage from polyesters, including two different types of filaments, characterized by different degrees of shrinkage in boiling water, individually including a polymeric polyester as the main component, where the polymeric polyester is a polymer obtained in as a result of polycondensation of an ester of an aromatic dibasic carboxylic acid in the presence of a catalyst, this catalyst contains a mixture (1) or a reaction product ii (2), the mixture (1) is a mixture of the following components (A) and (B): (A) a component in the form of a titanium compound containing at least one compound selected from the group consisting of titanium alkoxide reaction products (a) described by the following general formula (I):

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

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

the catalyst mixture (1) 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 in the form of a 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 in the form of a 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 in the form of 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) a component in the form of a phosphorus compound containing at least one phosphoric acid phosphorus compound 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 (P: Ti) of component (D) and component (C) when calculated through the ratio between moles of phosphorus atoms in component (D) and moles of titanium in component (C) (P / Ti) is from 1: 1 to 3: 1 and p represents an integer of 1. 2. The blended yarn according to claim 1, wherein the phosphorus compound described by the general formula (IV) used in the reaction product of the catalyst (2) is selected from monoalkyl phosphates. 3. The blended yarn of claim 1, wherein the aromatic dibasic carboxylic acid ester is a diester obtained by transesterification between an aromatic dibasic carboxylic acid dialkyl ester and an alkylene glycol ester in the presence of a catalyst containing a titanium compound. 4. The blended yarn according to claim 1, 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 is selected from ethylene glycol, butylene glycol glycol , propylene glycol, neopentyl glycol, hexanemethylene glycol and dodecanmethylene glycol. 5. The blended yarn according to claim 1, wherein the difference in degrees of shrinkage in boiling water between two filaments is 2% or more. 6. The blended yarn according to claim 1, in which both filaments are conjugated filaments with a hidden crimp ability, formed from two different polymeric polyesters, conjugated by a side-by-side method or by an eccentric arrangement in the core-shell structure, the degree of shrinkage in boiling water for one type of filament is in the range of 0.5-8.0%, and the degree of shrinkage in boiling water for another type of filament is at least 10%. 7. The blended yarn according to claim 1, wherein the degree of crimp of the filaments with a high degree of shrinkage in boiling water (filaments with a high degree of shrinkage) after processing in boiling water is at least 1.5%. 8. The blended yarn according to claim 1, in which the filaments with a low degree of shrinkage in boiling water are filaments that are produced at a reception speed in the range of 2000-4000 m / min when forming fibers from the melt and which are subjected to relaxation heat treatment . 9. The blended yarn according to claim 1, in which the mass number of an individual elementary thread for elementary threads with a high degree of shrinkage exceeds the corresponding characteristic of elementary threads for a low degree of shrinkage, while the mass number of individual elementary threads for elementary threads with a low degree of shrinkage is in the range 0.05-3.5 dtex, the mass number of individual filaments for elementary filaments with a high degree of shrinkage is in the range of 0.55-15.0 dtex, and the difference in mass numbers between the filaments yields equal to 0.5 dtex or more. 10. The blended yarn of claim 1, wherein the two different types of filaments are yarn formed by partially oriented polyester fibers having a degree of shrinkage in boiling water of not more than 5%, and polyester yarn with a degree of shrinkage in boiling water equal to 8% or more.