RU2301855C2 - Fibrous polyester structure - Google Patents

Abstract

FIELD: polymer fibers.

SUBSTANCE: invention relates to fabrication of fibrous articles, in particular fibrous structures from polyesters. These structures are obtained from polyester fiber prepared in presence of catalyst, which comprises (A) mixture consisting of (i) component in the form of Ti compound formed from one or several compounds selected from titanium alkoxides described by presented below general formula (I) and products of reaction between those alkoxides and carboxylic acids described by general formula (II) or their anhydrides and (ii) component in the form of P compound consisting of compound having general formula (III) and/or (B) product obtained by reaction between component in the form of Ti compound formed from one or several compounds selected from titanium alkoxides described by general formula (IV) and product of reaction between those alkoxides and carboxylic acids described by general formula (II) or their anhydrides, and component in the form of P compound consisting of compound having general formula (V).

EFFECT: improved color tones and moldability.

13 cl, 6 tbl, 59 ex

Description

FIELD OF THE INVENTION

The present invention relates to a polyester fibrous structure. More specifically, it relates to a polyester fibrous structure obtained using a polyester resin with a satisfactory color tone and excellent formability.

State of the art

Polyester resins, in particular polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate resins, exhibit excellent mechanical, physical and chemical performance properties and are therefore widely used for the manufacture of fibers, films and other molded products. As is known, they demonstrate excellent mechanical strength and dimensional stability, especially when used in fibrous structures.

Such polymers intended for the manufacture of fibrous structures, for example polyethylene terephthalate, are usually obtained by first synthesizing an ethylene glycol ester of terephthalic acid and / or its lower polymer, and then heating it under reduced pressure in the presence of a polymerization catalyst to carry out the reaction until the desired degree of polymerization is achieved . 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 problem associated with the use of antimony compounds is that the continuous continuous spinning of fibers from a melt of polyesters results in the accumulation of foreign materials sticking in the vicinity of the spinning hole (hereinafter referred to simply as “sticking to the die”), and to a change in the direction of flow of the molten polymer (bending), which, ultimately, causes napping and rupture of the threads or the formation of inhomogeneous physical properties olokna during fiber spinning and drawing stages. In addition, the use of polyester fibers containing such polyesters to produce polyester fiber structures has resulted in problems such as poor process stability and poor quality of the obtained polyester fiber structures.

As a means of solving these problems, the use of reaction products between titanium compounds and trimellitic acid as catalysts (for example, in Japanese Patent Publication SHO No. 59-46258) and the use of reaction products between titanium compounds and polyesters as catalysts have been described. esters of phosphorous acid (for example, in the layout for the grant of a patent in Japan SHO No. 58-38722). Despite the fact that these methods, to some extent, improve the heat resistance of the melt of the polyesters, the effect of the improvement is insufficient, and for the obtained polyester resins an improvement in the color tone is required.

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

Disclosure of the invention

The aim of the invention is to solve the above-mentioned problems of the prior art by offering a polyester fiber structure characterized by a satisfactory color tone (high L * value and low b * value) obtained from high-quality polyester fiber.

The polyester fiber structure of the invention is a polyester fiber structure comprising a polyester fiber containing, as a main component, a polymeric polyester, characterized in that

the fibrous structure is at least one type of fibrous structure selected from the group consisting of nonwoven materials containing polyester fiber, cotton wool containing polyester fiber, and fibrous structures having thicknesses in the range of 5-100 mm, including the main fiber formed from staple fiber from a complex polyester, and obtained by the method of thermal bonding conjugated staple fiber, where the polymer complex polyester is present in either one of the two or both nentes formed by the main fiber and obtained by the method of thermal bonding multicomponent staple fiber,

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

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

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

(A) a component in the form of a titanium compound, consisting of at least one compound selected from the group consisting of

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

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one link selected from among C _1-20 alkyl groups and phenyl groups, m is an integer in the range 1-4, and if m is an integer a number equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ can be the same or different, and

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

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

either their anhydrides, and

(B) a component in the form of a phosphorus compound, consisting of at least one compound described by the following general formula (III):

where each of R ⁵ , R ⁶ and R ⁷ independently represents C _1-4 alkyl, and X represents at least one unit selected from —CH ₂ - and —CH ₂ (Y) (where Y represents phenyl),

the mixture (1) is used at such a ratio of the concentrations of the components in the mixture, 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 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 relative expressions (i) and (ii):

1≤M _P / M _Ti ≤15 (i)

10≤M _P + M _Ti ≤100 (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, consisting of at least one compound selected from the group consisting of

(c) titanium alkoxides described by the following general formula (IV):

where each of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represents C _1-20 alkyl, p is an integer in the range 1-3, and if p is 2 or 3, then two or three groups of R ⁹ and R ¹⁰ may be the same or different, and

(d) reaction products between titanium alkoxides described by the above general formula (IV) 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, consisting of at least one phosphorus compound described by the following general formula (V):

where R ¹² represents C _1-20 alkyl or C _6-20 aryl, aq is 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 a polyester fiber structure of the invention preferably contain the corresponding titanium alkoxide (a) and titanium alkoxide (c), each with a molar ratio in the reaction according to relative to aromatic polyvalent carboxylic acid or its anhydride in the range from 2: 1 to 2: 5.

In the product of the reaction (2) of the catalyst, in the case of the fibrous structure of the polyester 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 through the ratio between moles of phosphorus atoms in the component (D) and moles of titanium atoms in component (C) (P / Ti).

The phosphorus compound described by the general formula (V) used in the reaction product (2) is preferably selected from monoalkyl phosphates in the case of the fibrous structure of the polyester of the invention.

An aromatic dibasic carboxylic acid ester in the case of a polyester fiber structure of the invention is preferably obtained by transesterification between a dialkyl ester of an aromatic dibasic carboxylic acid and an alkylene glycol ester.

The aromatic dibasic carboxylic acid in the case of the fibrous structure of the polyester 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, propylene glycol, glycol, butylene glycol, butylene neopentyl glycol, hexanemethylene glycol and dodecanmethylene glycol.

The polyester fiber complex polyester of the invention preferably has a L * value in the range of 77-85 and a b * value in the range of 2-5, based on the L * a * b * colorimetric system (JIS Z8729).

The conjugated staple fiber of the inventive polyester fabricated by the thermal bonding method may have a side-by-side structure, or the conjugated staple fiber obtained by the thermal bonding method may have a concentric or eccentric core-shell structure, where a concentric or eccentric core can form a fiber-forming thermoplastic polymer, and a concentric or eccentric shell can form a heat sealable polymer.

In the fibrous structure of the polyester of the invention, the fiber-forming thermoplastic polymer of the conjugated staple fiber obtained by the thermal bonding method is preferably a polymeric polyester. The heat sealable polymer of the conjugated staple fiber obtained by the thermal bonding method is preferably selected from among polyurethane elastomers, polyesters, inelastic homopolymers and copolymers of polyesters, polyolefin homopolymers and copolymers and polymeric polyvinyl alcohols.

The fibrous structure with a thickness in the range of 5-100 mm in the polyester fibrous structure according to the invention is preferably thermofixed at least at some of the contact points between the conjugated staple fibers obtained by the thermal joining method and the main fibers and / or the contact points between by the conjugated staple fibers obtained by the method of thermal bonding.

The polyester fiber structure of the invention can also be used for purposes that include contacting with food.

The best way to implement the invention

The polyester fiber structure of the invention is obtained using a polyester fiber containing a polymeric polyester as a main component.

The polymeric polyester is obtained by polycondensation involving an ester of an aromatic dibasic carboxylic acid in the presence of a catalyst. 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 mixture (1) of the polycondensation catalyst consists of at least one compound selected from the group consisting of

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

where each of R ¹ , R ² , R ³ and R ⁴ independently represents one link selected from among C _1-20 , and preferably C _1-6 , alkyl groups and phenyl groups, m is an integer in the range 1- 4, and preferably 2-4, and if m is an integer equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ may be the same or different, and

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

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

or their anhydrides.

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

where each of R ⁵ , R ⁶ and R ⁷ independently represents C _1-4 alkyl, and X represents at least one unit selected from -CH ₂ - and -CH ₂ (Y) (where Y represents phenyl).

The component in the form of a titanium compound (C) of the reaction product (2) of the polycondensation catalyst consists of at least one compound selected from the group consisting of

(c) titanium alkoxides described by the following general formula (IV):

where each of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represents C _1-20 , and preferably C _1-6 , alkyl, p is an integer in the range 1-3, and preferably 1-2, and if p is 2 or 3, then two or three groups R ⁹ and R ¹⁰ can be the same or different, and

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

The component in the form of a phosphorus compound (D) of the reaction product (2) of the polycondensation catalyst consists of at least one phosphorus compound described by the following general formula (V):

where R ¹² represents C _1-20 alkyl or C _6-20 aryl, aq 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) described by the general formula (I) or the reaction product (b) between titanium alkoxide (a) and aromatic carboxylic acid described by the general formula (II), or its anhydride, used as a component 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 ok component in the form of a titanium compound (A) and remains in the polymeric polyester obtained by polycondensation, during the formation of fibers from the melt in the vicinity of the die there will be no accumulation of foreign material, so that with a high efficiency of forming the fibers it will be possible to obtain an elementary thread polyester with satisfactory quality.

As described by the general formula (I), titanium alkoxides (a) used in the component according to the invention in the form of a titanium compound (A) of a polycondensation catalyst, tetraisopropoxy titanium, tetrapropoxy titanium, tetra-n-butoxy titanium, tetra ethoxy titanium, tetraphenoxy titanium, octa alkane alkane are preferred.

As described by the general formula (IV), titanium alkoxides (c) used in the component according to the invention in the form of a titanium compound (C) of a polycondensation catalyst, mention may be made of titanium tetraalkoxides, such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide and titanium tetraethoxide, and alkyl titanates such as octaalkyl trititanate and hexaalkyl dithitanate, but titanium tetraalkoxides are preferred for use, which is due to their satisfactory reactivity with respect to With respect to the components in the form of phosphorus compounds used in the invention, it is particularly preferable to use titanium tetrabutoxide.

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) 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, add dropwise to a solution of titanium alkoxide (a) or (c) and heat the mixture for at least 30 minutes at a temperature of 0-200 ° C. The solvent used in this case is preferably selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene and xylene as appropriate.

The molar ratio in the reaction between titanium alkoxide (a) or (c) and aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride does not impose any particular restrictions, but if the proportion of titanium alkoxide is excessively high, then the color tone the resulting polyester may be deteriorated, or the softening temperature may be lowered, while if the proportion of titanium alkoxide is excessively low, then there may be difficulties in the reaction condensation. Therefore, the molar ratio in the reaction between titanium alkoxide (a) or (c) and the aromatic polyvalent carboxylic acid described by the general formula (II) or its anhydride is preferably in the range from 2: 1 to 2: 5.

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

The phosphorus compound (phosphonate derivative) described by the general formula (III) used in the component as the phosphorus compound (B) of the polycondensation catalyst mixture (1) 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 that, carbomethoxyphenylmethanphosphonic acid, carbethoxyphenylmethanphosphonic acid, carbopropoxyphenylmethanphosphonic acid, carbobutoxyphenylmethanphosphonic acid and the like.

If for the polycondensation reaction involving an ester of an aromatic dibasic carboxylic acid, a component 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 the mixture (1) is used as the polycondensation catalyst according to the invention, then the mixture (1) will be 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 phosphorus compound (B) and the number of moles of aromatic dibasic carboxylic ester th acid will satisfy the following relative expressions (i) and (ii):

1≤M _P / M _Ti ≤15 (i)

10≤M _P + M _Ti ≤100 (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 of the invention is relatively narrow compared to the range used for conventional Ti-P catalysts, but maintaining this range provides an excellent result that was not obtained with commonly used Ti-P catalysts.

The value of the sum (M _P + M _Ti ) is in the range from 10 to 100, and preferably from 20 to 70. If the value (M _P + M _Ti ) is less than 10, then the fiber-forming properties of the obtained polymeric polyester, the productivity of the molding method fibers from the melt and the performance of the resulting fibers will be unsatisfactory. If the value (M _P + M _Ti ) is greater than 100, then when using the obtained 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 according to the invention, then the phosphorus compound described by the general formula (V) 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 q in formula (V) 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 (V), 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 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 efficiently 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 (VI):

where each of R ¹³ and R ¹⁴ independently represents at least one unit selected from among C _1-10 alkyl groups formed from R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the General formula (IV) describing titanium alkoxide of a component in the form of a titanium compound (C), and R ¹² in the general formula (V) describing a phosphorus compound of a component in the form of a phosphorus compound (D), and C _6-12 aryl groups formed from R ¹² in a phosphorus compound (V )

Since the reaction product between the titanium compound and the phosphorus compound (V) described by formula (VI) has a high catalytic activity, the polyester polyesters obtained using it exhibit a satisfactory color tone (low b value) and demonstrate satisfactory practical polymer performance at the level of acetaldehydes, residual metals and cyclic trimers is low enough for practical use. The reaction product described by formula (VI) is preferably present at a content 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 the polyester directly, without separation of glycol and precipitated reaction product (2) obtained by the above method. In addition, after separating the precipitate from the solution in glycol containing the precipitated reaction product (2), using methods such as centrifugal precipitation or filtration, the precipitated reaction product (2) for purification can be recrystallized using, for example , acetone, methyl alcohol and / or water and use the purified product as a catalyst. The structure of the catalyst can be confirmed using the solid-state NMR method and the method of quantitative analysis of the content of metal PMA.

The polymer polyester used in the invention is obtained by polycondensation involving an aromatic dibasic carboxylic acid ester 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 the reaction product (2) between the component in the form of a titanium compound (C) with the 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 mol%, based on the total amount of the component as an aromatic dibasic carboxylic acid. 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 mol%, based on the total number of repeating units in the polyester.

The polymeric 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. - (3-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 previously. 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 transesterification reaction between a dialkyl ester of an aromatic dibasic carboxylic acid (formed mainly from terephthalic acid) and ethylene glycol is preferably carried out in the presence of a component in the form of a titanium compound (A) containing (a) at least one compound selected from the group consisting of titanium alkoxides described by the above general formula (I), and (b) reaction products between titanium alkoxides described by the general formula (I), aromatic polyvalent carboxylic acids described by the above general formula (II), or their anhydrides. Preferably, a phosphorus compound (phosphonate derivative) described by the above general formula (III) or a reaction product between 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 recycled polyesters from recyclable PET bottles, fiber products, polyester film products and the like.

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

The polyester used in the invention, which is obtained by the polycondensation method described above, can optionally be subjected to solid phase polycondensation. Solid-state polycondensation consists of one or several stages, and it is carried out at a temperature in the range of 190-230 ° C and a pressure in the range of 1 to 200 kPa in an inert gas atmosphere such as nitrogen, argon or gaseous carbon dioxide.

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

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

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

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

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

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

The titanium dioxide used is preferably characterized by an average particle size in the range of 0.01-2 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 polymeric polyester sample for measurement by dissolving the polymeric polyester in hexafluoroisopropanol, feeding the solution by centrifugation to isolate and precipitate titanium dioxide particles 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 exceeding 1 wt.%, 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. Space-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.

In accordance with the invention, there are no particular restrictions on the method for producing fibers from a polymeric polyester, and any conventional well-known method for forming fibers from a melt of a polyester can be used. For example, the polymeric polyester can be melted and spun from it in a temperature range of 270-300 ° C, where the melt spinning speed of the fibers is preferably in the range of 400-5000 m / min. The speed of the formation of fibers in this range will lead to fibers having sufficient strength, and make it possible to conduct stable winding. Extraction can be carried out after winding unextended polyester fibers or continuously without winding.

The shape of the hole of the die used to make fiber from polyester is also not limited, and it can have a round or irregular shape (triangular or other polygonal shape, flat and the like) and allow the fibers to be either solid or hollow.

No restrictions are imposed on the shape of the polyester fibers used in the invention, and they can be long fibers or staple fibers. The polyester fibers used in the invention may also be twisted or not twisted. In addition to this, for the polyester fibers used in the invention, operations of false twisting / crimping, Taslan processing, meshing and the like can be performed.

The polyester fibrous structure of the invention is a fibrous structure comprising a polyester fiber containing the aforementioned polymeric polyester as a main component, and variants thereof are one or more fibrous structures selected from (1) non-woven materials including fiber from polyester, (2) cotton wool, including fiber from complex polyester, and (3) fibrous structures having thicknesses in the range of 5-100 mm, including the main fiber, images Goes staple fiber of polyester, and obtained by the method of thermal bonding conjugated staple fiber wherein said polyester polymer above is present in either one of the two or in both components formed by the main fiber and obtained by the method of thermal bonding staple multicomponent fibers.

Clarifications regarding the nonwoven fabric as the first embodiment of the invention will be given first. Such a non-woven fabric is first formed using polyester fibers made using at least the catalyst mentioned above in a dry process (carding method), where relatively long staple fibers are loosened and mixed using a needle-fed roller in a wet process (paging method), where relatively short staple fibers are dispersed in water and accumulated on a wire mesh, or by the pneumatic method of canvas formation (also called holstoobrazovaniya or pneumatic way of dry pulp), where the relatively short staple fibers are fed into the perforated drum and dispersed by feeding air to form a web, after which the structure is connected in a single unit, using a step of entangling / heat treatment.

Since the optimal conditions will vary depending on the method of obtaining non-woven material, they will be explained separately.

<Dry ways>

Non-woven materials obtained by the dry method are characterized in that there is the possibility of their production in a wide range of bulk from low to high.

In the case of using the dry method to obtain a nonwoven material, the bulk is preferably 15-2000 g / m ² , and more preferably 20-1200 g / m ² . At values less than 15 g / m ² , the continuous production of a uniform web becomes very difficult, while at values greater than 2000 g / m ² , productivity becomes undesirably low.

The proportion of polyester fiber used in the non-woven material is not particularly limited, but from the point of view of demonstrating the effect on the technological properties, it is preferably 50 wt.% Or more. In most cases, fibers suitable for use in non-woven fabrics obtained by the dry method (for example, natural fibers such as cotton, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as PVA fiber, polyolefin fiber, nylon fiber, aramid fiber, acrylic fiber and carbon fiber, or conjugate fibers consisting of several polymers with different melting points).

A suitable method of combining the fibers into a single whole can be used, such as entangling the fibers using a needle (needle piercing method), entangling the fibers under the influence of water supplied under high pressure (injection molding method with the formation of a mesh structure), bonding with a binder fiber (method with pneumatic purge), entanglement as a result of shrinkage or compression under the action of a heated roller.

In the case of using the dry method to obtain a nonwoven material, the fiber lengths are preferably 30-150 mm, and more preferably 5-100 mm. At values less than 30 mm, the adhesion of the web during loosening of the fibers is weakened, and there are more significant losses of fiber, while at values exceeding 150 mm, entanglement tends to take place to a greater extent, which leads to the appearance of nodules on fibers and the like.

In the case of using the dry method for producing a nonwoven material, the mass number of the polyester fiber used is preferably in the range from 0.5 to 120 dtex. It is more preferable to have a range of from 1 to 50 dtex. At values less than 0.5 dtex, the ability of the fibers to loosen is unsatisfactory, so that the speed of the production line should be reduced, and productivity will deteriorate significantly, while at values exceeding 120 dtex, it becomes difficult to obtain a uniform fabric.

When using the dry method for producing a non-woven material, polyester fibers are preferably crimped. The tortuosity used may be enhanced tortuosity, serrated tortuosity or three-dimensional tortuosity resulting from the use of anisotropy during the spinning of fibers.

<Wet Ways>

Non-woven materials obtained by wet methods are characterized by the presence of excellent texture, the ability to provide fabrics with a low bulk, equal to several grams, and high performance.

In the case of using the wet method to obtain a nonwoven material, the bulk is preferably 5-200 g / m ² , and more preferably 20-100 g / m ² . At values less than 5 g / m ² , the preparation becomes very difficult, while at values exceeding 100 g / m ² , the productivity in the production of non-woven material is undesirably low.

There is no particular limitation on the proportion of polyester fiber used in the nonwoven material, but from the point of view of demonstrating the effect on the processing properties, it is preferably 50 wt.% Or more. In most cases, fibers suitable for use in nonwovens obtained by the wet process (for example, natural fibers such as wood pulp and non-wood cellulose, semi-synthetic fibers such as rayon and acetate silk can also be used as additional mixed materials) synthetic fibers such as PVA fiber, polyolefin fiber, nylon fiber, aramid fiber, acrylic fiber and carbon fiber, or conjugated fibers consisting of n how many polymers with different melting points).

The proportion of binder in the non-woven material obtained by the wet method is preferably in the range of 5-60%, and more preferably 10-50%, based on the weight. At values less than 5%, the lack of bonding points can result in poor strength, while a fraction in excess of 60% will result in strong bonding, but it is undesirable from the point of view of technological properties such as shrinkage and grip during heat treatment.

There are no particular restrictions on the state of the binder as long as it is a commonly used state. The material in the liquid state can even be supplied by introducing it into the liquid medium for molding the nonwoven material by the wet method, but the fibrous binder is preferable, taking into account the ease of handling. An example of such a binder is a non-stretched polyester fiber.

In the case of using a wet process to obtain a nonwoven material, the fiber lengths are preferably 0.1–25 mm, and more preferably 3–20 mm. At values less than 0.1 mm, entanglement between the fibers will occur to a lesser extent, which will make it difficult to obtain a durable non-woven material, while at values exceeding 25 mm, it becomes very difficult to ensure uniform dispersion.

In the case of using the wet method to obtain a nonwoven material, the mass number of the polyester fiber used is preferably in the range from 0.05 to 10 dtex, and more preferably from 0.1 to 7 dtex. At values less than 0.05 dtex, it becomes difficult to ensure strength, while at values greater than 10 dtex, it becomes difficult to ensure uniform dispersion.

In the case of using the wet method to obtain a nonwoven material, no special restrictions are imposed on the degree of crimp of the used fiber from polyester, but in order to give bulk, the zigzag crimp achieved as a result of mechanical processing, or a spiral three-dimensional crimp, or In cases where bulkiness is not required, the fibers can be straight fibers without crimping.

In the case of using the wet method to obtain a nonwoven material, the technological method will mainly consist of (1) a paging step and (2) a heat treatment step. At the paging stage, you can use a short-mesh paper machine, a cylinder paper machine and the like, or it can be multi-layer paging with a combination of such systems or with a combination of various systems. The heat treatment step can be carried out using a drum dryer, a multi-cylinder dryer, a calender, and the like, either individually or in combinations depending on the conditions of use. Subsequent processing, such as resin processing or fiber entanglement using a high-pressure jet, can also be carried out.

<Non-woven materials obtained by the pneumatic method of canvas formation>

Non-woven materials obtained by the pneumatic method of canvas formation have a texture similar to the texture of non-woven materials obtained by the wet method, characterized by the presence of structure (bulk) with low density.

In the case of using the pneumatic method of canvas formation to obtain a nonwoven material, the bulk is preferably 10-400 g / m ² , and more preferably 20-300 g / m ² . A bulk of less than 10 g / m ² makes production very difficult, while a bulk of more than 300 g / m ² degrades the productivity of the non-woven fabric.

There is no particular limitation on the proportion of polyester fiber used in the nonwoven material, but from the point of view of demonstrating the effect on the processing properties, it is preferably 50 wt.% Or more. In most cases, it is also possible to use fibers suitable for use in non-woven materials produced by the pneumatic method of canvas formation as additional mixed materials (for example, natural fibers such as wood pulp and non-wood cellulose, semi-synthetic fibers such as rayon and acetate silk synthetic fibers, such as PVA fiber, polyolefin fiber, nylon fiber, aramid fiber, acrylic fiber and carbon fiber, or mating GOVERNMENTAL fibers consisting of several polymers with different melting points).

The proportion of binder in the non-woven material obtained by the pneumatic method of canvas formation is preferably in the range of 5-60%, and more preferably 10-55%, based on the weight. At values less than 5%, the lack of bonding points can result in poor strength, while a fraction in excess of 60% will result in strong bonding, but it is undesirable from the point of view of technological properties such as shrinkage and grip during heat treatment. An example of a preferred binder is the conjugated staple fiber obtained by the thermal bonding method, described hereinafter.

In the case of using the pneumatic canvas formation method for producing a nonwoven fabric, the lengths of the polyester fibers used are preferably 1-15 mm, and more preferably 3-7 mm. At values less than 1 mm, entanglement between the fibers will occur to a lesser extent, which will make it difficult to obtain a durable non-woven material, while at values exceeding 15 mm, it becomes very difficult to ensure uniform dispersion.

If a pneumatic canvas forming method is used to produce a nonwoven material, the mass number of the polyester fiber used is preferably in the range from 0.3 to 100 dtex, and more preferably from 1 to 20 dtex. At values less than 0.3 dtex, it becomes difficult to ensure strength, while at values greater than 100 dtex, it becomes difficult to ensure uniform dispersion.

In the case of using the pneumatic method of canvas formation to obtain a nonwoven material, no special restrictions are imposed on the degree of crimp of the used polyester fiber, but in order to give bulk, the zigzag crimp imparted as a result of mechanical processing, or a spiral three-dimensional crimp, or In cases where bulkiness is not required, the fibers can be straight fibers without crimping.

The technological method for producing a nonwoven material according to the pneumatic method of canvas formation of the invention will mainly consist of (1) a stage of canvas formation and (2) a heat treatment stage. The stage of canvas formation can be a well-known method of molding under the influence of centrifugal forces and rarefaction resulting from the rotation of two perforated drums (known as "nozzles") (pneumatic canvas formation Dan-Web). As a result of the sequential placement of several nozzles, it is possible to directly produce non-woven material, including a stack of layers with different compositions of cotton wool. The heat treatment step can be carried out by processing using hot air and vacuum, calendaring, embossing and the like, either individually or in combinations depending on the conditions of use. Subsequent processing, such as resin processing or fiber entanglement using a high-pressure jet, can also be carried out.

The thickness of the nonwoven material is preferably in the range from 0.05 to 5 mm, regardless of which method is used, wet, dry or with pneumatic canvas formation.

Explanations will be given below regarding cotton wool as a second embodiment of the invention. From the point of view of demonstrating the effect on the technological properties of the wool, it preferably consists solely of polyester fiber obtained using the catalyst mentioned above. However, if necessary, in combination with it, you can usually use other mixed materials, such as natural fibers that do not contain a polycondensation catalyst, or various synthetic fibers that do not contain an antimony catalyst, to the extent that the fibers are suitable for cotton wool . However, also in such cases, in order to properly demonstrate the effect on technological properties, the proportion of fibers used in combination with these materials preferably does not exceed 50%.

The optimal fiber length for polyester fibers used in cotton wool will vary depending on the application in which they are used, and, for example, it is preferable to have 20-60 mm for blowing into printed products or 30-120 mm for applications requiring manufacture using a conventional fiber loosening machine, such as in the case of sofa beds with a removable mattress on a metal frame and polymer wool. In the case of blowing, it is not easy to obtain the bulk of the product, and the durability of the bulk is unsatisfactory at lengths of 20 mm or less, while the ability to loosen the fibers during blowing is insufficient, and it is also difficult to obtain bulk at lengths of 60 mm or more. For purposes when the fibers are passed through a fiber loosening machine, lengths of 30 mm or less result in less tangling of the fibers and therefore more inconvenient at the stages, such as loss of cotton or cuts on the carded web, while lengths of 120 mm or more tend to cause problems, such as poor fiber loosening and poor web removal.

The mass number of the polyester fiber used to make the wool is preferably in the range from 1.0 to 40 dtex, and more preferably from 3.3 to 20 dtex. At values less than 1.0 dtex, it is difficult to obtain a product characterized by the presence of bulk, and the passage of the carding tape is also deteriorating, while at values exceeding 40 dtex, the texture of the product and the passage of the carding tape are deteriorating.

No special restrictions are imposed on the shape of the crimp of the polyester fiber used for the manufacture of cotton wool, but in order to give a larger volume, in comparison with the zigzag reinforced crimp, a spiral three-dimensional crimp is more preferable. As a method of producing wool, you can use the commonly used method.

The term “wool” in accordance with the invention means a stuffing material used for packing masses of loosened staple fibers directly into the lining fabric, as in the case of sofa beds with a removable mattress on a metal frame or printed products, or polymer wool used as the material of pillows for upholstered furniture, insulating stuffing material for clothing and the like, and it does not include non-woven materials obtained by the method of thermal bonding, produced as a result of eremeshivaniya and heat treatment obtained according to the process heat-bonding conjugate fibers, wool or rigid.

Explanations will be given below with respect to the third embodiment of the invention, namely fibrous structures having thicknesses in the range of 5-100 mm, including a base fiber formed from staple fiber from polyester and obtained by the thermal bonding method of conjugated staple fiber, where the polymer is polyester or in one of the two or in both components formed by the main fiber and obtained by the method of thermal bonding with a multicomponent staple fiber, obtained by using the above talizator.

Such fibrous structures consist of a conjugated staple fiber and a staple polyester staple fiber (main fiber) obtained by the thermal bonding method, and preferably have heat-fixing points created by heat treatment at least at some contact points between both types of fiber and / or points contact between the conjugated staple fibers obtained by the thermal bonding method themselves.

During this stage, the polymeric polyester must be present in either one of the two or both components formed by staple fiber from the polyester (the main fiber) and obtained by the method of thermal bonding conjugated staple fiber.

The conjugated staple fiber obtained by the thermal bonding method mentioned above consists of staple fibers containing a heat-sealable polymer and a fiber-forming thermoplastic polymer, wherein at least the heat-sealable polymer extends to the surface of the fiber.

As heat sealable polymers, mention may be made of polyurethane elastomers, polyester elastomers, inelastic polymers and copolymers of polyesters, polyolefin polymers and copolymers and polymeric polyvinyl alcohols. Polymeric polyesters and their copolymers and polyester elastomers obtained using the aforementioned catalyst are preferred.

As copolymerized polymeric polyesters, mention may be made of copolymer esters containing a given number of units of aliphatic dibasic carboxylic acids, such as adipic acid and sebacic acid, aromatic dibasic carboxylic acids, such as phthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and / or a carboxylic acids, such as hexahydroterephthalic acid and hexahydroisophthalic acid, and aliphatic or alicyclic units diols, such as diethylene glycol, polyethylene glycol, propylene glycol and paraxylene glycol, if necessary with the addition of hydroxy acids such as parahydroxybenzoic acid, and a preferred example is the polyester obtained by the addition of copolymerization of isophthalic acid and 1,6-hexanediol with t-acid ethylene glycol.

As examples of polyolefin polymers, mention may be made of low density polyethylene, high density polyethylene, polypropylene and the like.

Examples of fiber-forming thermoplastic polymers used in combination with a heat sealable polymer include polyesters such as polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and polyolefin polymers. Particularly preferred are the aforementioned polymeric polyesters obtained using the aforementioned catalyst.

In the combination of a heat-sealable polymer and a fiber-forming thermoplastic polymer, it is most preferable to use a polyester elastomer with a melting point in the range of 70-210 ° C (more preferably 100-180 ° C) as the heat-sealing polymer and, as a fiber-forming thermoplastic polymer, a polymeric polymer with a melting point 10 ° C higher than the melting temperature of the polyester-based elastomer.

The conjugated staple fiber obtained by the thermal bonding method is preferably such a conjugated fiber that the heat-sealable polymer (E) and the fiber-forming thermoplastic polymer (P) are characterized by the ratio of the cross-sectional area of the fiber E: P = from 20:80 to 80:20. The conjugation form of components (E) and (P) can be any well-known conjugation form, such as a concentric core-shell structure, an eccentric core-shell structure, a side-by-side structure, a conjugate fiber with an island in sea ”or a mixed fiber with an“ island in the sea ”structure, a (leno) fiber oriented in the“ orange section ”structure and the like, but the distribution should be such that part of component (E) extends to the surface of the fiber, and preferably component (E) was It would be at least 30% of the circumference of the fiber cross section. Particularly suitable are fibers with a side-by-side structure or fibers with an eccentric core-shell structure due to the fact that in this case the function of latent crimping ability can easily be imparted to develop a slight crimp during heat treatment when forming fibrous structure, so that to improve the binding ability, the entanglement between the fibers can be improved.

The mass number of a single fiber in the case of a conjugated staple fiber obtained by the thermal bonding method is preferably in the range of 0.5-200 decitex, and more preferably 2-100 decitex. These ranges are preferable to obtain the optimal number of thermal connection points formed in the fibrous structure as a result of processing in the form of the thermal connection used to obtain the fibrous structure, thereby ensuring sufficient strength and minimizing bonding during manufacture of the thermal compound obtained by the method conjugated staple fiber.

The fiber cross-sectional shapes do not have to be circular, and instead they can be polygonal, have a rib shape, a spherical shape and the like, although from the point of view of forming staple fibers and passing through the carding stage, they are preferably circular. Fibers can also have one or more hollow sections.

The conjugated staple fibers obtained by the thermal bonding method can be manufactured by the commonly used widely known method.

When the conjugate fiber obtained by the thermal bonding method is cut to form a staple fiber, the cutting lengths are preferably in the range of 5-100 mm, in particular in the range of 15-95 mm. This range makes it possible to obtain particularly favorable carding characteristics and binding properties of the fibrous structure.

The conjugated staple fiber obtained by the thermal bonding method can also be crimped to the extent that it does not cause problems during the process, in which case the number of crimps is preferably in the range of 8-20 by 25 mm with the degree of crimp in the range 6-18%.

The polyester staple fiber used as the base fiber may be composed of the well-known polyester, but preferably it consists of the aforementioned polyester polyester obtained using the catalyst described above. In terms of bulk, damping and elasticity, as well as the texture of the fibrous structure, the mass number of a single fiber in the case of staple polyester staple fiber is preferably in the range of 0.5-150 decitex, and more preferably 2-50 decitex. In terms of volume and damping ability of the fibrous structure, the number of convolutions of the staple polyester staple fiber is preferably in the range of 3-30 by 25 mm, and more preferably in the range of 5-20 by 25 mm, and the degree of crimp is preferably in the range of 6-50 %, and more preferably in the range of 12-40%. The cutting lengths are preferably in the range of 5-100 mm, in particular in the range of 15-90 mm.

The cross-sectional shapes of the staple polyester staple fiber are preferably circular, flat, triangular, hexagonal or hollow in accordance with what is suitably selected for the intended use case.

Polyester staple fiber can be obtained using a conventional, widely known method of winding or drawing a fiber formed from an individual component or a conjugated fiber obtained by pairing two or more than two components.

The proportion with stirring of both types of staple fibers of the aforementioned fibrous structure according to the third embodiment of the invention is preferably in the range obtained by the thermal bonding method of conjugated staple fiber: staple fiber from polyester = from 5:95 to 70:30, and more preferably from 10: 90 to 60:40 based on the mass. If in proportion with stirring the proportion of the conjugated staple fiber obtained by the thermal bonding method is excessively high, then the excessively large number of heat-setting points formed in the fibrous structure can result in excessive structure hardness, while if it is excessively low then a small number of heat-setting points as a result can lead to a deterioration in the elasticity and durability of the structure.

The thickness of the fibrous structure should be in the range of 5-100 mm. The density is suitably in the range of 0.01-0.10 g / cm ³ .

A method of manufacturing a fibrous structure can be any well-known method to the extent that it allows the formation of heat-fixing points, at least at some points of contact between the conjugated staple fibers and staple fibers made of complex polyester and / or contact points between obtained by the method of heat setting conjugated staple fibers.

The heat treatment temperature is preferably about 100-215 ° C., and the heat treatment time is preferably about 10-30 minutes.

Examples

Further, the present invention will be further clarified by using the following examples with the understanding that the examples do not limit the scope of the invention.

For examples 1-21 and comparative examples 1-12, using the methods described below, the ultimate viscosity, color tone, metal content, strength / elongation of the nonwoven material, fluctuation in the quality of the nonwoven material, the formation of fumes during fiber loosening, the variation in the quality of the wool, hardness were measured (elasticity) of the fibrous structure, the residual deformation of the fibrous structure upon repeated compression (durability), the presence of solid masses in the fibrous structure, the thickness of the fibrous structure, be fibrous structure and sticking to the die for each of the polymeric polyesters.

(1) Ultimate Viscosity

After heating, 0.6 g of the polyester was calculated until it was dissolved in 50 cubic meters. cm o-chlorophenol, cooling the solution and using an Ostwald capillary viscometer to measure the viscosity of the solution in accordance with the usual method at a temperature of 35 ° C.

(2) Hue (L * color value / b * color value)

Measured using a CM-7500 Color Machine from Color Machines Co. after heat treatment of the sample in the form of polymer particles in an oven at 160 ° C × 90 min and recrystallization.

(3) Metals

To determine the content of the titanium atom and the content of the phosphorus atom in the catalytic system, which is in the form of a catalyst solution, the liquid cell was filled with the catalyst solution, while for the determination in the polymer complex polyester, the sample of the polymer complex was heated until melting on an aluminum flat cup, and after this was placed in a direct compression press and molded to obtain a flat molded product. The sample was placed in a fluorescence x-ray analyzer (Model 3270 from Rigaku Corp.) for quantitative analysis of metal content.

(4) Strength / Elongation of Nonwoven Fabric

According to the method of JIS P8113, a constant speed machine was used for the measurement to measure tensile and determine impact strength.

(5) Fluctuation in the quality of the nonwoven fabric

The definition of quality variation was based on the standard deviation of n = 30 for the tensile strength of the nonwoven material. (A lower value indicates a lower amount of oscillation and, thus, greater stability of quality).

(6) Carbon formation during fiber loosening

The mass of fumes formed in one hour under normal operating conditions of a roller carding machine in the manufacture of cotton wool for sofa beds with a removable mattress on a metal frame was measured in the region of 1 m ² in the vicinity of the carding machine.

(7) Variations in the quality of cotton wool

The definition of quality variation was based on a standard deviation of n = 10 to measure the mass of waste produced in one hour. (A lower value indicates a lower amount of oscillation and, thus, greater stability of quality).

(8) Hardness of the fibrous structure (elasticity)

This characteristic was measured based on a compression hardness of 25% in accordance with JIS-K6401.

(9) Residual deformation of the fibrous structure upon repeated compression (durability)

This characteristic was measured in accordance with JIS-K6401.

(10) Solid masses in the fibrous structure

Ten experts were randomly selected to study the surface of the fibrous structure as a result of hand contact with it, and the state of the solid masses received an organoleptic rating in accordance with the following scale:

5 - extremely satisfactory (very high uniformity in the absence of tangible quantities of mass),

4 - quite satisfactory (for the most part, uniformity in the absence of masses),

3 - satisfactory (partial but insignificant presence of masses),

2 - somewhat unsatisfactory (tangible presence of masses),

1 - very unsatisfactory (the presence of large quantities of mass was determined).

(11) The thickness of the fibrous structure

Thickness (mm) was measured in accordance with JISL1096.

(12) Density of the fibrous structure

Density (g / cm ³ ) was measured in accordance with JISL1097.

(13) Diethylene glycol content (DEG)

Hydrazine hydrate was used to decompose the polymer, and gas chromatography (Model 263-70 from Hitachi Laboratories) was used to measure in accordance with a conventional method.

(14) Adhesive layer formed on a die

The polyester was turned into granules, melted at 290 ° C, and then released from a die having 12 holes, each with a hole size of 0.15 mm ⌀, to form the fiber at a speed of 600 m / min for 2 days, after which measurements were made the height of the adhesive layer obtained on the outer edge of the outlet of the mouthpiece. A greater height of the adhesive layer tends to result in more significant bending of the polyester melt stream forming the filament through the outlet and thus reduces the formability of the polyester. That is, the height of the adhesive layer obtained on the die was used as an indicator of the formability of the polyester.

Example 1

After loading 0.009 parts of tetra-n-butyl titanate into a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, a pressure of 0.07 MPa was created in a stainless steel reactor suitable for carrying out the transesterification reaction with an increase in temperature from 140 to 240 ° C. and then 0.04 parts by weight of triethylphosphonoacetate 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 complex (not containing a matting agent) polyester with a maximum viscosity of 0.60, the content level diethylene glycol 1.5 wt.% and a melting point of 254 ° C.

The resulting polyester was transformed into granules and dried in accordance with conventional methods. The dried granules were used for forming fibers, drawing, cutting, and the like in accordance with conventional methods, and a stretched polyester yarn was obtained (mass number 1.7 dtex, fiber length 5 mm, number of twists 0) and not subjected to stretching as a binder polyester thread (mass number 1.2 dtex, fiber length 5 mm, number of twists 0). The stretched polyester thread and the non-stretched polyester thread were mixed in a 60/40 ratio and, using the paging method, a web with a bulk of 50 g / m ^{2 was formed} using a conventional cylinder paper machine, and then dried using a Yankee dryer and additionally subjected to calendaring. The properties obtained by the wet method of non-woven material are shown in table 1.

Reference example

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.

Example 2

The same procedure was used as in Example 1, except that 0.016 parts of titanium trimellitate synthesized by the method described in the reference example was used as the titanium compound. The results are shown in table 1.

Examples 3-5, comparative examples 1-3

The same procedure was implemented as in Example 1, except for the addition of titanium compounds and phosphorus compounds listed in Table 1 in the indicated amounts. The results are shown in Table 1.

Example 6

The polyester granules obtained in Example 1 were used for forming fibers, drawing, cutting and the like in accordance with conventional methods, and a stretched polyester thread was obtained (mass number 1.7 dtex, fiber length 51 mm, number of crimps 12 /inch). A fabric with a main mass of 100 g / m ^{2 was formed} from the drawn polyester yarn using a conventional roller carding machine, and after that a sewing machine was used to twist the fibers and a non-woven material made by the dry method was obtained. Its properties are shown in table 1.

Example 7

The molding of fibers, drawing, cutting and the like was carried out in accordance with conventional methods using the polyester granules obtained in Example 1 as a core component, and granule shells consisting of a copolymer polyester containing acid component units obtained as a core component. as a result of mixing the units of terephthalic acid and isophthalic acid with a ratio of 60/40 (in molar percent), and the units of the diol component obtained by mixing the units of ethylene glycol and 1,6-hexanediol with a ratio of 85/15 (in molar percent) (ultimate viscosity 0.36, softening point 70 ° C) obtained using such a catalyst, and received conjugated fiber from a complex polyester with a core-shell structure "(Core / shell ratio 50/50, mass number 2.2 dtex, fiber length 5 mm). The conjugated polyester fiber with a core-shell structure was mixed with refined wood pulp in a proportion of 60/40 and used for canvas forming to obtain a web with a characteristic of 50 g / m ² using a pneumatic canvas forming machine, and then subjected to heat treatment using air purge dryers. The properties obtained by the pneumatic method of canvas formation of non-woven material are shown in table 1.

Reference Example 4

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

Then, the reaction product was transferred to the polymerization reactor, in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C, and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain a polyester. The obtained polyester was converted into fiber, and then used to obtain a non-woven material in the same manner as in example 1. The results are shown in table 1.

Example 8

The granules were dried from the same polyethylene terephthalate as in Example 1. The dried granules were used to form fibers, stretch, cut and the like in accordance with conventional methods, and a stretched polyester thread was obtained (mass number 6.6 dtex, fiber length 51 mm, the number of spiral three-dimensional twists 9.0 / 25 mm). The stretched polyester yarn was subjected to loosening using a conventional roller carding machine and a carded bed for sofa beds with a removable mattress on a metal frame was formed. The amount of fumes formed is shown in table 2.

Example 9

The same procedure was used as in Example 8, except that 0.016 parts of titanium trimellitate synthesized by the method described in the reference example were used as the titanium compound. The results are shown in table 2.

Examples 10-14, comparative examples 5-7

The same procedure was implemented as in Example 8, except for the addition of titanium compounds and phosphorus compounds listed in Table 2 in the indicated amounts. The results are shown in Table 2.

Reference Example 8

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

Then, the reaction product was transferred to the polymerization reactor, in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C, and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain a polyester. The resulting polyester was converted into fiber, and then used to obtain the cotton wool in the same manner as in example 8. The results are shown in table 2.

Example 15

Granules from the same polyethylene terephthalate as in Example 1 were dried according to the conventional method and used to produce staple fibers from polyester with a single fiber mass number of 12 dtex, 8 crimps / 25 mm and a degree of crimp of 30%. The same granules were also used as a core component, while the same catalyst was used to polymerize a mixed acid component including terephthalic acid and isophthalic acid in a ratio of 80/20 (in mole percent), and butylene glycol, and the resulting terephthalate on based on polybutylene was additionally subjected to reaction with heating with polybutylene glycol (molecular weight 2000) with a ratio of the amounts of both reagents 38 wt.%: 62 wt.% and received a block copolymer elastomeric polyether p based on esters and ethers (thermoplastic elastomer) with a limiting viscosity of 1.0 and a melting point of 155 ° C. The obtained thermoplastic elastomer was used as a component of the sheath and, with a cross-sectional area ratio of the fiber with the core / sheath structure 60/40, fiber forming, drawing, cutting, and the like were performed and a conjugated staple fiber obtained by the thermal bonding method (core / sheath ratio) 60/40, mass number of fiber 6 dtex, 11 curls / 25 mm, degree of crimp 8%).

The polyester staple fiber and the conjugated staple fiber obtained by the thermal bonding method were mixed with a mass ratio of 70:30 and passed through a rolling carding machine twice to form a mixed web. The canvas was placed in a forming frame at a set density and heat-treated at 180 ° C × 15 min using a dryer with heating with circulating hot air and a fibrous structure with a density of 0.04 g / cm ³ and a thickness of 5 cm was obtained. The properties of the resulting fibrous structure were evaluated , and the results are shown in table 3.

Example 16

The same procedure was used to obtain the fibrous structure as in Example 15, except that 0.016 parts of titanium trimellitate synthesized by the method described in the reference example were used as the titanium compound. The results are shown in table 3.

Examples 17-21, comparative examples 9-11

To obtain the fibrous structure, the same procedure was carried out as in Example 15, except for the addition of titanium compounds and phosphorus compounds listed in Table 3 in the indicated amounts. The results are shown in Table 3.

Reference Example 12

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

Then the reaction product was transferred to the polymerization reactor in the amount indicated in the table, antimony trioxide was added, the temperature was increased to 290 ° C, and in high vacuum at a pressure not exceeding 26.67 Pa, the polycondensation reaction was carried out to obtain a polyester. The obtained polyester was converted into fiber, and then used to obtain the fibrous structure in the same manner as in example 15. The results are shown in table 3.

For examples 22-36 and comparative examples 13-23, using the methods described below, the ultimate viscosity, color tone, metal content, strength / elongation of the nonwoven material, fluctuation in the quality of the nonwoven material, the formation of fumes during loosening of the fiber, the variation in the quality of the wool, hardness were measured (elasticity) of the fibrous structure, the residual deformation of the fibrous structure upon repeated compression (durability), the presence of solid masses in the fibrous structure, the thickness of the fibrous structure, st fibrous structure and sticking to the die for each of the polymeric polyesters.

(1) Ultimate Viscosity

After heating, 0.6 g of the polyester was calculated until it was dissolved in 50 cubic meters. cm o-chlorophenol, cooling the solution and using an Ostwald capillary viscometer to measure the viscosity of the solution in accordance with the usual method at a temperature of 35 ° C.

(2) Hue (L color value / b color value)

Measured using a CM-7500 Color Machine from Color Machines Co. after heat treatment of the sample in the form of polymer particles in an oven at 160 ° C × 90 min and recrystallization.

(3) Analysis of metal content

Quantitative analysis of the concentrations of titanium and phosphorus atoms in the catalyst deposited in the reaction was carried out by placing the dried sample in a scanning electron microscope (SEM, S570 from Hitachi Instruments Service) and using an X-ray microanalyzer connected to it based on the energy dispersion method (РМА, ЕМАХ-7000 from Horiba Co., Ltd.).

Quantitative analysis of the concentration of catalyst metal in the polyester was carried out by heating the particulate sample before melting on an aluminum flat cup, and then forming a flat molded product from it using a direct compression press and using a fluorescence X-ray radiometric analyzer (Model 3270 from Rigaku Corp .).

(4) Strength / Elongation of Nonwoven Fabric

According to the method of JIS P8113, a constant speed machine for tensile testing and impact strength testing was used for measurement.

(5) Fluctuation in the quality of the nonwoven fabric

The definition of quality variation was based on the standard deviation of n = 30 for the tensile strength of the nonwoven material. (A lower value indicates a lower amount of oscillation and, thus, greater stability of quality).

(6) Carbon formation during fiber loosening

The mass of fumes formed in one hour under normal operating conditions of a roller carding machine in the manufacture of cotton wool for sofa beds with a removable mattress on a metal frame was measured in the region of 1 m ² in the vicinity of the carding machine.

(7) Fluctuation in the waste of the resulting fiber

The definition of quality variation was based on a standard deviation of n = 10 to measure the mass of waste produced in one hour. (A lower value indicates a lower amount of oscillation and, thus, greater stability of quality).

(8) Hardness of the fibrous structure (elasticity)

This characteristic was measured based on a compression hardness of 25% in accordance with JIS-K6401.

(9) Residual deformation of the fibrous structure upon repeated compression (durability)

This characteristic was measured in accordance with JIS-K6401.

(10) Solid masses in the fibrous structure

Ten experts were randomly selected to study the surface of the fibrous structure as a result of hand contact with it, and the state of the solid mass received an organoleptic rating in accordance with the following scale:

5 - extremely satisfactory (very high uniformity in the absence of tangible quantities of mass),

4 - quite satisfactory (for the most part, uniformity in the absence of masses),

3 - satisfactory (partial but insignificant presence of masses),

2 - somewhat unsatisfactory (tangible presence of masses),

1 - very unsatisfactory (definitely the presence of large quantities of mass).

(11) The thickness of the fibrous structure

Thickness (mm) was measured in accordance with JISL1096.

(12) Density of the fibrous structure

Density (g / cm ³ ) was measured in accordance with JISL1097.

Example 22

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

Catalyst Preparation

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

In order to analyze the precipitate obtained in the reaction, 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 2.0. 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 m. d. 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, in a reactor already containing 225 parts of an oligomer (ethylene glycol terephthalate diester oligomer), under stirring in a nitrogen atmosphere under conditions of keeping 255 ° C and normal pressure at a constant speed, a suspension was obtained, obtained by mixing 179 parts of high-purity terephthalic acid and 95 parts of ethylene glycol, and the esterification reaction was carried out for 4 hours until 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 of the oligomer obtained as a result of the esterification reaction, the previously obtained 3.34 mass parts of the TP1-2.0 catalyst were loaded into the polycondensation reactor as a polycondensation catalyst. To undergo the polycondensation reaction, the reaction temperature in the system was increased from 255 to 280 ° C, and the pressure in the reaction was gradually reduced from atmospheric pressure to 60 Pa when water and ethylene glycol formed during the reaction were removed from the system.

The degree of completion of the polycondensation reaction was confirmed by monitoring the load on the mixing paddle in the system, and when the desired degree of polymerization was 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 quality of the obtained polyethylene terephthalate is shown in table 4.

The granules were dried and used for forming fibers, drawing, cutting, and the like in accordance with conventional methods, and a stretched polyester yarn was obtained (mass number 1.7 dtex, fiber length 5 mm, number of twists 0) and not subjected to binder an extract from a polyester thread (mass number 1.2 dtex, fiber length 5 mm, number of twists 0). The stretched polyester thread and the non-stretched polyester thread were mixed in a 60/40 ratio and, using the paging method, a web with a bulk of 50 g / m ^{2 was formed} using a conventional cylinder paper machine, and then dried using a Yankee dryer and additionally subjected to calendaring. The properties of the non-woven fabric obtained by the wet process are shown in Table 4.

Example 23

The same procedure was used as in Example 22, except that monobutyl phosphate was used instead of monolauryl phosphate. The quantity added and the conditions were also changed as follows.

After heating and dissolving 28.3 g of monobutyl phosphate in 537 g of ethylene glycol (hereinafter abbreviated as “solution P2”), 435 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P2 solution was 2.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as “TP2-2.0 catalyst”. The heating temperature was 70 ° C, and the reaction time was 1 hour.

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 in the same manner as before, resulting in 17.0% titanium, 21.2% phosphorus and a molar ratio between phosphorus atoms and titanium atoms of 1.9. The catalyst was used to produce polyester fiber in the same manner as in Example 1, after which leafing and drying were carried out using the wet method to obtain a nonwoven material. The results are shown in table 4.

Example 24

The same procedure was used as in Example 22, except that the amount of the obtained TP1 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 31.3 g of monolauryl phosphate in 594 g of ethylene glycol (hereinafter abbreviated as “P3 solution”), 375 g of TB solution were placed here and the reaction product was obtained. The ratio of the concentrations of the components in the mixture for the TB solution and the RE solution was 1.5, representing the molar ratio between the phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP3-1.5 catalyst." The catalyst was used to produce polyester fiber in the same manner as in Example 22, after which leafing and drying were carried out using the wet method to obtain a nonwoven material. The results are shown in table 4.

Example 25

The same procedure was implemented as in Example 23, except that the amount of the obtained TP2 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 33.0 g of monobutyl phosphate in 627 g of ethylene glycol (hereinafter abbreviated as “P4 solution”) 340 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P4 solution was 3.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP4-3.0 catalyst". The catalyst was used to produce polyester fiber in the same manner as in Example 22, after which leafing and drying were carried out using the wet method to obtain a nonwoven material. The results are shown in table 4.

Example 26

The polyester granules obtained in Example 22 were used for forming fibers, drawing, cutting, and the like in accordance with conventional methods, and a stretched polyester thread was obtained (mass number 1.7 dtex, fiber length 51 mm, number of crimps 12 /inch). A fabric with a main mass of 100 g / m ^{2 was formed} from a stretched polyester yarn using a conventional roller carding machine, and then a sewing machine was used to twist the fibers and a non-woven material made by the dry method was obtained. Its properties are shown in table 4.

Example 27

The molding of fibers, drawing, cutting and the like was carried out in accordance with conventional methods using the polyester granules obtained in Example 22 as a core component, and granule shells consisting of a copolymer polyester containing acid component units obtained as a core component. as a result of mixing the units of terephthalic acid and isophthalic acid with a ratio of 60/40 (in molar percent), and the units of the diol component obtained by mixing the units of ethyl glycol and 1,6-hexanediol with a ratio of 85/15 (in molar percent) (ultimate viscosity 0.36, softening point 70 ° C.) obtained using such a catalyst, and a conjugated polyester fiber with a core-shell structure was obtained "(Core / shell ratio 50/50, mass number 2.2 dtex, fiber length 5 mm). The conjugated polyester fiber with a core-shell structure was mixed with refined wood pulp in a proportion of 60/40 and used for canvas forming to obtain a web with a characteristic of 50 g / m ² using a pneumatic canvas forming machine, and then subjected to heat treatment using air purge dryers. The properties obtained by the pneumatic method of canvas formation of non-woven material are shown in table 4.

Reference Example 13

The same procedure was carried out as in Example 22, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the loading amount was 4.83 parts, and 0.121 parts were additionally charged as stabilizer a solution of trimethyl phosphate in ethylene glycol with a concentration of 25%. The results are shown in table 4.

Reference Example 14

The same procedure was used as in Example 22, except that only the TB solution obtained in Example 1 was used as the polycondensation catalyst, and the loading amount was 1.03 parts. The polycondensation reaction time was 95 minutes. The results are shown in table 4.

Reference Example 15

The same procedure was used as in Example 22, except that the polycondensation catalyst was formed by separately loading each representative into the polycondensation reaction system selected from 1.03 parts of TB solution and 2.30 parts of solution P1, without carrying out the reaction between the TB solution and the P1 solution. The results are shown in table 4.

Reference Example 16

The same procedure was used as in Example 23, except that the polycondensation catalyst was formed by separately loading each representative into the polycondensation reaction system selected from 1.03 parts of TB solution and 2.3 parts of solution P2, without carrying out the reaction between the TB solution and the P2 solution. The results are shown in table 4.

Table 4 Polymer quality Nonwoven Properties Catalyst Catalyst content Reaction molar ratio between P atoms and Ti atoms Ultimate viscosity Color Way The length of the thread tearing under its own weight (in the longitudinal direction) Elongation at break Quality fluctuation Ti (ppm) / P (ppm) L * value / b * value (km) (%) Example 22 TR 1-2.0 52/64 2.0 0.64 81 / 2.0 Wet 0.12 1,5 0.06 Example 23 TP2-2.0 48/60 1.9 0.64 81 / 2.2 Wet 0.13 1,6 0,03 Example 24 TP3-1.5 32/28 1,5 0.64 81 / 3.0 Wet 0.11 1,5 0.05 Example 25 TP4-3.0 152/260 3.0 0.64 81 / 2.4 Wet 0.14 1.7 0.05 Example 26 TP1-2.0 52/64 2.0 0.64 81 / 2.0 Dry 1.21 89.1 0.11 Example 27 TP1-2.0 52/64 2.0 0.64 81 / 2.0 Pneumatic canvas formation 0.43 22.1 0.09 Reference Example 13 Sb ₂ O ₃ 250 (Sb) - 0.64 75 / 2.5 Wet 0.11 2.4 0.3 Reference Example 14 TV solution 52 / - - 0.64 81 / 8.0 Wet 0.12 2.1 0.2 Reference Example 15 TV + P1 solution 52/56 - 0.64 81 / 7.6 Wet 0.14 2,5 0.13 Reference Example 16 TV + P2 solution 52/56 - 0.64 81 / 7.9 Wet 0.13 1.9 0.13

Example 28

Pellets from the same polyethylene terephthalate as in Example 22 were dried and used to form fibers, stretch, cut and the like in accordance with conventional methods, and a stretched polyester thread was obtained (mass number 6.6 dtex, fiber length 51 mm, the number of spiral three-dimensional twists 9.0 / 25 mm). The stretched polyester yarn was subjected to loosening using a conventional roller carding machine and a carded bed for sofa beds with a removable mattress on a metal frame was formed. The amount of fumes formed is shown in table 5.

Example 29

The same procedure was used as in Example 28, except that monobutyl phosphate was used instead of monolauryl phosphate. The quantity added and the conditions were also changed as follows.

After heating and dissolving 28.3 g of monobutyl phosphate in 537 g of ethylene glycol (hereinafter abbreviated as “solution P2”), 435 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P2 solution was 2.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as “TP2-2.0 catalyst”. The heating temperature was 70 ° C, and the reaction time was 1 hour.

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 in the same manner as before, resulting in 17.0% titanium, 21.2% phosphorus and a molar ratio between phosphorus atoms and titanium atoms of 1.9. The catalyst was used to make polyester fibers in the same manner as in Example 7, after which the fibers were loosened using a conventional roller carding machine and a carded bed for sofa beds with a removable mattress on a metal frame was formed. The results are shown in table 5.

Example 30

The same procedure was implemented as in Example 28, except that the amount of the obtained TP1 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 31.3 g of monolauryl phosphate in 594 g of ethylene glycol (hereinafter abbreviated as “P3 solution”), 375 g of TB solution were placed here and the reaction product was obtained. The ratio of the concentrations of the components in the mixture for the TB solution and the P3 solution was 1.5, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP3-1.5 catalyst." The catalyst was used to produce polyester fibers in the same manner as in Example 1, after which the fibers were loosened using a conventional roller carding machine and a carded bed for sofa beds with a removable mattress on a metal frame was formed. The results are shown in table 5.

Example 31

The same procedure was implemented as in Example 29, except that the amount of the obtained TP2 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 33.0 g of monobutyl phosphate in 627 g of ethylene glycol (hereinafter abbreviated as “P4 solution”) 340 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P4 solution was 3.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP4-3.0 catalyst". The catalyst was used to produce polyester fibers in the same manner as in Example 1, after which the fibers were loosened using a conventional roller carding machine and a carded bed for sofa beds with a removable mattress on a metal frame was formed. The results are shown in table 5.

Reference Example 17

The same procedure was carried out as in Example 28, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the loading amount was 4.83 parts, and 0.121 parts were additionally charged as stabilizer a solution of trimethyl phosphate in ethylene glycol with a concentration of 25%. The results are shown in table 5.

Reference Example 18

The same procedure was carried out as in Example 28, except that only the TB solution obtained in Example 7 was used as the polycondensation catalyst, and the charge amount was 1.03 parts. The polycondensation reaction time was 95 minutes. The results are shown in table 5.

Reference Example 19

The same procedure was used as in Example 28, except that the polycondensation catalyst was formed by separately loading each representative into the polycondensation reaction system selected from 1.03 parts of TB solution and 2.30 parts of solution P1, without carrying out the reaction between the TB solution and the P1 solution. The results are shown in table 5.

Reference Example 20

The same procedure was used as in Example 29, except that the polycondensation catalyst was formed by separately loading each representative into the polycondensation reaction system selected from 1.03 parts of TB solution and 2.3 parts of solution P2, without carrying out the reaction between the TB solution and the P2 solution. The results are shown in table 5.

Table 5 Polymer quality Technological properties of cotton wool Catalyst Catalyst content Reaction molar ratio between P atoms and Ti atoms Ultimate viscosity Color Average fiber waste Quality fluctuation Ti (ppm) / P (ppm) L * value / b * value (g / hour) Example 28 TP1-2.0 52/64 2.0 0.64 81 / 2.0 eleven 0.06 Example 29 TP2-2.0 48/60 1.9 0.64 81 / 2.2 6 0,03 Example 30 TP3-1.5 32/28 1,5 0.64 81 / 3.0 9 0.05 Example 31 TP4-3.0 152/260 3.0 0.64 81 / 2.4 10 0.05 Reference Example 17 Sb ₂ O ₃ 250 (Sb) - 0.64 75 / 2.5 28 0.3 Reference Example 18 TV solution 52 / - - 0.64 81 / 8.0 25 0.2 Reference Example 19 TV + P1 solution 52/56 - 0.64 81 / 7.6 eighteen 0.13 Reference Example 20 TV + P2 solution 52/56 - 0.64 81 / 7.9 19 0.13

Example 32

Pellets from the same polyethylene terephthalate as in Example 22 were dried by the usual method and used to produce staple fibers from polyester with a single fiber mass number of 12 dtex, 8 crimps / 25 mm and a degree of crimp of 30%. The same granules were also used as a core component, while the same catalyst was used to polymerize a mixed acid component including terephthalic acid and isophthalic acid in a ratio of 80/20 (in mole percent), and butylene glycol, and the resulting terephthalate on based on polybutylene was additionally subjected to reaction with heating with polybutylene glycol (molecular weight 2000) with a ratio of the amounts of both reagents 38 wt.%: 62 wt.% and received block copolymer elastomeric polyether p based on ethers and esters (thermoplastic elastomer) with an ultimate viscosity of 1.0 and a melting point of 155 ° C, which was used as a component of the shell. When the ratio of the areas in the cross section of the fiber with the structure of the "core / cladding" 60/40 was carried out forming the fiber, drawing, cutting and the like, and received conjugated staple fiber from polyesters (ratio of the core / cladding 60/40, fiber mass number 6 dtex, 11 curls / 25 mm, degree of crimp 8%).

The polyester staple fiber and the conjugated staple polyester staple fiber obtained by the thermal bonding method were mixed with a mass ratio of 70:30 and passed through a roller carding machine twice to form a mixed web. The canvas was placed in the forming frame at a set density and heat treated at 180 ° C × 15 min using a dryer with heating with circulating hot air, a fibrous structure with a density of 0.04 g / cm ³ and a thickness of 5 cm was obtained. The properties of the resulting fibrous structure were evaluated , and the results are shown in table 6.

Example 33

The same procedure was used as in Example 32, except that monobutyl phosphate was used instead of monolauryl phosphate. The quantity added and the conditions were also changed as follows.

After heating and dissolving 28.3 g of monobutyl phosphate in 537 g of ethylene glycol (hereinafter abbreviated as “solution P2”), 435 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P2 solution was 2.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as “TP2-2.0 catalyst”. The heating temperature was 70 ° C, and the reaction time was 1 hour.

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 in the same manner as before, resulting in 17.0% titanium, 21.2% phosphorus and a molar ratio between phosphorus atoms and titanium atoms of 1.9. The catalyst was used to produce polyester fiber in the same manner as in Example 11, after which canvas formation, heat treatment, and the like were performed to obtain the fibrous structure. The results are shown in table 6.

Example 34

The same procedure was implemented as in Example 32, except that the amount of the obtained TP1 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 31.3 g of monolauryl phosphate in 594 g of ethylene glycol (hereinafter abbreviated as “P3 solution”), 375 g of TB solution were placed here and the reaction product was obtained. The ratio of the concentrations of the components in the mixture for the TB solution and the P3 solution was 1.5, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP3-1.5 catalyst." The catalyst was used to produce polyester fiber in the same manner as in Example 1, after which canvas formation, heat treatment, and the like were performed to obtain a fibrous structure. The results are shown in table 6.

Example 35

The same procedure was implemented as in Example 33, except that the amount of the obtained TP2 solution and the amount of the added TB solution were changed. The amounts obtained and added were as follows.

After heating and dissolving 33.0 g of monobutyl phosphate in 627 g of ethylene glycol (hereinafter abbreviated as “P4 solution”) 340 g of TB solution were placed here and the reaction product was obtained. The concentration ratio of the components in the mixture for the TB solution and the P4 solution was 3.0, representing a molar ratio between phosphorus atoms and titanium atoms. This solution hereinafter in this document will be abbreviated as "TP4-3.0 catalyst". The catalyst was used to produce polyester fiber in the same manner as in Example 11, after which canvas formation, heat treatment, and the like were performed to obtain the fibrous structure. The results are shown in table 6.

Example 36

In accordance with conventional methods, fiber forming, drawing, cutting and the like were carried out using granules obtained by the additive copolymerization of isophthalic acid and 1,6-hexanediol using the same catalyst as that used for the polyester granules obtained in Example 32, and a conjugated polyester fiber with a core-shell structure was obtained (core / shell ratio 50/50, mass number 4.4 dtex, fiber length 51 mm). In all other respects, the methodology of Example 11 was followed and staple fiber made of polyester was obtained, after which canvas formation, heat treatment, and the like were performed to obtain a fibrous structure. However, the heat treatment temperature was 150 ° C. The results are shown in table 6.

Reference Example 21

The same procedure was carried out as in Example 32, except that the polycondensation catalyst was replaced with a solution of antimony trioxide in ethylene glycol at a concentration of 1.3%, the loading amount was 4.83 parts, and 0.121 parts were additionally charged as stabilizer a solution of trimethyl phosphate in ethylene glycol with a concentration of 25%. The results are shown in table 6.

Reference Example 22

The same procedure was carried out as in Example 32, except that only the TB solution obtained in Example 1 was used as the polycondensation catalyst, and the loading amount was 1.03 parts. The polycondensation reaction time was 95 minutes. The results are shown in table 6.

Reference Example 23

The same procedure was used as in Example 32, except that the polycondensation catalyst was formed by separately loading each representative into the polycondensation reaction system selected from 1.03 parts of TB solution and 2.30 parts of solution P1, without carrying out the reaction between the TB solution and the P1 solution. The results are shown in table 6.

Table 6 Polymer quality Fiber quality Catalyst Catalyst content Reaction molar ratio between P atoms and Ti atoms Ultimate viscosity Color Hardness Residual deformation during repeated compression Solid masses Ti (ppm) / P (ppm) L * value / b * value n % Level Example 32 TR 1-2.0 52/64 2.0 0.64 81 / 2.0 361 7.1 5 Example 33 TP2-2.0 48/60 1.9 0.64 81 / 2.2 363 8.4 5 Example 34 TP3-1.5 32/28 1,5 0.64 81 / 3.0 360 6.9 5 Example 35 TP4-3.0 152/260 3.0 0.64 81 / 2.4 374 9.3 5 Example 36 TR 1-2.0 52/64 2.0 0.64 81 / 2.0 420 12.6 5 Reference Example 21 Sb ₂ O ₃ 250 (Sb) - 0.64 75 / 2.5 397 12,4 3 Reference Example 22 TV solution 52 / - - 0.64 81 / 8.0 393 12 2 Reference Example 23 TV + P1 solution 52/56 - 0.64 81 / 7.6 309 11.1 3

Industrial Applicability

The polyester fibrous structure of the present invention is characterized by a satisfactory color tone (b * color value) and excellent quality, and therefore, when the polyester fibrous structure is a nonwoven material, it is particularly highly suitable for purposes that include contacting food products such as food packaging materials, food filters such as black tea bags, green tea bags and fil Coffee mats, sheets for removing roughness, sheets for filtering oil, sheets for wiping in the kitchen, supporting layers of membranes for reverse osmosis, sanitary and hygienic materials and materials for filtering drinks. It can also be used for such purposes as various types of filters, wallpaper, paper for window bindings, business cards, documents, household / industrial cleaning materials, base paper for printing, bases for electrical materials, carpets, technical plates, soundproof / insulating materials, agricultural / horticultural sheets, and the like.

Then, when the fibrous structure of the polyester is cotton, it can be used as various types of cotton, including general-purpose packing material for bedding items, such as bedspreads, sheets, mattress covers, pillows and sofas pillows, or for products with stuffing and the like, printed stuff for domestic use for the backs of sofas and chairs and clothes, or industrial polymer wool designed to provide thermal insulation lyatsii, sound absorption or sound-proofing.

Then, when the fibrous structure of the polyester is a fibrous structure, including the main fiber formed from staple fiber from complex polyester, and obtained by the method of thermal bonding conjugated staple fiber, it can be used for such purposes as bedding, furniture, materials for automotive industry (shock-absorbing materials, materials for covering the ceiling, protective materials, etc.), clothing, filtering materials, building / technical materials purposes (soundproof or insulating materials), agricultural materials, sanitary and hygienic materials (lotions, diapers, wipes, etc.) and the like.

Claims (13)

1. The fibrous structure of the polyester, including fiber from a complex polyester containing as the main component a polymer complex polyester, which is at least one type of fibrous structure selected from the group consisting of non-woven materials containing the fiber from the complex polyester, cotton wool containing said polyester fiber, and fibrous structures having thicknesses in the range of 5-100 mm, including a base fiber formed from staple fiber of complex o polyester, a thermocouple conjugated staple fiber, wherein said polymeric polyester is present in either one of two or both of the components formed by the aforementioned main fiber and thermocomposed by a multicomponent staple fiber, said polymeric polyester is obtained by polycondensation involving a complex aromatic dibasic carboxylic acid ester in the presence of a catalyst, said catalyst contains at least one ingre ient selected from the following mixtures (1) and reaction (2) of a product mixture (1) is a mixture of the following components (A) and (B): (A) a component in the form of a titanium compound, consisting of 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 unit selected from among C _1-20 alkyl groups and phenyl groups, m is an integer in the range 1-4, and if m is an integer a number equal to 2, 3 or 4, then two, three or four groups of R ² and R ³ can be the same or different, (b) reaction products between titanium alkoxides having the general formula (I) and aromatic polyvalent carboxylic acids having the general formula (II)

where n is an integer in the range of 2-4, or their anhydrides, and the molar ratio of titanium alkoxides to aromatic polyvalent carboxylic acids or their anhydrides is in the range from 2: 1 to 2: 5; (B) a component in the form of a phosphorus compound, consisting of at least one compound having the general formula (III)

where each of R ⁵ , R ⁶ and R ⁷ independently represents C _1-4 alkyl, and X represents at least one unit selected from —CH ₂ - and —CH ₂ (Y), where Y represents phenyl, the mixture (1) for the polycondensation catalyst is used in an amount satisfying the following relative expressions (i) and (ii): 1 <M _p / M _Ti <15 (i) 10 <M _p + M _Ti <100 (ii) where M _Ti represents the ratio (%) between the value in millimoles of the titanium element in said component in the form of a titanium compound (A) to the number of moles of said aromatic dibasic carboxylic acid ester and M _p represents the ratio (%) between the value in millimoles of the phosphorus element in a component in the form of a phosphorus compound (B) and the number of moles of said aromatic dibasic carboxylic acid ester, 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, consisting of at least one compound selected from the group consisting of (c) titanium alkoxides having the general formula (IV)

where each of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ independently represents C _1-20 alkyl, p is an integer in the range 1-3, and if p is 2 or 3, then two or three R ⁹ groups and R ¹⁰ may be the same or different, and (d) reaction products between titanium alkoxides having the general formula (IV) and aromatic polyvalent carboxylic acids having the general formula (II) or their anhydrides, wherein the molar ratio of titanium alkoxides to aromatic polyvalent carboxylic acids or their anhydrides is from 2: 1 to 2: 5, (D) a component in the form of a phosphorus compound, consisting of at least one phosphorus compound having the general formula (V)

where R ¹² represents C _1-20 alkyl or C _6-20 aryl, aq represents an integer equal to 1 or 2, and the molar ratio in the reaction between component (D) and component (C) is in the range from 1: 1 up to 3: 1 when calculated through the ratio between moles of phosphorus atoms in component (D) and moles of titanium atoms in component (C) (P / Ti). 2. The polyester fiber structure according to claim 1, wherein the phosphorus compound having the general formula (V) of said reaction product (2) is selected from among monoalkyl phosphates. 3. The polyester fiber structure according to claim 1, wherein the aromatic dibasic carboxylic acid ester is obtained by transesterification between an aromatic dibasic carboxylic acid dialkyl ester and an alkylene glycol ester. 4. The polyester fiber structure 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 or their derivatives forming an ester, and said alkylene glycol is preferably selected from the group consisting of ethylene glycol, butylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanemethylene glycol and dodecanomethylene glycol. 5. The fiber structure of the polyester according to claim 1, in which the polymeric polyester has a L * value in the range of 77-85 and a b * value in the range of 2-5, based on the L * a * b * colorimetric system (JIS Z8729 ) 6. The fibrous structure of the polyester according to claim 1, in which the conjugated staple fiber obtained by the thermal bonding method comprises a heat-sealable polymer and a fiber-forming thermoplastic polymer, wherein the heat-sealable polymer extends to the surface of the fiber. 7. The fibrous structure of the polyester according to claim 1, in which the conjugated staple fiber obtained by the thermal bonding method has a side-by-side structure. 8. The fiber structure of the polyester according to claim 1, where the aforementioned conjugated staple fiber obtained by the thermal bonding method has a concentric or eccentric core-shell structure, where a concentric or eccentric core forms said thermoforming fiber-forming polymer, and the concentric or eccentric sheath forms a thermoset polymer. 9. The fiber structure of the polyester according to claim 1, in which the fiber-forming thermoplastic polymer is the aforementioned polymer complex polyester. 10. The polyester fiber structure according to claim 1, wherein the heat sealable polymer is selected from polyurethane elastomers, polyester elastomers, inelastic homopolymers and copolymers of polyesters, polyolefin homopolymers and copolymers and polymeric polyvinyl alcohols. 11. The fibrous structure of the polyester according to claim 1, in which the main fiber contains the aforementioned polymeric polyester. 12. The fiber structure of the polyester according to claim 1, in which the fiber structure with a thickness in the range of 5-100 mm is subjected to heat setting, at least at some of the points of contact between the conjugated staple fibers and the main fibers and / or points of contact between the conjugated staple fibers obtained by the method of thermal bonding in said fiber structure. 13. The fibrous structure of the polyester according to claim 1, which is used for purposes that include the introduction into contact with food.