JP2002531612A - Terephthalate-based sulfopolyesters - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to (i) terephthalic acid, (ii) at least one containing at least one sulfonate group bonded to an aromatic ring in an amount sufficient to impart water dispersibility to the sulfopolyester. species difunctional sulfomonomer, (iii) less than 5 mol%, not terephthalic acid or sulfomonomer, at least one dicarboxylic acid, (iv) 25 to 90 mol%, the structural formula: H- (OCH ₂ At least one polyethylene glycol having CH ₂ ) _n -OH, where 2 ≦ n <20 and the mole% of polyethylene glycol is inversely proportional to the amount n in the range, and (v) the hydroxyl equivalent More than 10 mol% but less than 75 mol% of a residue of glycol or a mixture of glycols that is not polyethylene glycol. About sex sulfopolyester. The water-dispersible sulfopolyesters according to the invention show improved abrasion and blocking resistance when used as sizing composition. Accordingly, in another aspect, the present invention relates to a fibrous article glued with a sizing composition comprising a water-dispersible sulfopolyester as described above and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to water-dispersible sulfopolyesters based on terephthalate units. The sulfopolyester of the present invention has easy dispersibility, excellent dispersion storage stability, and is useful as a textile fiber sizing agent having improved abrasion resistance and blocking resistance.

[0002] water-dispersible sulfopolyester containing background terephthalate units and polyethylene glycol units of the present invention are well known in the art. Such sulfopolyesters are taught, for example, by U.S. Patent Nos. 3,546,008, 3,734,874 and 3,779,993. These patents disclose that when terephthalic acid is used as the dicarboxylic acid component, at least 5 mol% of an additional acid should be used to obtain a sulfopolyester having sufficient dispersibility. . U.S. Pat. No. 5,290,631 discloses water-dispersible sulfopolyesters based on repeating structural units of terephthalate, isophthalate, sulfomonomer, ethylene glycol and polyoxyethylene glycol. There is no disclosure of sulfopolyesters based on acid components consisting of less than 5 mol% of terephthalic acid or acids other than sulfomonomers.
In fact, the sulfopolyesters disclosed by this patent include 10-75
It contains a combination of mol% terephthalate units and 15-70 mol% isophthalate units.

[0003] Sulfopolyester compositions that are only dispersible in water / alcohol mixtures are disclosed in US Pat. No. 4,525,524. This sulfopolyester is
It comprises 20 to 90 mol% of repeating units derived from a diacid component consisting of dimethyl terephthalate or terephthalic acid. The glycol component may contain 80 mol% or less of glycol having 3 to 12 carbon atoms and glycol ether having 4 to 12 carbon atoms based on the total glycol. None of these compositions are dispersible in water alone.

It is known in the art that the dispersibility of a sulfopolyester can be increased when the glycol component comprises high molecular weight polyethylene glycol. For example, water dissipative sulfopolyesters based on high molecular weight polyethylene glycols are disclosed in U.S. Pat. No. 4,233,196. The molecular weight of this polyethylene glycol component ranges from 106 to 22,018 g / mol, and the total glycol component contains less than 15 mol% of polyethylene glycol. Like the aforementioned patent, this patent discloses that when terephthalic acid is used as the dicarboxylic acid component of the polyester, the desired result is only achieved when at least 5 mol% of the additional acid is used. ing. Furthermore, increasing the molecular weight of the polyethylene glycol subsequently leads to blocking of the glued particles,
It results in a polyester having a lower glass transition temperature.

[0005] Accordingly, there remains a need for water-dispersible sulfopolyesters based on terephthalate units that have easy water-dispersibility and improved abrasion and blocking resistance.

[0006] Summary water dispersible invention, improved abrasion resistance and blocking resistance, the substantially water dispersible sulfopolyester terephthalic acid ester (terephthalate) units based on the acid component, terephthalic acid ester , A sulfomonomer (when the sulfomonomer is present in the acid form) and less than 5 mol% of additional acid, and the glycol component has at least 25 mol% and less than 90 mol% of the following formula: _(OCH 2 _{CH 2)} (wherein, 2 ≦ n <a 20) n -OH when included at least one polyethylene glycol of has been found that it is possible to obtain.

Accordingly, the present invention relates to (i) terephthalic acid or a derivative thereof; (ii) at least one terephthalic acid or a derivative thereof or less than about 5 mol%, based on the total number of moles of acid, which is not a sulphomonomer. the _{H- (OCH} 2 _CH 2) (wherein, a 2 ≦ n <20) n -OH : dicarboxylic acids, (iii) from about 25 to about 90 mole% in the total mole% basis of hydroxyl equivalents, structure At least one polyethylene glycol (mol% of polyethylene glycol present is inversely proportional to the value of n); (iv) greater than about 10 mol% but not greater than about 75 mol%, based on total mol% of hydroxyl equivalents.
Less than mole% of glycol or mixture of glycols which is not polyethylene glycol, and (v) at least one of an amount sufficient to impart water dispersibility to the sulfopolyester.
Water-dispersible sulfopolyesters comprising at least two difunctional sulfomonomers.

[0008] The sulfopolyester has a substantially equal molar ratio of acid mole equivalents (about 100 mole%) such that the sum of acid equivalents and hydroxyl equivalents is equal to about 200 mole%.
) And hydroxyl equivalents (about 100 mol%). The inherent viscosity of the sulfopolyesters according to the invention is at least 0.1 dL / g, measured in a 60/40 parts by weight solution of phenol / tetrachloroethane at 25 ° C. in a concentration of about 0.25 g of polymer in 100 ml of solvent. .

The bifunctional sulfomonomer that imparts water dispersibility to the water-dispersible sulfopolyester of the present invention is a dicarboxylic acid containing at least one sulfonate group bonded to an aromatic ring or a derivative thereof, or a dicarboxylic acid bonded to an aromatic ring. Selected from diols containing at least one sulfonate group and hydroxy acids or derivatives thereof containing at least one sulfonate group bonded to an aromatic ring.

The water-dispersible sulfopolyesters according to the invention show improved abrasion and blocking resistance when used as sizing composition. Accordingly, in another aspect, the present invention relates to a fibrous article glued with a sizing composition comprising a water-dispersible sulfopolyester as described above.

[0011] The invention relates to an improved water-dispersible, has a wear resistance and blocking resistance, relates to water-dispersible sulfopolyester based substantially terephthalate units. Such sulfopolyesters include terephthalic acid esters, an acid component containing the sulfomonomer and less than 5 mole% additional acid when the sulfo monomer is present in the acid form, and at least 25 mole% and less than 90 mole%, It has a glycol component consisting of at least one kind of polyethylene glycol represented by the following formula H- (OCH ₂ CH ₂ ) _n -OH ( _where 2 ≦ n <20).

The term “water dispersible” often refers to “water dissipative,” “water soluble,” or “water dissipative.”
Used interchangeably with other descriptions such as In the context of the present invention, all of these terms are to refer to the activity of water on the sulfopolyesters described herein. For this terminology, it is intended to include conditions in which the sulfopolyester is dissolved to form a true solution or dispersed in an aqueous medium to obtain a stable product. Often, due to the statistical properties of the polyester composition, it is possible for a single sulfopolyester to have a soluble portion and a dispersible portion when affected by an aqueous medium.

As noted above, the present invention relates to (i) terephthalic acid or a derivative thereof, (ii) less than about 5 mol% based on the total moles of acid, at least not terephthalic acid or a derivative thereof or a sulfomonomer. one dicarboxylic acid, (iii) a hydroxyl equivalent weight of from about 25 to about 90 mole% in the total mole% basis, the structural formula: _{H- (OCH} 2 _CH 2) in n -OH (wherein, in 2 ≦ n <20 And the mole% of polyethylene glycol present is n
At least one polyethylene glycol having the formula: (iv) more than about 10 mol% but about 75 mol%, based on total mol% of hydroxyl equivalents.
Less than mole% of glycol or mixture of glycols which is not polyethylene glycol, and (v) at least one of an amount sufficient to impart water dispersibility to the sulfopolyester.
Water-dispersible sulfopolyesters comprising at least two difunctional sulfomonomers.

The sulfopolyester is prepared in substantially equal molar proportions of the acid mole equivalent (about 100 mole%) such that the sum of the acid equivalent and the hydroxyl equivalent is equal to about 200 mole%.
) And hydroxyl equivalents (about 100 mol%). The water-dispersible sulfopolyester according to the invention has an inherent viscosity of at least 0.1 dL / g, measured in a 60/40 parts by weight solution of phenol / tetrachloroethane at 25 ° C. in a concentration of about 0.25 g of polymer in 100 ml of solvent. Having. This inherent viscosity is at least, preferably 0.25 dL / g, more preferably 0.3 dL / g. For improved adhesion properties, the glass transition temperature of the water-dispersible sulfopolyester according to the invention is at least 25C, more preferably 25-75C, most preferably 30-65C.

[0015] As described above, the water-dispersible sulfopolyester according to the present invention contains terephthalic acid as an acid component, wherein at least 95 mol% of the total moles of the acid are formed by converting the sulfomonomer into an acid. When present in the form, it consists of a combination of terephthalic acid and a sulfomonomer. In the context of the present invention, the term "terephthalic acid" embraces the use of terephthalic acid and its corresponding acid anhydride, ester and acid chloride derivatives. Preferred terephthalic acid diesters useful in the sulfopolyester according to the present invention include dimethyl terephthalate. However, the inclusion of higher alkyl esters, such as ethyl, propyl, isopropyl and butyl, is acceptable. In addition, aromatic esters, especially phenyl esters, can be used. Preferably, the terephthalic acid component is selected from terephthalic acid and dimethyl terephthalate.

As mentioned above, the sulfopolyesters of the present invention contain less than 5 mol% of additional dicarboxylic acids that are not terephthalic acid or its derivatives or sulfomonomers. Preferably, the sulfopolyester according to the invention does not contain any additional acid, i.e. component (ii). Examples of dicarboxylic acids that can be used as component (ii) include aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, aromatic dicarboxylic acids or mixtures of two or more of these acids. Preferred dicarboxylic acids include, but are not limited to, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, 2,5-norbornanedicarboxylic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenic acid, , 4
'-Oxydibenzoic acid and 4,4'-sulfonyldibenzoic acid are included. the term"
"Dicarboxylic acids" include the use of the corresponding acid anhydrides, esters and acid chloride derivatives of these acids. Diesters are preferred and dimethyl esters are most preferred as compared to acid anhydrides and acid chlorides. Ethyl, propyl, isopropyl,
It is also acceptable to include higher alkyl esters such as butyl and the like. Furthermore, aromatic esters, especially phenyl esters, can be considered.

The polyethylene glycol component (iii) provides a hydrophilic but non-ionic moiety in the sulfopolyester backbone. For polyethylene glycol,
In addition to the benefits of tailoring the hydrophilicity of the sulfopolyester, a number of other benefits can be obtained. For example, from a particular glycol composition, lower melt viscosity, improved adhesion and increased abrasion resistance can be achieved. However, simply maximizing the amount of polyethylene glycol (PEG) does not lead to the easiest dispersibility or dispersion transparency / stability. The best results are obtained by combining a hydrophilic glycol (i.e., PEG component (iii)) with a hydrophobic glycol (i.e., a glycol component that is more hydrophobic than the PEG component) to achieve a best dispersibility at Tg above 25 <0> C. Obtained when given the combination of Suitable hydrophobic glycols (ie, glycol component (iv)) useful in the sulfopolyesters of the present invention are described below.

As the molecular weight of PEG increases, the maximum loading level decreases. In other words, the molecular weight and mol% of the PEG component (iii) are inversely proportional to each other. In particular, as the molecular weight increases, the mole percent of PEG decreases. Generally, the mole percent of PEG is in the range of about 25-90 mole percent, based on the total mole percent of hydroxyl equivalents.
In a preferred embodiment, a PEG having a molecular weight of 106 (ie, n = 2) comprises less than 90 mole% of the total glycol, while a molecular weight of 850 (ie, n = 19).
Is typically contained at a level of less than 10 mol% of the total glycol.

The PEG component (iv) has the following general formula: HO— (CH ₂ CH ₂ —O) _n —H, where n is at least 2 but less than 20. Preferably, 2 ≦ n ≦ 10, and more preferably, 2 ≦ n ≦ 6. Most preferred are lower molecular weight polyethylene glycols, diethylene glycol, triethylene glycol and tetraethylene glycol.

It is important to recognize that certain glycols of (iv) can be formed in situ due to side reactions that can be controlled by changing process conditions. Examples thereof include altered ratios of diethylene glycol, triethylene glycol from ethylene glycol based on acid catalyzed dehydration, which readily occur when no buffer is added to raise the pH of the reaction mixture (ie, lower acidity). And the production of tetraethylene glycol. Additional compositional tolerances are possible when the buffer is omitted from a feed containing various ratios of ethylene glycol and diethylene glycol or ethylene glycol, diethylene glycol and triethylene glycol and combinations and the like.

As mentioned above, the glycol component of the sulfopolyester of the present invention is
Including a hydrophobic glycol in combination with the G component (iii) results in improved dispersibility. Suitable hydrophobic glycols, i.e., component (iv) of the sulfopolyesters of the present invention, include aliphatic glycols, cycloaliphatic glycols and aralkyl glycols, since more than about 10 mole% of the total mole% of hydroxyl equivalents. Consist up to less than about 75 mol%. More preferably, the glycol component (iv) comprises:
Make up about 20 to about 50 mole% of the total mole% of hydroxyl equivalents. Examples of these glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol,
2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-
Propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,2- Cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 2,2,4
4-tetramethyl-1,3-cyclobutanediol and p-xylylenediol are included. Ethylene glycol is preferred.

The bifunctional sulfomonomer for imparting water dispersibility to the water-dispersible sulfopolyester of the present invention is a dicarboxylic acid containing at least one sulfonate group bonded to an aromatic ring or a derivative thereof, bonded to an aromatic ring. It is selected from diols containing at least one sulfonate group and hydroxy acids or derivatives thereof containing at least one sulfonate group attached to an aromatic ring. The difunctional sulfomonomer is advantageously a diol containing a sulfonate group derived from a dicarboxylic acid or an ester thereof having a sulfonate group (—SO ₃ M) or a reaction product of a dicarboxylic acid or an ester thereof with a glycol. It may be. The cations of the sulfonate are Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Cu ⁺⁺ , Ni ⁺⁺ , Fe ⁺
It may be a metal ion such as ⁺⁺ . It is noted that the sulfonate salt is non-metallic and may be a nitrogenous base as disclosed in US Pat. No. 4,304,901, the disclosure of which is incorporated herein by reference. Within the boundaries of the disclosure.
Suitable nitrogen base cations are 10 ⁻³ to 10 ⁻¹⁰ , preferably 10 ⁻⁵ to 10
It is derived from a nitrogen-containing base, which may be an aliphatic, cycloaliphatic or aromatic compound, having an ionization constant in water at 25 ° C. of ⁻⁸ . Examples of suitable nitrogen-containing bases are ammonia, pyridine, morpholine and piperidine.

It is known that the choice of cation is often significant and affects the water dispersibility of the resulting polymer. Depending on the end use application of the polymer, more easily dispersible products or less easily dispersible products may be desirable.
For example, it is possible to prepare a sulfopolyester using sulfonic acid sodium salt and then, when the polymer is in dispersed form, replace sodium by a different ion such as zinc by ion exchange. This type of ion exchange procedure is generally superior for producing polymers with divalent and trivalent salts, as the sodium salt is usually more soluble in the polymer reactant melt phase. Also, since amine salts tend to be unstable under typical melt processing conditions, ion exchange procedures are usually required to obtain nitrogenous counterions.

Preferred bifunctional sulfomonomers are those in which the sulfonate base is bound to an aromatic acid nucleus such as benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or methylenediphenyl. More preferably, the sulfomonomer is a sulfophthalic acid, a sulfoterephthalic acid, a sulfoisophthalic acid, such as described in US Pat. No. 3,779,993, the disclosure of which is incorporated herein by reference. -Sulfonaphthalene-2,7-dicarboxylic acids and their esters. Even more preferably, the bifunctional sulfomonomer is 5-
Sodiosulfoisophthalic acid or an ester thereof. Preferably, the difunctional sulfomonomer is present in an amount of from 6 to 40 mol%, more preferably from about 8 to 30 mol%, most preferably from about 9 to 25 mol%, based on total acid equivalents.

[0025] The process for preparing the sulfopolyesters of the present invention involves two distinct steps, a transesterification or esterification step and a polycondensation step. The transesterification or esterification is carried out under an inert atmosphere at a temperature of 150 to 250 ° C for 0.5 to 8 hours, preferably at 180 to 230 ° C for 1 to 4 hours. The difunctional sulfomonomer is usually added directly to the reaction mixture from which the polymer is made. Other methods are known and can be used. Representative examples from the art are U.S. Patent Nos. 3,018,272, 3,075,952 and 3,033.
No., 822 (the disclosures of which are incorporated herein by reference). Glycols are usually used in a molar excess of 1.05 to 2.5 mol per total mol of acid-functional monomer, depending on their reactivity and the specific experimental conditions used. Preferably, the esterification reaction is performed at ambient or superatmospheric pressure. In either situation, an inert atmosphere such as nitrogen or argon will give excellent results. The second stage, referred to as polycondensation, is carried out under reduced pressure at 230-350 ° C, preferably
At a temperature of 40 to 310C, more preferably 250 to 290C, for 0.1 to 6 hours,
Preferably, it is performed for 0.25 to 2 hours. Agitation or appropriate conditions are used at both stages to ensure proper heat transfer and surface renewal of the reaction mixture.

[0026] Both steps of the reaction are suitable catalysts, especially those known in the art and are described, for example, in US Pat. Nos. 4,167,395 and 5,290,631 (with reference to these disclosures). (Included herein). Suitable catalysts include, but are not limited to, alkoxytitanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyltin compounds, metal oxides, and the like. When terephthalic acid is used as one of the starting materials, the esterification step will be autocatalytic. US Patent 5,29
A three-step production process similar to that disclosed in U.S. Pat. No. 0,631 (incorporated herein by reference to this disclosure) can also be used, especially when using a mixed monomer feed of acid and ester. Multi-stage in which ethylene, diethylene, triethylene and the like are interconverted by accidental side reactions is also a useful method for controlling the glycol composition as described above.

The sulfopolyester according to the invention is preferably produced using a buffer. Buffers and their use are known in the art, and those skilled in the art are well aware of their use for making sulfopolyesters. 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 up to 0.2 mole per mole of bifunctional sulfomonomer. Preferably,
The buffer is present in an amount of about 0.1 mole per mole of bifunctional sulfomonomer.

The aqueous dispersion of the water-dispersible sulfopolyester of the present invention can be obtained by adding a molten or solid polymer to sufficiently stirred and heated water.

As mentioned above, the water-dispersible sulfopolyester according to the invention is particularly useful as a textile fiber size due to its improved abrasion and blocking resistance. Furthermore, the sulfopolyesters according to the invention have easy dispersibility and excellent dispersion shelf life stability. Accordingly, one aspect of the present invention relates to a sizing composition for woven yarns made from linear polyester and fibrous articles of manufacture glued therewith.

When fabricating multifilament polyester yarns into a fabric, it is desirable to treat the warp yarns with a sizing composition that bonds and bonds together at least several filaments before weaving. This processing step, known as "glue", gives the yarn strength and abrasion resistance during the weaving step. In most cases, it is also preferred that the sizing composition be completely removable from the woven fabric (sometimes referred to as "desizing"). The increased abrasion resistance results in fewer breaks during the weaving process, improving the quality and process speed of the woven product. Although the above applications have referred to polyester yarns such as poly (ethylene terephthalate) or poly (1,4-cyclohexane dimethylene terephthalate), the compositions described below can be used to glue various natural and synthetic yarns. Can be used as Examples of non-polyester yarns include rayon, acrylic, polyolefin, cotton, nylon and cellulose acetate. Blend of polyester yarn and non-polyester yarn,
It is within the range of fibers that can be effectively glued.

Thus, in another aspect, the invention relates to a method for sizing textile yarns by applying thereto the water-dispersible sulfopolyester of the invention in an aqueous medium. Generally, the woven yarn is combined with the desired concentration (e.g., 1-30% by weight) and temperature (e.g.,
(E.g. 60-100 <0> C) in a water bath containing the sulfopolyester, followed by draining it by passing the woven yarn between rollers, and finally drying the glued yarn in a drying chamber. The tow is then prepared for weaving. Common methods of sizing woven yarns include European systems, classic or British systems and single-ended sizing or Japanese systems.

[0032] In one embodiment, the sized textile yarn is subjected to a desizing operation to remove the sizing composition, followed by a bleaching, drying and finishing operation. In other embodiments, the sizing composition is, for example, known in the art, for example, as described in US Pat.
Permanently applied to the woven yarn by using a crosslinking agent as taught by US Pat. Nos. 67,207 and 3,666,400, which are incorporated herein by reference to their disclosure. .

The sizing composition according to the invention is generally an aqueous dispersion consisting of from about 1 to about 30% by weight, depending on the type of yarn, of the sulfopolyester according to the invention. Various additives are known in the art and are described, for example, in US Pat. No. 3,546,008.
As taught by U.S. Pat.
It can be included in the sizing composition of the present invention. Examples of suitable additives include talc, brighteners, dyes, thickeners, buffers, biocides and stabilizers.

[0034] The sizing composition must have adequate resistance to blocking, which is most important when the fibers are wound on a warp beam or bobbin and stored under long-term environmental conditions. Blocking binds the glued fibers together and prevents them from unwinding at the desired time. The tendency to block under normal and extreme environmental conditions of temperature and humidity may be directly related to the Tg of the glue composition. Thus, a Tg in the range of 25-75C, preferably 30-65C, more preferably 35-60C generally avoids the blocking problem.
Very high (> 75 ° C.) Tg often indicates a brittle sulfopolyester with poor adhesion, productivity and abrasion resistance. Therefore, consideration should be given to the choice of the glycol component. For example, too high a level of PEG disadvantageously lowers Tg,
Causes blocking. In general, as the length or molecular weight of the polyethylene glycol monomer increases, for a given mole percent of content, the Tg of the final polymer decreases proportionately.

Adhesion, flexibility and, in part, desizing and water resistance are also related to the PEG molecular weight and content of the sulfopolyester. As the PEG content increases, the hydrophilicity, flexibility and adhesion also increase. If the PEG content and / or molecular weight is too high, the resulting paste will have a low Tg and insufficient water resistance. The properties of desizing, water resistance, flexibility and adhesion are also related to the sulfomonomer content. If the sulfomonomer level is too high, the water resistance, flexibility and economy of the sizing agent will be reduced, while functionally low levels of the sulfomonomer will tend to impair the adhesion, dispersibility, and after weaving operation Will interfere with proper desizing.

For optimal glue performance, the inherent viscosity of the sulfopolyester is at least 0.25 dL / g, preferably greater than 0.3 dL / g, and the glass transition temperature (
Tg) is at least 25C, preferably 30-65C.

Thus, in a preferred embodiment, the glue material according to the invention comprises a polymer in 100 ml of solvent at 25 ° C. in a solution of 60/40 parts by weight of dry Tg and phenol / tetrachloroethane in the range of 30 to 65 ° C. Has an inherent viscosity of at least 0.1 dL / g, measured at a concentration of about 0.25 g, and (i) terephthalic acid or a derivative thereof; (ii) less than about 5 mol% based on the total moles of acid; not terephthalic acid or its derivative or sulfomonomer, at least one dicarboxylic acid, from about 25 to about 90 mole% in the total mole% basis of (iii) a hydroxyl equivalent weight, the structural _{formula: H- (OCH 2 CH 2)} n At least one polyethylene glycol having the formula —OH (where 2 ≦ n <20) (Iv) is inversely proportional to the value of n), (iv) greater than about 10 mol% but not greater than about 75 mol%, based on total mol% of hydroxyl equivalents.
Less than mol% of glycol or a mixture of glycols that are not polyethylene glycol; and (v) a dicarboxylic acid or derivative thereof containing at least one sulfonate group attached to an aromatic ring, at least one attached to an aromatic ring. At least one difunctional sulfomonomer selected from a sulfonic acid group-containing diol and a hydroxy acid or a derivative thereof containing at least one sulfonate group bonded to an aromatic ring to impart water dispersibility to the sulfopolyester And substantially equivalent molar ratios of the acid molar equivalent (about 100 mol%) and the hydroxyl equivalent (about 100 mol%) such that the sum of the acid equivalent and the hydroxyl equivalent is about 200 mol%. Mol%) of a water-dispersible sulfopolyester.

EXAMPLES The following examples illustrate the scope of the present invention, but are not intended to limit the scope of the invention. The materials and test procedures used for the results presented here are as follows.

The abrasion resistance for the sized yarns was measured using a Duplan Cohesion Tester, as is known to those skilled in the art. The Duplan test is performed on a sample of glued yarn that is polished by a friction plate that moves back and forth over the yarn at a constant speed under a constant tension. The average number of cycles to separate the yarn filaments is reported as abrasion resistance or Duplan value. Thus, a higher Duplan value is a direct indicator of the suitability of the sulfopolyester as a sizing material.

The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC).

The inherent viscosity (IV) is 60/40 for phenol / tetrachloroethane
Measurements were made at 25 ° C. in a weight part solution at a concentration of about 0.25 g of polymer in 100 mL of solvent.

Examples 1 and 2 show the in-situ production of useful glycol combinations. Example 3
FIG. 4 illustrates how buffers can be used to control the glycol composition relative to the feed. Example 4 is a preferred embodiment of the present invention. Examples 5 and 6 are included for comparison to demonstrate the importance of proper glycol selection to obtain a sufficiently high Tg (Example 5) or a processable polymer (Example 6). Example 7 is a comparative example, and Example 8 is a preferred embodiment of the present invention. Example 9 compares the abrasion resistance of the sulfopolyester of Example 1 with a commercially available sulfopolyester glue product. Example 10 is an example of a sulfopolyester using 5 mole% additional acid.

Example 1 11 mol% of 5-sodiosulfoisophthalic acid with 70 mol% of mixed PEG
Preparation of Water-Dispersible Sulfopolyester Containing Ester 86.3 g (0.445) are placed in a 500 mL round bottom flask equipped with a crushed glass head, a stirrer shaft, a nitrogen inlet and side arms to allow for the removal of volatiles.
Mol) of dimethyl terephthalate, 16.3 g (0.055 mol) of dimethyl 5-sodiosulfoisophthalate, 36.0 g (0.58 mol) of ethylene glycol, 44.5 g (0.42 mol) of diethylene glycol And 1.10 mL of n
-A 1.03% (w / v) solution of titanium isopropoxide in butanol was charged. The flask was purged with nitrogen and immersed in a Belmont metal bath for 70 minutes at 200 ° C. and an additional 120 minutes at 210 ° C. with good agitation and a slow nitrogen sweep. After increasing the temperature to 275 ° C., the pressure was increased to 76
The polycondensation was performed by slowly lowering from 0 mm to 0.5 mm over 35 minutes and holding for an additional 85 minutes. The vacuum was then replaced with a nitrogen atmosphere and the clear amber polymer was allowed to cool before being removed from the flask. An inherent viscosity of 0.56 dL / g was determined by ASTM D 3835-79 on the recovered polymer. By NMR analysis, the actual glycol composition was 30 mol% EG,
It was shown that 56 mol% of DEG and 14 mol% of TEG were produced by side reaction. A glass transition temperature (Tg) of 38 ° C. was found for this polymer to have a DS
C obtained from thermal analysis. The polymer was ground to a particle size of ≦ 3 mm.

EXAMPLE 2 11 mol% of 5-sodiosulfoisophthalic acid ester and 82 mol% of mixed P
Preparation of Water Dispersible Sulfopolyester Containing EG The equipment and general procedure described in Example 1 was used except that the polycondensation time was varied. Initial amounts charged to the flask were 86.3 g (0.445 mol) of dimethyl terephthalate, 16.3 g (0.055 mol) of dimethyl 5-sodiosulfoisophthalate, 26.7 g (0.43 mol). Mol) of ethylene glycol, 60.4 g (0
. 57 mol) of diethylene glycol and 1.14 mL of a 1.03% (w / v) solution of titanium (IV) isopropoxide in n-butanol. The polycondensation was performed at 275 ° C. for 120 minutes at a pressure of 0.2 mm Hg. The recovered polymer had an inherent viscosity of 0.55 (ASTM D3835-79) and 34
C. and had a dry Tg measured by DSC. Analysis by NMR indicated that the actual glycol composition was 18 mol% EG, 68 mol% DEG and 14 mol% TEG. The clear yellow polymer was ground to a particle size of ≦ 3 mm.

Example 3 15 mol% of 5-sodiosulfoisophthalic acid ester and 72 mol% of DEG
Preparation of a Water-dispersible Sulfopolyester Containing the Apparatus The general procedure and apparatus described in Example 1 was used except that the transesterification and polycondensation times were varied. The initial reactant charge was 82.5 g (0.425 mol) of dimethyl terephthalate, 22.2 g (0.075 mol) of dimethyl 5-sodiosulfoisophthalate, 11.2 g (0.18 mol) ) Ethylene glycol, 7
6.3 g (0.72 mol) of diethylene glycol, 0.62 g (0.0075)
Mol) of sodium acetate and 0.44 mL of titanium (IV) in n-butanol.
) A 1.46% (w / v) solution of isopropoxide. Polyesterification,
Performed at 200 ° C. for 60 minutes and 230 ° C. for 90 minutes, followed by a polycondensation step of 280
C. and 6 mmHg for 104 minutes. Inherent viscosities and Tg values of 0.39 and 49 ° C., respectively, were obtained in the same manner as above. By NMR analysis, the polymeric acid composition was consistent with 85 mole% terephthalate units, 15 mole% 5-sodiosulfoisophthalate units, while the glycol portion was 28 mole% EG and 72 mole%. DEG.

Example 4 (Example) Production of a water-dispersible sulfopolyester from terephthalic acid 316 SS Parr (Parr) equipped with stirrer, heat transfer coil and distillation column
) In a high pressure reactor, 739.6 g (4.46 mol) terephthalic acid, 147.5 g
(0.55 mol) of 5-sodiosulfoisophthalic acid, 446.1 g (4.2 mol) of diethylene glycol and 360.0 g (5.8 mol) of ethylene glycol were charged. Nitrogen was used to create a pressure of 40 psig, maintaining a temperature of 225 ° C. for 60 minutes, followed by a 80 minute hold time at 245 ° C. 150
Water was removed through a column maintained at ° C. The solid oligomer from the above reaction was removed from the Pall reactor and transferred to a 500 mL round bottom flask equipped with a crushed glass head, stirrer, nitrogen inlet and side arms to allow for the removal of volatiles. After purging the flask with nitrogen, enough catalyst solution was added to give 100 ppm of titanium. The reactor was then placed in a Belmont metal bath for 2 hours.
The polycondensation was performed by immersing the oligomer at 25 ° C. for 10 minutes to melt the oligomer, then raising the temperature to 275 ° C., then reaching a vacuum of 0.6 mm and holding for 35 minutes. The vacuum was replaced using nitrogen to allow the polymer to cool and then was removed from the flask. The polymer was ground to a particle size of ≦ 6 mm prior to analysis. An inherent viscosity of 0.73 dL / g was measured and GC analysis indicated that the glycol composition was 25 mol% EG, 44 mol% DEG, and 31 mol% TEG. A glass transition temperature of 26 ° C. indicates a DSC
From thermal analysis.

Example 5 (Comparative Example) Water containing 7 mol% of 5-sodiosulfoisophthalic acid ester and TEG
The equipment and procedure used was such that the transesterification reaction was carried out at 200 ° C. for 60 minutes and at 230 ° C.
C. for 90 minutes, while the polycondensation was carried out at 280 ° C. and 0.5 mm for 95 minutes. The reactants and their respective amounts are 89.2
g (0.46 mol) of dimethyl terephthalate, 11.8 g (0.04 mol) of 5
-Dimethyl sodiosulfoisophthalate, 150.0 g (1.0 mol) of triethylene glycol, 0.33 g (0.004 mol) of sodium acetate and 0.64
mL of 1.46% of titanium (IV) isopropoxide in n-butanol (w
/ V) solution. The recovered polymer was analyzed in the same manner as described above and gave an inherent viscosity of 0.52 dL / g and a Tg of 4 ° C. By NMR analysis, the polymer structure (total mol% = containing 200 equivalents of acid units and glycol units) was 93 mol% terephthalate, 7 mol% 5-sodiosulfoisophthalate and 100 mol% Of TEG. The low Tg of this polymer will lead to blocking. When dispersed at 30% solids, a cloudy, unstable (ie, separated phase) product was obtained.

Example 6 (Comparative Example) Water containing 30 mol% of 5-sodiosulfoisophthalic acid ester and EG
The equipment and procedures used were such that the transesterification reaction was carried out at 160 ° C. for 120 minutes,
The temperature is then raised to 230 ° C., after which the pressure is increased to 0.35 m for 25 minutes.
Same as Example 1 except that it was gradually reduced to mHg. After a polycondensation time of about 25 minutes, the reaction was stopped when the polymer wrapped around the stirrer due to the very high melt viscosity. The initial reactant charge was 67.9 g (0.35 mol) of dimethyl terephthalate, 44.4 g (0.15 mol) of dimethyl 5-sodiosulfoisophthalate, 62.0 g (1.0 mol) Of ethylene glycol, 0.5 g (0.
006 mol) of sodium acetate, 0.25 g of antimony (III) oxide and 0
. Consisted of 25 g of zinc (II) acetate. Inherent viscosities and Tg values of 0.11 and 97 ° C., respectively, were obtained as before. By NMR analysis, the polymer composition was consistent with 71.5 mole% terephthalate, 28.5 mole% 5-sodiosulfoisophthalate, 91 mole% EG and 9 mole% DEG structural units. The extremely high melt viscosity of this polymer hinders production in typical equipment and is therefore not suitable for the present invention.

Examples 7 and 8 (Examples) Comparison of fiber sizing properties Table I shows comparative fiber sizing properties of the polymers synthesized according to the preceding examples. Both polymers were dispersed in deionized water at a solids level of 30% by weight and diluted appropriately for slashing. A typical procedure for dispersion is to heat water to 80-90 ° C. and shift (sif) into solid pellets with good stirring.
t).

The fiber test was performed by passing a 150 denier warp drawn polyester yarn through an aqueous dispersion of the sizing composition (ie, slush) and drying. The results in Table I show that the inclusion of more than 5 mol% of co-acid (i.e., isophthalic acid) results in a sizing agent having essentially the same anti-blocking properties as a similar composition containing only terephthalic acid. It is shown that. Example 8, the preferred embodiment, has a lower Tg than Example 7, supporting the non-obviousness and effectiveness of the all-terephthalate sulfopolyester as a sizing material. As known to those skilled in the art, lowering the Tg of the sulfopolyester usually increases the tendency to block. Example 7 is outside the scope and teachings of the present invention and is included for the sole purpose of distinguishing these non-obvious teachings from the prior art, while Example 8 is a preferred embodiment of the present invention. The pickup level or amount of dry paste applied to the fibers was essentially constant for both examples.

[0051]

[Table 1]

The blocking test was performed by wrapping 500 meters of glued yarn on a spool and conditioning for 7 days at 40 ° C. and 90% relative humidity. The average force required to break the yarn was determined by sampling the output of the tensiometer 25 times / second for 2 minutes to ensure a high degree of accuracy.
The 3000 readings are averaged and the final blocking value is reported as a value in volts. Values range from 0 to 5, with higher values increasing the amount of blocking.

Example 9 ( Comparative Abrasion Resistance ) A sulfopolyester produced in the same manner as in Example 1 was used in comparison with a commercially available sulfopolyester glue product (Eastman WD Size).
The wear resistance was compared. The results are shown in Table II. In Table II, abrasion resistance is reported as the number of Duplan cycles obtained for the sized natural yarn. It is known that good abrasion resistance is directly related to good weaving efficiency.

[0054]

[Table 2]

The test procedure consisted of stretching the yarn 20 times across the test fixture and passing 417 g of thread back and forth until notice of breakage. Test 3
Performed in cycle increments, failure was associated with the separation of any filament in at least half of the yarn. The higher the number of cycles, the greater the wear resistance.

EXAMPLE 10 Preparation of a Water-Dispersible Sulfopolyester Using Up to 5 Mole% of an Additional Acid Ground Glass Head, Stirring Shaft, Nitrogen Inlet and Sides to Enable Removal of Volatile By-Products 163.0 g in a 1000 mL round bottom flask equipped with an arm
(0.84 mol) of dimethyl terephthalate, 8.3 g (0.05 mol) of isophthalic acid, 32.6 g (0.11 mol) of dimethyl 5-sodiosulfoisophthalate, 91.2 g (0.86 mol) Mol) of diethylene glycol, 71.9 g (1.2 mol) of ethylene glycol and 2.34 mL of titanium (I) in n-butanol.
V) A 0.98% (w / v) solution of isopropoxide was charged. The flask was purged with nitrogen and immersed in a Belmont metal bath for 70 minutes at 200 ° C. and an additional 120 minutes at 210 ° C. with a slow nitrogen flow at a stirring speed of 200 rpm. After increasing the temperature to 275 ° C., the pressure was slowly reduced from 760 mm to less than 1 mm over 25 minutes. The pressure is maintained at less than 1 mm for 13 minutes and 10
mm and held for an additional 34 minutes to complete the polycondensation. The vacuum was replaced using nitrogen and the clear, light yellow polymer melt was allowed to cool before being collected. The resulting glassy polymer had an inherent viscosity of 0.44 dL / g (AST
MD3835-79) and a dry (second run) Tg of 39 ° C. Analysis by hydrolysis GC showed that the actual glycol composition was 32 mol% EG, 56
It was shown to be mole% DEG and 12 mole% TEG.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Menturo, Bernard J. Inventors. 37664, Tennessee, USA, Kingsport, Lotiel Court 4520 F-term (reference) 4J029 AA03 AB01 AC02 AD01 AD07 AE18 BA02 BA03 BA04 BA05 BA07 BA08 BA09 BA10 BB13A BD02 BD07A BF08 BF09 BF25 BH02 CA02 CA04 CA05 CA06 CA09 CB05 CD06 CF08 CH02 DB02 DB06 DB13 GA13 GA14 GA17 HB01 HB03A 4L033 AB05 AC12 CA45

Claims (20)

[Claims] 1. having an inherent viscosity of at least 0.1 dL / g, measured in a 60/40 parts by weight solution of phenol / tetrachloroethane at 25 ° C. at a concentration of about 0.25 g of polymer in 100 ml of solvent; (Ii) at least one dicarboxylic acid that is not terephthalic acid or a derivative thereof or a sulfomonomer, less than about 5 mole%, based on the total moles of acid; (iii) hydroxyl equivalents from about 25 to about 90 mole% in the total mole% basis, the structural formula: _{H- (OCH} 2 _CH 2) in n -OH (wherein, a 2 ≦ n <20, mole% of the polyethylene glycol present is, n
(Iv) more than about 10 mol% but not more than about 75 mol%, based on the total mol% of hydroxyl equivalents.
Less than mol% of glycol or a mixture of glycols that are not polyethylene glycol; and (v) a dicarboxylic acid or derivative thereof containing at least one sulfonate group attached to an aromatic ring, at least one attached to an aromatic ring. At least one difunctional sulfomonomer selected from a sulfonic acid group-containing diol and a hydroxy acid or a derivative thereof containing at least one sulfonate group bonded to an aromatic ring to impart water dispersibility to the sulfopolyester And the molar equivalents of the acid (about 100 mol%) and the hydroxyl equivalent (about 100 mol%) such that the sum of the acid and hydroxyl equivalents is equal to about 200 mol%.
(Approximately 100 mol%). 2. The terephthalic acid or its derivative component (i) is selected from the group consisting of terephthalic acid, dimethyl terephthalate and a mixture thereof, and the dicarboxylic acid component (ii) is succinic acid, glutaric acid, adipic acid, azelaic acid. , Sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, 2,5
-From norbornane dicarboxylic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenic acid, 4,4'-oxydibenzoic acid, 4,4'-sulfonyldibenzoic acid and mixtures thereof Wherein the value of n in the polyethylene glycol component (iii) is 2 ≦ n ≦ 10, and the glycol component (iv) is selected from aliphatic glycols, alicyclic glycols, aralkyl glycols, and mixtures thereof. The sulfopolyester according to claim 1, wherein the difunctional sulfomonomer component (v) is selected from the group consisting of: a dicarboxylic acid containing at least one sulfonate group bonded to an aromatic ring or a derivative thereof. 3. The terephthalic acid or derivative thereof is selected from the group consisting of terephthalic acid and dimethyl terephthalate, wherein the terephthalic acid or dimethyl terephthalate is present in an amount of more than 60 mol% based on the total acid equivalent, and the polyethylene glycol component (iii) is in an amount of 80 to 50 mol%. Is present, the value of n is 2 ≦ n ≦ 6, and the glycol component (iv) is ethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 2,4- Dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1 1,3-propanediol, 1,3-butanediol, 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 Selected from the group consisting of 2,4-tetramethyl-1,3-cyclobutanediol and p-xylylenediol, present at 20-50 mol% based on total hydroxyl equivalents, and wherein the difunctional sulfomonomer is sulfophthalic acid And esters thereof, sulfoterephthalic acid and esters thereof, sulfoisophthalic acid and esters thereof, 4-sulfonaphthalene-2,7-dicarboxylic acid and esters thereof, 5-sodiosulfoisophthalic acid and esters thereof, and mixtures thereof. From about 6 to about 40 moles on a total acid equivalent basis. The sulfopolyester of claim 1 which is present in percent by weight. 4. The sulfopolyester according to claim 1, wherein the sulfopolyester is free of terephthalic acid or a derivative thereof or any dicarboxylic acid that is not a sulfomonomer. 5. The sulfopolyester of claim 3, wherein the difunctional sulfomonomer is 5-sodiosulfoisophthalic acid or an ester thereof, and is present in an amount of about 8 to about 30 mole percent, based on total acid equivalents. 6. The sulfopolyester of claim 5, wherein the bifunctional sulfomonomer is present in an amount from about 9 to about 25 mole percent, based on total acid equivalents. 7. The glycol component (v) is selected from the group consisting of diethylene glycol, triethylene glycol and tetraethylene glycol.
The sulfopolyester according to the above. 8. The sulfopolyester of claim 1 having an inherent viscosity of at least 0.25 dL / g and a Tg of at least 25 ° C. 9. The sulfopolyester of claim 1 wherein the inherent viscosity is at least 0.3 dL / g and the Tg is in the range of 25 ° C. to 75 ° C. 10. The sulfopolyester according to claim 1, wherein the Tg is in the range of 30 ° C. to 65 ° C. 11. A sizing composition comprising from about 1 to about 25% by weight of the sulfopolyester of claim 1. 12. A fibrous article glued with the sizing composition comprising the water-dispersible sulfopolyester according to claim 1. 13. having an inherent viscosity of at least 0.1 dL / g in a 60/40 parts by weight solution of phenol / tetrachloroethane, measured at 25 ° C. at a concentration of about 0.25 g of polymer in 100 mL of solvent; (Ii) at least one dicarboxylic acid that is not terephthalic acid or a derivative thereof or a sulfomonomer, less than about 5 mole%, based on the total moles of acid; (iii) hydroxyl equivalents from about 25 to about 90 mole% in the total mole% basis, the structural formula: _{H- (OCH} 2 _CH 2) in n -OH (wherein, a 2 ≦ n <20, mole% of the polyethylene glycol present is, n
(Iv) more than about 10 mol% but not more than about 75 mol%, based on the total mol% of hydroxyl equivalents.
Less than mol% of glycol or a mixture of glycols that are not polyethylene glycol; and (v) a dicarboxylic acid or derivative thereof containing at least one sulfonate group attached to an aromatic ring, at least one attached to an aromatic ring. At least one difunctional sulfomonomer selected from a sulfonic acid group-containing diol and a hydroxy acid or a derivative thereof containing at least one sulfonate group bonded to an aromatic ring to impart water dispersibility to the sulfopolyester And the molar equivalents of the acid (about 100 mol%) and the hydroxyl equivalent (about 100 mol%) such that the sum of the acid and hydroxyl equivalents is equal to about 200 mol%.
Fibrous articles glued with a sizing composition comprising a water-dispersible sulfopolyester comprising about 100 mole%). 14. The sizing composition has a Tg higher than 25 ° C. and at least 0
. 14. The fibrous article according to claim 13, having an inherent viscosity of 25 dL / g. 15. The sizing composition having a Tg of from about 30 to about 65 ° C.
4. The fibrous article according to 3. 16. The sizing composition having a Tg of from about 35 to about 60 ° C.
4. The fibrous article according to 3. 17. The fibrous article according to claim 21, wherein the sulfopolyester has an inherent viscosity greater than 0.3 dL / g. 18. A method of sizing a woven yarn comprising contacting the woven yarn with a sizing composition comprising the water-dispersible sulfopolyester of claim 1 in an amount effective to sinter the woven yarn. . 19. The method according to claim 18, comprising the steps of weaving the glued textile yarn and subsequently desizing the glued textile yarn to remove the gluing composition. 20. The method according to claim 18, wherein the sizing composition is permanently applied to the woven yarn.
The method described in.