MXPA98001203A

MXPA98001203A - Compositions of ether dispersible copolyester in a

Info

Publication number: MXPA98001203A
Application number: MXPA/A/1998/001203A
Authority: MX
Inventors: Ellery George Scott; William Lefler Edgar Iv; Marshall Spain James Jr
Original assignee: Eastman Chemical Company
Priority date: 1995-08-15
Filing date: 1998-02-12
Publication date: 1998-04-01

Abstract

The present invention relates to linear, water-dispersible sulfopolyesters that incorporate polyalkylene glycol units of higher order. Sulfopolyesters provide improved abrasion and blocking resistance in fiberglass adhesion applications

Description

COMPOSITIONS OF COPOLYSTER ETHER DISPERSIBLE IN WATER DESCRIPTION PE THE INVENTION This invention relates to sulfopoliesters dispersible in water, linear which incorporate units of polyalkylene glycol. Water-dispersible sulfopoliesters incorporating polyalkylene glycol units are known. U.S. Patent Nos. 3,374,874 and No. 3,779,993 describe linear water dispersible sulfopoliesters containing polyethylene glycol (PEG). The Patents define polyethylene glycol as a compound having the formula: H - (OCH 2 CH 2) -OH where x is an integer from 2 to 20, which corresponds to a molecular weight range of polyethylene glycol from 106 to 898 g / mol. The glycol component of U.S. Patent Nos. 3,374,874 and 3,779,993 contains at least 15 mole percent PEG based on 100% mole of total glycol. U.S. Patent No. 4,233,196 describes linear water dispersible sulfopoliesters containing polyethylene glycol. The polyethylene glycol component is present in a molecular weight range of 106 to 22.018 g / mol. The glycol component of U.S. Patent No. 4,233,196 contains at least 15 mole percent PEG based on 100% mole of total glycol. Copolyether ether compositions containing polyalkylene glycols of higher order have been described in the area of thermoplastic elastomers. U.S. Patent No. 4,665,153 discloses ether copolyester compositions containing 5 to 12 mol% of higher polyalkylene glycols, such as polypropylene glycol and polytetramethylene glycol, and 2.5 to 10 mol% of a difunctional sulfomonomer. However, the ether copolyester compositions described in U.S. Patent No. 4,665,153 are not water dispersible. Therefore, what is necessary is a linear dispersible sulfopolyester in water which uses polyalkylene glycols of higher order. The present invention has solved the problem of incorporating polyalkylene glycols of higher order into linear water-dispersible sulfopoliesters. The higher order polyalkylene glycols in a linear, water dispersible sulfopolyester composition which is used as a textile fiber glue results in an improved antiblocking tendency and abrasion resistance. The linear water-dispersible sulfopolyester having a Tg of -20 ° C to 100 ° C and an inherent viscosity of 0.1 to 1.1 dl / g, the sulfopolyester comprising the reaction product of: (A) 60 to 95% by weight mole, based on the moles of the acid in the sulfopolyester, of at least one difuncíonal dicarboxylic acid which is not a sulfomonomer, the dicarboxylic acid which is selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms , saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms and cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms; (B) 5 to 40% by mol, based on moles of acid in the sulfopolyester, of at least one difunctional sulfomonomer containing at least one sulfonated metal group attached to an aromatic ring in which the functional groups are ester or Carboxyl; (C) 0.1 to 50 mol%, based on the moles of the glycol in the sulfopolyester, of at least one polyalkylene glycol of higher order having the structure: H - [OCH2 (CH) -} - -OH Wherein R is selected from the group consisting of hydrogen and an alkyl group having 1 to 12 carbon atoms, n is an integer from 2 to 200, m is an integer from 1 to 10 when R is an alkyl group or is an integer from 2 to 10 when R is hydrogen, with the proviso that the mol% of the higher order polyalkylene glycol is inversely proportional to the value of n; and (D) 0.1 to 99.9 mol%, based on the moles of the glycol in the sulfopolyester, of at least one polyethylene glycol having the structure: H- (OCH 2 CH 2) n, -OH where n is a whole number of 2 to 500, with the condition of% mol of polyethylene glycol is inversely proportional to the value of n "; the sulfupolyester having substantially equal molar proportions of acid equivalents (100 mole percent) and glycol equivalents (100 mole percent). The sulfopoliesters of the present invention are linear, water-dispersible sulfopoliesters. The term "water dispersible" is often used interchangeably with other descriptions, such as "water-soluble", "water-soluble", or "water-dissipable". In the context of this invention, all these terms refer to the activity of water or water mixture and a water-miscible organic cosolvent over the sulfopoliesters described herein. This terminology is proposed to include conditions where the sulfopolyester is dissolved to form a true solution or dispersed within the aqueous medium to obtain a stable product. Frequently, due to the statistical nature of the sulfopolyester compositions, it is possible to have soluble and dispersible fractions when the sulfopolyester acts only by an aqueous medium. The linear, water-dispersible sulfopoliesters are prepared using a dicarboxylic acid, component (A), which is not a sulfomonomer; a difunctional sulfomonomer, component (B); a polyalkylene glycol of higher order, component (C); and a polyethylene glycol, component (D); and optionally a glycol, component (E), which does not include polyethylene glycol, or a polyalkylene glycol of higher order. The linear, water-dispersible sulfopoliesters contain substantially equimolar proportions of equivalents of the acid (100 mole percent) and the glycol (100 mole percent), such that the total equivalents of acid and glycol is equal to 200 cent in mol. Water-dispersible sulfopoliesters have an inherent viscosity of 0.1 to 1.1 dl / g, preferably 0.2 to 0.7 dl / g, and more preferably 0.3 to 0.5 dl / g as measured in 60/40 parts by weight of phenol / tetrachloroethane solution at 25 ° C and a concentration of 0.25 grams of the polymer in 100 ml of the solvent. Component (A) is a dicarboxylic acid which is not a sulfomonomer. The dicarboxylic acids useful as component (A) are aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, saturated aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and preferably cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms . Specific examples of carboxylic acids to be used as component (A) include: succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1,3-cyclohexanedicarboxylic, 1,4-cyclohexanedicarboxylic, diglycolic, 2,5- norbornandicarboxylic, phthalic, terephthalic, 1,4-naphthalenedicarboxylic, 2,5-naphthalenedicarboxylic, diphenic, 4,4'-oxydibenzoic, 4,4'-sulphonyldibenzoic, and isophthalic. Mixtures of two or more dicarboxylic acids can also be used. Preferred dicarboxylic acids are isophthalic and terephthalic acid. It is understood that the use of the corresponding acid anhydrides, esters and acid chlorides of these dicarboxylic acids are included in the term "dicarboxylic acid". Preferred diesters are dimethyl terephthalate, dimethyl isophthalate, and dimethyl-1,4-cyclohexanedicarboxylate. Although the methyl ester is most preferred, it is also acceptable to use higher alkyl esters, such as ethyl, propyl, isopropyl, butyl, and successively. In addition, aromatic esters, particularly phenyl, can be used. The dicarboxylic acid, component (A), is present in an amount of 60 to 95% mol, based on the total moles of the acid in the sulfopolyester. Preferably, the amount of the dicarboxylic acid, component (A) is 80 to 95% mol, based on the total moles of the acid in the sulfopolyester. Component (B) is a difunctional sulfomonomer which is selected from the dicarboxylic acid or ester thereof which contains a metal sulfonate group (-S03M) or a hydroxy acid containing a metal sulfonate group. The sulfonate group has a cation which can be a metal or a non-metallic cation. Examples of suitable metal cations are Li +, Na +, and K +. An example of a suitable non-metallic cation is a nitrogenous base. The nitrogen base may be an aliphatic, cycloaliphatic, or aromatic compound having an ionization constant in water at 25 ° C of 10"3 to 10 * 10, preferably 10" 5 to 10"S. Examples of nitrogen-containing bases Suitable are ammonia, pyridine, morpholine, and piperidine The choice of cation may influence the dispersibility in water of the sulfopolyester Depending on the end-use application of the sulfopolyester, either more or less easily dispersible product may be desirable. polyester using, for example, a sodium sulfonate salt and then by ion exchange methods replacing the sodium with a different ion, such as zinc, when the sulfopolyester is in the dispersed form This type of ion exchange process is generally superior to prepare the sulfopolyester with divalent and trivalent salts since the sodium salts are usually more soluble in the molten phase of the sulfo reagent Also, the ion exchange process is usually necessary to obtain the nitrogen counter-ions, since the amine salts tend to be unstable under typical melt processing conditions. The difunctional sulfomonomer contains a sulfonate salt group which is attached to an aromatic acid core, such as benzene, naphthalene, diphenyl, oxidephenyl, sulfonyldiphenyl, or methylenediphenyl. The preferred results are obtained through the use of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and their esters. Particularly superior results are achieved when the difunctional sulfomonomer is 5-sodiosulfoisophthalic acid or esters thereof. The difunctional sulfomonomer is present in an amount of 5 to 40 percent mol, based on the total moles of the acid and glycol in the sulfopolyester. Preferably, the difunctional sulfomonomer is present in an amount of 8 to 30 mole percent, more preferably 9 to 25 mole percent, based on the moles of the acid or glycol in the sulfopolyester. An alternative range is 5 to 25% mol. Optionally, the sulfopolyester of the present invention are prepared using up to 50 mole percent, based on the total moles of the acid and glycol in the sulfopolyester, of a hydroxycarboxylic acid. Useful hydroxycarboxylic acids are aromatic, cycloaliphatic, and aliphatic hydroxycarboxylic acids. The hydroxycarboxylic acids contain 2 to 20 carbon atoms, a group -CH 2 OH and a group COOH or COOR 1 wherein the group R 1 is an alkyl, alicyclic or aryl group having 1 to 6 carbon atoms. The component (O is a higher order polyalkylene glycol) As used herein, the term "higher order polyalkylene glycol" refers to an alkylene glycol having the structure: H- [0 H2 (^ H) - ^ - OH Where R is selected from hydrogen or an alkyl group having 1 to 12 carbon atoms, n is an integer from 2 to 200, m is an integer from 1 to 10 when R is an alkyl group or is an integer of 2 to 10 when R is hydrogen. The higher order polyalkylene glycol can be in the range of a low molecular weight compound containing a single ether attached to a polymeric segment that can be used to place nonionic blocks within the polyester backbone. As used herein, the term "lower molecular weight higher polyalkylene glycol" refers to a higher order polyalkylene glycol having an average molecular weight number of less than 500 g / mol. Examples of higher molecular weight polyalkylene glycols are dipropylene, tripropylene, tetrabutylene, and tripentylene glycols and successively. As used herein, the term "higher molecular weight higher polyalkylene glycol" refers to a higher order polyalkylene glycol having an average molecular weight number of 500 to 20,000 g / mol. The average molecular weight of the higher order polyalkylene glycol will preferably be in the range of 500 to 5000, more preferably 650 to 2000 grams / mole. Higher order higher molecular weight polyalkylene glycols include: polypropylene glycol, polybutylene glycol, and polytetramethylene glycol ether. The higher order polyalkylene glycol is present in an amount of 0.1 to 50 mole percent, based on the total moles of the glycol in the sulfopolyester. Preferably, the higher order polyalkylene glycol is present in an amount of 0.5 to 20 weight percent, based on the moles of the glycol in the sulfopolyester. The mol% of the polyalkylene glycol of higher order is inversely proportional to the value of n. The polyalkylene glycols of higher order may possess secondary hydroxyl groups which are not desirable as primary hydroxyls for polyester forming reactions due to the decreased reactivity. It is not harmful for the practice of this invention to use end capping processes that convert secondary hydroxyls to end groups of primary hydroxyls. It is illustrative of this technique where ethylene oxide is used to cap polypropylene glycols of higher molecular weight at the end to produce poly (ethylene-b-propylene-b-ethylene) glycols. The molecular weight and the mole% of the polyalkylene glycol of higher order are inversely proportional to each other. As soon as the molecular weight increases, the mole% of the higher order polyalkylene glycol will decrease. For example, a higher order polyalkylene glycol having a molecular weight of 500 may constitute up to 30% mol of total glycol, while the higher order polyalkylene glycol having a molecular weight of 10,000 could typically be incorporated at a level of one mole percent less of the total glycol in the sulfopolyester. Higher order molecular weight polyalkylene glycols, which have molecular weights of less than 500 g / mol can constitute up to 50 mol% of the total glycol in the sulfopolyester. The component (D) is a polyethylene glycol which has the formula: H- (OCH 2 CH 2) n, -OH where n 'is 2 to 500. The polyethylene glycol can be in the range of a low molecular weight polyethylene glycol containing a single ether bond to a polymeric segment that can be used to place hydrophilic, but nonionic blocks within the main structure. Regardless of molecular weight, the incorporation of one or more polyethylene glycols provides a secondary means to form the hydrophilicity of a sulfopolyester. As used herein, the term "lower molecular weight polyethylene glycol" refers to a polyethylene glycol having an average molecular weight number of less than 300 g / mol. Examples of lower molecular weight polyethylene glycols include: diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol. As used herein, the term "polyethylene glycol" of higher molecular weight "refers to a polyethylene glycol having an average molecular weight number of from 300 to about 20,000 g / mol.The higher molecular weight polyethylene glycol can be a material polymeric such as CARBOWAX which is commercially available from Union Carbide A preferred polyethylene glycol has a molecular weight of 600 to 10,000 g / mol Polyethylene glycol is present in an amount of 0.1 to 99.9 mole percent, preferably 10 to 50 mole percent in mole, based on the total moles of the glycol in the sulfopolyester.

The molecular weight of the polyethylene glycol and the% mol of the polyethylene glycol are inversely proportional to each other. As soon as the molecular weight increases, the mol% of the polyethylene glycol will decrease. For example, a polyethylene glycol having a molecular weight of 1000 can constitute up to 15 mol% of the total glycol, while a polyethylene glycol having. a molecular weight of 10,000 could typically be incorporated at a level of less than one percent in mol of total glycol. It is important to recognize that certain glycols can be formed in situ, due to the lateral reactions that can be controlled by varying the process conditions. For example, varying the proportions of diethylene, triethylene and tetraethylene glycol from ethylene glycol can be formed due to acid-catalyzed dehydration, which occurs easily when a buffer is not added to raise the pH (ie, less acid) to the reaction mixture. Additional compositional flexibility is possible if the feed buffer containing various proportions of ethylene and diethylene glycols, or ethylene, diethylene, triethylene glycols, and other combinations readily apparent to those skilled in the art is omitted. Component (E) is a glycol which does not include polyethylene glycol or polyalkylene glycol of higher order. Component (E) is not necessary to prepare the sulfopolyester of the present invention. However, when the sulfopolyester is used to prepare an adhesion or glue composition, this optional glycol is necessary. Component (E) includes cycloaliphatic glycols preferably having 6 to 20 carbon atoms and preferably aliphatic glycols having 3 to 20 carbon atoms. Specific examples of such glycols are ethylene glycol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexan-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl- 2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butane-diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2, 2, 4-trimethyl-1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and -xililendiol. Mixtures of glycols can also be used. If component (E) is used to prepare the sulfopolyester, component (E) is used in an amount of 0.1 to 99.8 mole percent, based on the total moles of the glycol in the sulfopolyester. Preferably, when the sulfopolyester is used to prepare an adhesion or adhesive composition, the component (E) is used in an amount of 10 to 75 mole percent, based on the total moles of the glycol in the sulfopolyester. Preferably, the component (E) is ethylene glycol or 1,4-cyclohexanedimethanol. The sulfopolyester of the present invention are preferably prepared using a buffer. The shock absorbers and their uses are well known in the art and do not require prolonged discussions. Preferred buffers include sodium acetate, potassium acetate, lithium acetate, sodium phosphate monobasic, potassium phosphate dibasic and sodium carbonate. The buffer is present in an amount of up to 0.2 moles per mole of the difunctional sulfomonomer, component (B). Preferably, the buffer is present in an amount of about 0.1 moles per mole of the difunctional sulfomonomer. A process for preparing the sulfopoliesters of the present invention involves an ester exchange or an esterification step and a polycondensation step. The ester or esterification exchange is carried out under an inert atmosphere at a temperature of 150 to 250 ° C for 0.5 to 8 hours, preferably 180 to 230 ° C for 1 to 4 hours. The glycols, depending on their reactivities and the specific experimental conditions employed, are commonly used in molar excesses of 1.05-2.5 moles per total moles of functional acidic monomers. The second stage, referred to as polycondensation, is carried out under reduced pressure at a temperature of 215 to 350 ° C, preferably 250 to 310 ° C, and more preferably 260 to 290 ° C for 0.1 to 6 hours, preferably 0.25 to 2 hours. Appropriate conditions or stirring are used in both stages to ensure heat transfer and surface renewal of the reaction mixture. The reactions of both steps are facilitated by appropriate catalysts, especially those well known in the art, such as alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like. A three-step manufacturing process, similar to the disclosure of U.S. Patent 5,290,631, can also be used, particularly when a monomer feed mixed with acids and esters is employed. Dispersions can be obtained by adding molten polymer or solid in water with sufficient agitation. Generally, the dispersion medium is heated above 50 ° C, preferably above 80 ° C to effect a good dispersion of the sulfopolyester in a reasonable amount of time. It is a requirement of this invention that the sulfopolyester must be dispersible at a solids level of at least 10% by weight in pure water. It is preferred that the sulfopolyester have dispersibilities of at least 20% (w / w) and more preferably 30% (w / w) in pure water. Dispersion turbidities can be in the range of essentially clear to a hazy to milky translucent. A requirement is that the dispersed product maintain self-stability without sedimentation or phase separation for at least several weeks, preferably several months or more. The sulfopolyester of the present invention can be advantageously used as adhesion or adhesive compositions for textile yarns made of linear polyesters. When multifilament polyester yarns are manufactured in textiles it is desirable to treat the warp yarn, before spinning, with an adhering adhesive or glue composition and a plurality of filaments together. The treatment process, known as "adhesion", imparts resistance and resistance to thread abrasion during the spinning process. It is also critical that the adhesion or adhesive composition be completely removable from the spun fabric. Improved abrasion resistance will result in few breaks during the spinning process, while improving the quality of the textile product. Thus, one aspect of this invention is directed towards the adhesion or adhesive compositions and fibrous articles of manufacture bonded thereto. Although the described application is made with reference to polyester yarns, such as poly (ethylene terephthalate) or poly (1,4-cyclohexane-dimethylene terephthalate), the compositions described hereinafter can be used as glues for a variety of natural and synthetic yarns. Examples of non-polyester yarns include rayon, acrylic, polyolefin, cotton, nylon, and cellulose acetate. Mixtures of polyester and non-polyester yarns are also within the range of fibers that can be adhered effectively. it is necessary that the adhesion or adhesive compositions possess adequate blocking resistance, which manifests most critically when the fiber is spun onto a warp arm or spool and stored for extended periods of time under ambient conditions. Blocking causes the bonded fibers to melt together, which prevents them from being frayed at the desired time. The tendency to block occurs under both normal and extreme environmental conditions of temperature and the humidity may be related not only to the Tg of the adhesion or glue composition, but also to the hardness of the film. An advantageous combination of both film hardness and Tg is necessary to achieve excellent blocking resistance. Thus, a dry Tg range of 30 to 60 ° C, preferably 35 to 50 ° C and a pendulum film hardness of at least 80 cycles in the adhesion or adhesive compositions is required to avoid blocking problems. This Tg and hardness requirement needs careful selection of the acid and glycol components. For example, at a very high level of higher molecular weight polyalkylene glycol will decrease the Tg and hardness detrimentally, resulting in blockage. In general, as soon as the length or molecular weight of a higher order polyalkylene glycol monomer increases, in a constant molar percentage of incorporation, the Tg and the hardness of the final polymer will decrease proportionally. Surprisingly, the present invention clearly demonstrates that polyalkylene glycols of higher molecular weight and higher order, when the Tg and the total molecular weight are kept constant, provide film hardness and block resistance which is superior to similar compositions that contain an amount functionally equivalent of polyethylene glycol of higher molecular weight. Adhesion, flexibility, debonding and water resistance are also related to adhesion compositions for the molecular weight of polyethylene glycol and sulfopolyester content. As soon as the content of polyethylene glycol increases, hydrophilicity, flexibility, and adhesion are also increased. If the content of polyethylene glycol and / or molecular weight is very high, then the resulting adhesion will have a low Tg and a marginal water resistance. In this way, the preferred polyethylene glycols are of low molecular weight in adhesion compositions. The properties of disunion, water resistance, flexibility, and adhesion in adhesion or glue compositions are also related to the sulfomonomer content (YEP) . If the SIP level is too high, water resistance, flexibility, and adhesion economy will be diminished, while a low level of SIP functionality will tend to detract from adhesion and avoid proper disunion after the spinning operation. It is critical for the adhesion or adhesive compositions that the sulfopolyester contain polyalkylene glycol blocks of higher order of higher molecular weight to obtain excellent resistance to abrasion and anti-blocking tendencies. Preferably in the adhesion or adhesive compositions, 0.25 to 5 mol% of a higher molecular weight higher polyalkylene glycol will provide a sulfopolyester having excellent adhesion properties. The molecular weight of the higher order polyalkylene glycol for use in adhesion compositions is preferably 650 to 2000 grams / mol. Polybutylene glycol and polytetramethylene glycol ether are examples of higher molecular weight higher polyalkylene glycols for use in adhesion compositions. The materials and test procedures used for the results shown herein are as follows: Abbreviations used in the examples include: DEG refers to diethylene glycol EG refers to ethylene glycol I refers to isophthalate PTMG refers to polytetramethylene glycol PEG refers to polyethylene glycol T refers to terephthalate. The Duplan cohesion apparatus measures the abrasion resistance for samples of bonded yarn. The Duplan test is carried out on samples of attached wire, under constant tension, which are subjected to abrasion by friction plates that move back and forth on the wire at a constant speed. The average number of cycles to separate filaments of yarn is reported as abrasion resistance or Duplan value. The high Duplan values are a direct indicator of the suitability of the sulfopolyester as an adhesion material. The glass transition temperature (Tg) is determined using a differential scanning calorimeter (DSC). The inherent viscosity (I.V.) is measured at 25 ° C. Using 0.25 grams of polymer per 100 ml of a solvent consisting of 60% by weight of phenol and 40% by weight of tetrachloroethane. The data of the pendulum hardness test are obtained at 50% RH and 25 ° C; the pendulum starts at 6 degrees out of the vertical and the reported values are taken as the number of cycles in which the dampening action of the sample decreases the oscillation amplitude to three degrees outside the vertical. The following examples are proposed to illustrate but not limit the scope of this invention. All parts and percentages in the examples are on a weight basis unless otherwise stated. EXAMPLE 1 Preparation of a Water Dispersible Copolyether Ether Containing 11% Mole of 5-Sodiosulfoisophthalate and 1.5% Mole of PTMG1000. A 500-ml round-bottom mast equipped with a ground-glass head, agitator shaft, nitrogen inlet, and a side limb is loaded to allow the removal of volatile materials with 86.3 grams (0.445 moles) of dimethyl terephthalate, 16.3 grams (0.055 moles) of dimethyl-5-sodiosulfoisophthalate, 24.2 grams (0.39 moles) of ethylene glycol, 31.8 grams (0.30 moles) of diethylene glycol, 7.5 grams (0.0075 moles) of TERATHANE® polytetramethylene glycol 1000, 0.45 grams (0.0055 moles) ) of anhydrous sodium acetate, and 1.72 ml of 0.296% (weight / volume) of a solution of titanium isopropoxide in n-butanol. The flask is purged with nitrogen and immersed in a Belmont metal bath at 200 ° C for 60 minutes under a slow nitrogen passage with sufficient agitation. After raising the temperature to 280 ° C, a vacuum of 0.5 mm Hg is obtained and it is maintained for 17 minutes to carry out the polycondensation. The vacuum is displaced with a nitrogen atmosphere and the polymer is allowed to cool before removing it from the flask. An inherent viscosity of 0.43 dl / g is determined for the polymer recovered according to ASTM D3835-79. NMR analyzes indicate that the current glycol composition is 55% mol of EG, 44% in mol of DEG, and 1.3% in mol of TERATHANE ® polyethamethylene glycol 1000. A glass transition temperature (Tg) of 43 ° C is obtained for the polymer by thermal analysis by DSC. The polymer is dispersed directly in water at 90 ° C to give a stable 30% (w / w) dispersion which has a similar appearance to a slightly yellow emulsion. EXAMPLE 2 Preparation of a Water Dispersible Copolyether Ether Containing 10% Mole of 5-Sodiosulfoisophthalate and 1.5% Mole of PBG1000. The apparatus and method described in Example 1 is used except that the polycondensation time is changed. The quantities initially charged to the flask are: 67.9 grams (0.35 moles) of dimethyl terephthalate, 19.4 grams (0.10 moles) of dimethylisophthalate, 14.8 grams (0.05 moles) of dimethyl-5-sodiosulfoisophthalate, 24.2 grams (0.39 moles) of ethylene glycol , 31.8 grams (0.30 moles) of diethylene glycol, 7.5 grams (0.0075 moles) of polybutylene glycol (Mn = 1000 g / mol), 0.41 grams (0.005 moles) of sodium acetate, and 1.72 ml of a 0.296% solution (weight / volume) of titanium (IV) isopropoxide in n-butanol. Polycondensation is carried out at 280 ° C for 13 minutes at a pressure of 0.6 mm Hg. The recovered polymer has an inherent viscosity of 0.30 (ASTM D3835-79) and a Tg, as measured by DSC, of 43 ° C. EXAMPLE 3 Preparation of a Water Dispersible Copolyether Ether Containing 11% Mole of 5-Sodiosulfoisophthalate and 1.5% Mole of PTMG1000. The apparatus and method described in Example 1 is used except that the transesterification and polycondensation times are changed. The initial reactant charge consists of: 73.9 grams (0.445 moles) of terephthalic acid, 54.3 grams of (0.055 moles of the sulfomonomer) of a 46% (w / w) solution of diethylene glycol-5-sodium-sulfoisophthalate in diethylene glycol, 124.0 grams (2.0 moles) of ethylene glycol, 7.50 grams (0.0075 moles) TERATHANE® PTMG1000, 0.45 grams (0.0055 moles) of sodium acetate, and 5.15 ml of a 0.285% (w / v) solution of titanium isopropoxide (IV ) in n-butanol. Polyesterification is carried out at 200 ° C for 60 minutes and 230 ° C for 120 minutes, followed by a polycondensation stage at 280 ° C and 0.4 mm Hg for 13 minutes. The values of inherent viscosity and Tg of 0.30 and 43 ° C, respectively, are obtained in the same way as previously described. NMR analyzes indicate that the acid composition of the polymer is consistent with 89 mol% terephthalate and 11 mol% 5-sodiosulfoisophthalate units, while the glycol portion consists of 57 mol% EG, 43 mol% of SDR, and 1.3 mol% of polytetramethylene glycol (MW = 1000). EXAMPLE 4 Preparation of a copolyether ether dispersible in aliphatic water containing 11 mol% of 5-sodiosulfoisophthalate and 1.5 mol% of PTMG650. The apparatus and method described in Example 1 except that the transesterification is carried out at 200 ° C for 60 minutes and 230 ° C for 100 minutes, while the polycondensation is carried out at 280 ° C and 0.5 mm for 34 minutes. The reactants and their respective amounts are: 71.2 grams (0.445 moles) of dimethyl glutarate, 16.3 grams of (0.055 moles) of dimethyl-5-sodiosulfoisophthalate, 62.0 grams (1.00 moles) of ethylene glycol, 21.2 grams (0.20 moles) of diethylene glycol, 7.5 grams (0.025 moles) of polytetramethylene glycol 300 (Mn = 300 g / mol), 0.45 grams (0.0055 moles) of sodium acetate, and 1.59 ml of a 0.285% (w / v) solution of titanium (IV) isopropoxide in n-butanol. The recovered polymer is analyzed in the same way as previously described and an inherent viscosity of 0.42 dl / g and a Tg of 59 ° C is obtained. The sulfopolyester is dispersed in deionized water at 85 ° C to give a yellow, hazy dispersion that is stable at 30% (w / w) solids. EXAMPLE 5 Preparation of a copolyester ether dispersible in water containing 20 mol% of 5-sodiosulfoisophthalate and 2.0 mol% of PTMG2000. The apparatus described in Example 1 and the procedure followed in Example 4 are used except that the polycondensation time is changed to 20 minutes. The initial reactant charge consists of: 97.6 grams (0.40 moles) of dimethyl-2,6-naphthalene dicarboxylate, 29.7 grams of (0.10 moles) of dimethyl-5-sodiosulfoisophthalate, 106.0 grams (1.00 moles) of diethylene glycol, 20.0 grams (0.010 moles) TERATHANE ® polytetramethylene glycol 2000 (Mn = 2000 g / mol), 0.82 grams (0.010 moles) of sodium acetate, and 3.32 ml of a 0.285% (w / v) solution of titanium isopropoxide (IV) in n-butanol. The values of inherent viscosity and Tg of 0.38 and 60 ° C, respectively, are obtained as above. EXAMPLE 6 Preparation of a Water Dispersible Copolyether Ether Containing 15% Mole of 5-Sodiosulfoisophthalate and 1.0% Mole of PTMG2900. The same apparatus described in example 1 is used. The initial reactant charges are: 70.6 grams (0.425 moles) of terephthalic acid, 22.2 grams of (0.075 moles) of dimethyl-5-sodiosulfoisophthalate, 106.0 grams (1.00 moles) of diethylene glycol, 14.5 grams (0.005 moles) TERATHANE ® polytetramethylene glycol 2900 (Mn = 9000), 0.62 grams (0.0075 moles) of sodium acetate, and 2.62 ml of a 0.285% (w / v) solution of titanium isopropoxide (IV) in n-butanol.

After purging the reactants with nitrogen, submerge the flask in a Belmont metal bath at 200 ° C for 60 minutes and 230 ° C for an additional 120 minutes under a nitrogen passage with sufficient agitation to complete the transesterification. After raising the temperature to 280 ° C, a vacuum of < 0.7 mm Hg and it is maintained for 85 minutes to carry out the polycondensation stage. Inherent viscosity and Tg measurements are carried out as described above with the respective values, 0.42 dl / g and 18 ° C, indicated for each one. EXAMPLE 7 Preparation of a copolyester ether dispersible in cycloaliphatic water containing 11 mol% of 5-sodiosulfoisophthalate and 3.0 mol% of PTMG1000. The apparatus and general procedure described in Example 1 is used except that the polycondensation time changes. The quantities initially charged in the flask are: 89.0 grams (0.445 moles) of dimethyl-1,4-cyclohexanedicarboxylate, 16.3 grams of (0.055 moles) of dimethyl-5-sodiosulfoisophthalate, 36.6 grams (0.59 moles) of ethylene glycol, 41.8 grams (0.29 moles) of 1,4-cyclohexanedimethanol, 15.0 grams (0.15 moles) of TERATHANE® poiitetramethylene glycol 1000 (Mn = 1000 g / mol), 0.45 grams (0.0055 moles) of sodium acetate, and 2.36 ml of a 0.285% (weight / volume) solution of titanium (IV) isopropoxide in n-butanol. The polycondensation is carried out at 280 ° C for 34 minutes at a pressure of 0.6 mm Hg. The recovered polymer has an inherent viscosity of 0.43 (ASTM D3835-79) and a Tg, as measured by DSC, of 74 ° C. The real relationship of the glyco, as determined by gas chromatography, is 47% EG, 1% SDR, and 52% CHDM. The polymer is dispersed in 70 ° C of water in 30% solids (w / w) to give a stable, slightly misty product. EXAMPLE 8 Preparation of a Water Dispersible Copolyether Ether Containing 24% Mole of 5-Sodiosulfoisophthalate and 1.5% Mole of PTMG650. The apparatus and general procedure described in Example 1 is used except that the transesterification and polycondensation times are changed. The initial charge of the reactant consists of: 63.1 grams (0.38 moles) of isophthalic acid, 35.5 grams (0.12 moles) of dimethyl-5-sodiosulfoisophthalate, 80.6 grams (0.80 moles) of diethylene glycol, 17.3 grams (0.12 moles) of 1, 4-cyclohexanedimethanol, 4.9 grams (0.0075 moles) of polytetramethylene glycol (Mn = 650), 0.98 grams (0.012 moles) of sodium acetate, and 2.41 ml of a 0.285% (w / v) solution of titanium isopropoxide (IV) in n-butanol. The transesterification is carried out at 200 ° C for 60 minutes and 230 ° C for 120 minutes, followed by a polycondensation stage at 280 ° C and 0.6 mm Hg for 45 minutes. The values of y of Tg of 0.33 and 32 ° C, respectively, are obtained in the same way as previously described. EXAMPLE 9 Preparation of a copolyester ether dispersible in water containing 13 mol% of 5-sodiosulfoisophthalate and 30.0 mol% of PTMG250. The apparatus and procedure is used as in the example 1 except that the transesterification is carried out at 200 ° C for 60 minutes and 230 ° C for 95 minutes, while the polycondensation is carried out at 280 ° C and 0.8 mm for 10 minutes.

The reactants and their respective are: 84.4 grams (0.435 moles) of dimethyl terephthalate, 19.2 grams of (0.065 moles) of dimethyl-5-sodiosulfoisophthalate, 62.0 grams (1.00 moles) of ethylene glycol, 37.5 grams (0.15 moles) polytetramethylene glycol 250 (Mn = 250 g / mol), 0.53 grams (0.0065 mol) of sodium acetate, and 2.44 ml of a 0.285% (w / v) solution of titanium (IV) isopropoxide in n-butanol. The recovered polymer is analyzed in the same way as previously described and an inherent viscosity of 0.42 (ASTM D3835-79) is obtained and a Tg of 22 ° C is obtained. EXAMPLE 10 Preparation of a copolyester ether dispersible in water containing 13 mol% of 5-sodiosulfoisophthalate and 50.0 mol% of PTMG250. The apparatus described in Example 1 is used and the procedure is followed as in Example 9 except that the polycondensation is carried out under a vacuum of 0.9 mm Hg for 20 minutes. The initial charge of the reactant consists of: 72.2 grams (0.065 moles) dimethyl-5-sodiosulfoisof alato, 62.0 grams (1.00 moles) of ethylene glycol, 62.5 grams (0.25 moles) polytetramethylene glycol 250 (Mn = 250 g / mol), 0.53 grams (0.0065 moles) of sodium acetate, and 2.67 ml of a solution 0. 285% (weight / volume) of titanium (IV) isopropoxide in n-butanol. The inherent viscosity values and tg of 0.53 and 10 ° C, respectively, are obtained as above. EXAMPLE 11 Preparation of a water-dispersible ether copolyester ether adhesion composition for fibrous articles. The apparatus is used and the procedure described in Example 1 is followed except that the polycondensation step is carried out under a vacuum of 0.6 mm for 23 minutes. The initial charge of the reactant consists of: 87.3 grams (0.45 moles) of dimethylterephthalate, 14.8 grams (0.05 moles) of dimethyl-5-sodiosulfoisophthalate, 24.2 grams (0.39 moles) of ethylene glycol, 31.8 grams (0.30 moles) of diethylene glycol, 7.5 grams (0.0075 moles) of TERATHANE ® polytetramethylene glycol 1000 (Mn = 1000 g / mol), 0.41 grams (0.005 moles) of anhydrous sodium acetate, and 1.72 ml of a 0.296% (w / v) solution of titanium (IV) isopropoxide in n-butanol. The polymer is recovered and triturated through a pitch of a 3 mm mesh and analyzed in the same manner as described in the previous examples. The results of the analyzes are given in Table 1. Table 1. Characterization data for an adhesion composition of water dispersible copolyester ether Composition of glycol *% SIP iv T ^ (° c) (% by moles) (% by moles) 53% by EG 10.5 10.38 43 45. 5% SDR, 1.5% PTMG1000 * based on 100 mol% of total glycol. The polymer is dispersed in deionized water at a solids level of 10 weight percent and diluted to less than 10 weight percent for the cut. The fiber test is carried out after cutting (ie, passing the yarn through the aqueous adhesion dispersion) and drying of a polyester yarn removed from the denier warp 150/40 filaments. The results in Table 2 show the excellent blocking resistance, film hardness, and abrasion resistance of the composition at a level of 2.9% by weight, based on the total weight of the fiber. Table 2 Fiber test results for copolyester ether adhesion composition -da Hardness, value He cycles H ^ complement pendulum block abrasion 2.9 111 2.12 160 EXAMPLE 12 Effect of modification of isophthalate on the film and adhesion properties of the fiber. Table 3 shows the fiber adhesion properties of selected polymers within the scope of the invention to demonstrate the effect of the isophthalate units on performance. Table 3 Comparative data for fiber properties as a result of modification of isophthalate Composition *% (mole%) complement Value of Locking cycles abrasionT = 69. 2.8 SIP = 10, 1.52 160 EG = 52, DEG = 46, PTMG1000 = 1.5 T = 60, 4.6 1 = 30, 2.54 110 SIP = 10, EG = 51, DEG = 47, PTMG1000 = 1.5 T = 50, 2.8 1 = 40, 3.59 100 SIP = 9.5, EG = 53, DEG = 45, PTMG1000 = 1.5 * total acid and glycol = 200% in mol all polymers are dispersed in deionized water at a solids level of 20% in weight and diluted appropriately for cutting. The fiber test is conducted by passing (ie, cutting) a polyester yarn removed from the denier warp 150/40 filaments through an aqueous dispersion of the adhesion and drying composition. The results in the Table 1 clearly demonstrate that modification of isophthalate results in poor blocking resistance. Blocking resistance numbers are obtained by measuring the relative strength of the fiber to be unraveled from a bundle or reel.

The beam is conditioned for a week at 40 ° C and 90% relative humidity before the blocking test is performed. It is also clear that the modification of isophthalate decreases the abrasion resistance. COMPARATIVE EXAMPLE 13 Effect of PEG against PTMG on blocking The results in Table 4 demonstrate that the higher polyalkylene glycols, specifically PTMG, impart superior antiblock resistance to the sulfopolyester adhesion compositions at a constant Tg. It is also evident that the Tg alone does not accurately predict the blocking tendency. Table 4 Effect of Tg and polyalkylene glycol of higher order Identity on blocking resistance Composition *% of Tg (° C) Value of (% mol) blocking complement T = 60. 1 = 30, 4.6 36 2.54 SIP = 10, EG = 51, SDR = 47, PTMG1000 = 1.5 T = 69, 1 = 19, 3.6 37 4.60 SIP = 12, EG = 44, DEG = 54, PTMG1000 = 1.8 * total acid and glycol = 200% mol The cutting and testing of the fiber is done in the same way as in the previous example. The results clearly show that the adhesive containing PTMG provides a less significant blocking tendency than a PEG-based analogue. In addition, the PTMG sample represents a weight scenario in which the% complement is greater (ie, 4.6% vs. 3.6%), which typically increases the blockage, and the level of isophthalate modification is 30% as compare with 20% for the PEG sample; it is shown in Example 13 that increasing the level of isophthalate modification increases the blocking tendency. EXAMPLE 14 Effectiveness of PTMG modification to improve abrasion resistance.

The results in Table 5 show that incorporation of a sufficient level of PTMG markedly improves the abrasion resistance of a sulfopolyester adhesion composition. The three polymers are synthesized under identical conditions with the proportions of acid and glycol remaining constant. The nominal composition (100 mol% acid and 100 mol% glycol = 200 mol% total), based on the monomer feed, is 70% terephthalate, 20% isophthalate, 10% SIP, 30% % of SDR, and 70% of SDR. The fiber is cut and tested in the same way as example 11. Table 5 Effect of the incorporation of PTMG on the abrasion resistance PTMG 1QQQ. % Co-plement o Abrasion cycles% in mole 0.25 6.96 20 0.50 6.77 30 1.50 6.44 110 * based on 100% on total glycol the linear water-dispersible sulfopoliesters of the present invention incorporate higher order polyalkylene glycol units. The sulfopoliesters provide improved abrasion and blocking resistance compared to sulfopolyester compositions containing a functionally equivalent amount of higher molecular weight polyethylene glycol. The sulfopoliesters of the present invention are particularly useful in fiber bonding applications where abrasion resistance is important. Many variations will be suggested by themselves to those with experience in this technique in light of the above detailed description. Such obvious modifications are within the total proposed scope of the appended claims.

Claims

CLAIMS 1. A linear water-dispersible sulfopolyester having a Tg of -20 ° C to 100 ° C, the sulfopolyester characterized in that it comprises the reaction product of: (A) 60 to 95 mol%, based on the moles of the acid in the sulfopolyester, of at least one difunctional dicarboxylic acid which is not a sulfomonomer, the dicarboxylic acid which is selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, saturated aliphatic dicarboxylic acids having 4 to 14 carbon atoms. to 12 carbon atoms and cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms; (B) 5 to 40% by mol, based on moles of acid in the sulfopolyester, of at least one difunctional sulfomonomer containing at least one sulfonated metal group attached to an aromatic ring in which the functional groups are ester or carboxyl; (C) 0.1 to 50% by mole, based on the moles of the glycol in the sulfopolyester, of at least one polyalkylene glycol of higher order having the structure: H - [OCH ^ CH) ^ OH where R is selected from the group which consists of hydrogen and an alkyl group having 1 to 12 carbon atoms, n is an integer from 2 to 200, m is an integer from 1 to 10 when R is an alkyl group or is an integer of 2 to 10 when R is hydrogen, with the proviso that the mole% of the higher order polyalkylene glycol is inversely proportional to the value of n; and (D) 0.1 to 99.9 mol%, based on the moles of the glycol in the sulfopolyester, of at least one polyethylene glycol having the structure: H- (OCH 2 CH 2) n, -OH where n 'is an integer from 2 to 500, with the condition of mol% of polyethylene glycol being inversely proportional to the value of n'; the sulfupolyester having substantially equal molar proportions of acid equivalents (100 mole percent) and glycol equivalents (100 mole percent).
2. A linear, water-dispersible sulfopolyester having a Tg of -20 ° C to 100 ° C, the sulfopolyester characterized in that it comprises the reaction product of: (A) 80 to 95 mol%, based on the moles of the acid in the sulfopolyester, of at least one difunctional dicarboxylic acid which is not a sulfomonomer, the dicarboxylic acid which is selected from the group consisting of succinic, glutaric, adipic, azelaic, sebasic, fumaric, maleic, itaconic acid, 1,3 - cyclohexanedicarboxylic, 1,4-cyclohexanedicarboxylic, diglycolic, 2,5-norbornandicarboxylic, phthalic, terephthalic, 1,4-naphthalenedicarboxylic, 2,5-naphthalenedicarboxylic, diphenic, 4,4'-oxydibenzoic, 4,4'-sulfonyldibenzoic, and isophthalic; (B) 5 to 20 mol%, based on moles of acid in the sulfopolyester, of at least one difunctional sulfomonomer selected from the group consisting of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphthalen-2, 7- acid dicarboxylic, and esters thereof; (C) 0.5 to 20 mol%, based on the moles of the glycol in the sulfopolyester, of at least one polyalkylene glycol of higher order having the structure: H -COCH ^ CH) - ^ OH where R is selected from the group consisting of hydrogen and an alkyl group having 1 to 12 carbon atoms, n is an integer from 2 to 200, m is an integer from 1 to 10 when R is an alkyl group or is an integer from 2 to 10 when R is hydrogen, with the proviso that the mol% of the higher order polyalkylene glycol is inversely proportional to the value of n; and (D) 50 to 50% by mole, based on the moles of the glycol in the sulfopolyester, of at least one polyethylene glycol having the structure: H- (OCH 2 CH 2) n, -OH where n 'is an integer from 2 to 500, with the condition of mol% of polyethylene glycol being inversely proportional to the value of n'; the sulfupolyester having substantially equal molar proportions of acid equivalents (100 mole percent) and glycol equivalents (100 mole percent).
3. The sulfopolyester in accordance with claim 1, characterized in that the dry Tg is in the range of 35 to 50 ° C.
4. The sulfopolyester according to claim 2, characterized in that the dicarboxylic acid, component (A), is selected from the group consisting of terephthalic acid and isophthalic acid.
5. The sulfopolyester in accordance with claim 1 characterized in that the sulfopolyester is prepared using 0.1 to 99.8 mol%, based on the moles of the glycol in the sulfopolyester, of a glycol which is not polyethylene glycol or higher polyalkylene glycol , the glycol which is selected from the group consisting of cycloaliphatic glycols having 6 to 20 carbon atoms, aliphatic glycols having 3 to 20 carbon atoms, and mixtures thereof.
6. The sulfopolyester according to claim 5, characterized in that the glycol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethyl-hexan-l, 3-diol , 2,2-dimethyl-1,3-propanediol, 2-ethyl-butyl-1,3-butane-diol, 1,4-butane-diol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl -l, 6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 2,4,4-tetramethyl-l, 3-cyclobutanediol, p-xylylenediol, and mixtures of the same.
7. The sulfopolyester in accordance with claim 6, characterized in that the glycol is selected from the group consisting of ethylene glycol, 1,4-cyclohexanedimethanol and mixtures thereof.
8. A fibrous article adhered with an adhesion composition comprising a sulfopolyester, dispersible in water, linear, having a dry Tg of 35 ° C to 50 ° C, the sulpoliester characterized in that it comprises the reaction product of: (A) 60 to 95% mol, based on the moles of the acid in the sulfopolyester, of at least one difunctional dicarboxylic acid which is not a sulfomonomer, the dicarboxylic acid which is selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms and cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms; (B) 5 to 40% by mol, based on moles of acid in the sulfopolyester, of at least one difunctional sulfomonomer containing at least one sulfonated metal group attached to an aromatic ring in which the functional groups are ester or carboxyl; I (C) 0.1 to 50% by mol, based on the moles of the glycol in the sulfopolyester, of at least one polyalkylene glycol of higher order having the structure: H -COCH ^ CH) ^ OH where R is selected from the group consisting of hydrogen and an alkyl group having 1 to 12 carbon atoms, n is an integer from 2 to 200, m is an integer from 1 to 10 when R is an alkyl group or is an integer from 2 to 10 when R is hydrogen, with the proviso that the mol% of the higher order polyalkylene glycol is inversely proportional to the value of n; (D) 0.1 to 99.9 mol%, based on the moles of the glycol in the sulfopolyester, of at least one polyethylene glycol having the structure: H- (OCH 2 CH 2) n, -OH where n 'is an integer from 2 to 500, with the condition of mol% of polyethylene glycol being inversely proportional to the value of n'; and (E) 10 to 75% mol, based on the moles of glycol in the sulfopolyester, of a glycol which is not polyethylene glycol, the glycol being selected from the group consisting of cycloaliphatic glycols having 6 to 20 atoms carbon, aliphatic glycols having 3 to 20 carbon atoms, and mixtures thereof; the sulfupolyester having substantially equal molar proportions of acid equivalents (100 mole percent) and glycol equivalents (100 mole percent).
9. The sulfopolyester according to claim 1, characterized in that the sulfopolyester is prepared using a buffer in an amount of 0.001 to 0.2 moles per mole of the difunctional sulfomonomer, component (B).
10. The sulfopolyester in accordance with claim 2, characterized in that the difunctional sulfomonomer, component B, 5-sodium-sulfoisophthalic acid.
11. The fibrous article according to claim 9, characterized in that the fibrous article is a textile yarn.
The sulfopolyester according to claim 1, characterized in that the sulfopolyester has an inherent viscosity of 0.1 to 1.1 dl / g as measured in 60/40 parts by weight of a solution of phenol / tetrachloroethane at 25 ° C and a concentration of 0.25 grams of the polymer in 100 ml of the solvent.
13. The sulfopolyester according to claim 12, characterized in that the sulfopolyester has an inherent viscosity of 0.2 to 0.7 dl / g as measured in 60/40 parts by weight of a solution of phenol / tetrachloroethane at 25 ° C and a concentration of 0.25 grams of a polymer in 100 ml of the solvent.