KR101900842B1 - Polyester composition with improved dyeing properties - Google Patents

Abstract

The present invention discloses a copolymer composition having advantages for textile fibers, yarns, blends, fabrics and garments. The composition comprises about 4.5% to 5.5% adipic acid, about 630 to about 770 ppm of pentaerythritol based on the amount of the copolymer, and about 770 ppm of adipic acid, based on the amount of the copolymer, Based on the amount, about 3.4% to 4.2% of polyethylene glycol.

Description

[0001] POLYESTER COMPOSITION WITH IMPROVED DYEING PROPERTIES [0002]

Related application

This application claims the benefit of Serial no. 15 / 258,308, "Polyester compositions with improved dyeing properties ".

The present invention relates to polyester copolymer compositions suitable for synthetic filaments and to fabrics and fabrics that can be made from such compositions. More particularly, the present invention relates to a composition for making fibers that can be blended and stained with cotton under more favorable conditions than cotton.

The use of the synthetic composition is then well established in the production of filaments, fibers and fabrics. Thus, improvements in such established compositions may be particularly advantageous. Of course, this improvement is even more valuable when increasing the desired characteristics of filaments, fibers, fabrics and items derived from such compositions - very often clothing.

Conversely, garments are typically formed from a yarn woven or knitted fabric. That is, the yarns are formed from individual fibers that are joined together, and are most commonly formed using a well-known and well-established spinning process.

Natural fibers - the most common of which are cotton and wool - have characteristics that create the properties desired in yarns, fabrics and clothing. For example, wool (among other benefits) has excellent thermal properties and maintains insulation even when wet. However, unless properly treated, the wool can become worn upon contact with the skin for extended periods of time, thus giving a feeling of discomfort. The cotton forms a comfortable and breathable fabric, but may lose its insulating properties when wet. Additional advantages of cotton, wool and other natural fibers are generally well understood in the art.

In the same way, synthetic fibers have some characteristics that are subjectively better than natural fibers, and some of these properties (especially in the case of polyester) may be strength, durability and "memory" and the like.

Thus, one of the goals of fabricating, designing or developing synthetic compositions to be used as fibers, yarns and fabrics, on the one hand, is, on the one hand, to be as close as possible to the desired characteristics of the natural fibers, The use of some of the desirable properties of the composition (e.g., to make the insulation of the wool less wearable, but to use the comfort of the face, but to have better thermal properties when wet).

In the apparel industry, the ability to make garments of the desired color is a fundamental goal. However, the nature of both natural and synthetic fibers and their underlying chemical composition require that the hue be obtained by some type of dyeing process. Depending on the situation, the fibers can be dyed as fibers, filaments, yarns, fabrics or even garments. Moreover, in many cases, because consumers expect the garment to be able to be cleaned and dried from the machine several times, the related object is to provide a garment capable of withstanding such repeated machine washing and drying, while still retaining most or all of the desired color ≪ / RTI > Relevant purposes include exposure to sweat, light fastness (typically associated with exposure to sunlight) and color stability (using another example of activewear).

Fundamentally, the relationship between the color of the garment and its lifetime will be based on the chemical composition of the base fibers and the chemical composition of a suitable dye composition. As will be appreciated by those skilled in the art, dyes are technically defined as " colorants that are " molecularly dispersed at some point during application to a substrate and exhibit some degree of permanence. Tortora, FAIRCHILD'S DICTIONARY OF TEXTILES, Seventh Edition, 2009 Fairchild Publications.

Dyes are typically categorized as natural dyes (e.g., from plants) or synthetic dyes (e.g., developed from other compositions, typically using principles and techniques of organic chemistry).

The dyeing characteristics of the fibers are based on the composition in which the fibers are formed. The desired property is referred to as "dyeability ", which is defined as" the ability of the fiber to accept dye "(Tortora, supra).

In the manufacture of garments, it is also common to blend synthetic fibers with natural fibers at a rate that produces finished garments with the desired characteristics. For a number of reasons, blends of cotton and polyester have long been popular. On this basis, compositions and methods for producing dyed colors in cotton-polyester blends have been and have been desired results. However, the nature of the two different fibers presents a practical problem. For example, the face may conveniently be dyed with a "reactive dye" that can be successfully added to the face substrate at a temperature of about 66 DEG C (150 DEG F).

On the other hand, the properties of the polyester (i. E., The condensation esterification of terephthalic acid with ethylene glycol and the polymer formed from the subsequent polymerization) are such that the polyester is a "disperse dye ", i.e., small particles of a colorant suspended in water . ≪ / RTI >

Coloring of the polyester with disperse dyes results in significantly higher temperatures; But typically tend to require more than 120 ° C (250 ° F), frequently more than 132 ° C (270 ° F). In many cases, high pressure (i. E., Above atmospheric pressure) is also required to reach the temperature required to successfully dye the polyester or dye the polyester.

As an additional comparative factor, cotton dyeing tends to be performed by the pH of the dye solution or composition (typically in a basic environment); On the other hand, polyester dyeing tends to be performed by temperature and usually requires the addition and performance of auxiliary chemicals commonly referred to as "carrier" or "leveling agent ". From an economic point of view, disperse dyes (sometimes referred to as "high energy" dyes due to the requisite conditions) are more expensive than reactive dyes and are often 5 to 10 times more expensive by comparison.

Due to differences in dye composition and dyeing conditions, it is common practice to individually dye cotton and polyester.

In some conventional methods, cotton-polyester blend fabrics are dyed in two separate steps. In a first step, the fabric is dyed in a weakly acidic bath (e.g., using disperse dyes) at a temperature of about 132 ° C (270 ° F) or higher to allow the polyester to accept the dye. The partially dyed fabric is then washed or rinsed and then dyed in cotton-free dyes (e.g., direct dyes or reactive dyes) at a basic pH and a temperature of about 66 ° C (150 ° F). Since many cotton pigments will be degraded at the polyester dyeing temperature, the two steps can not be combined.

As another factor to be solved, high dyeing temperatures tend to degrade the elasticity of stretch fibers such as spandex often contained in cotton-polyester fabrics and garments. Some versions of the spandex are able to withstand high dyeing temperatures (e.g., 132 占 폚 (270 占))), but they are more proportional to versions that have essentially the same end-use properties but tend to deteriorate when stained at these higher temperatures Is more expensive.

As a different factor, the perceived color (eg, of a garment) is a combination of light, the material this light illuminates, and consequently the perception of the human eye. In textile dyeing, the color of the dye is based on the functional group in the dye molecule. To put it another way, the different colors of textile are the function of dye molecules with different compositions. However, not all dye colors (i.e., basic molecules) behave in the same manner as natural or synthetic fibers, yarns and garments. Thus, fibers, yarns, blends or fabrics can accept certain dye colors relatively directly, while rejecting (somewhat) other dye colors under the same conditions.

Moreover, additives are often used to control or adjust the properties of the polymer melt, and the characteristics of such additives are likely to change the dyeing or emissive characteristics, or both.

As another factor, synthetic fibers - and obviously including polyesters - are typically prepared by polymerizing the starting material and then extruding the polymer melt through small openings in a device referred to as a spinneret ; This process is referred to as "spinning. &Quot; Synthetic fibers, and natural fibers, will immediately recognize that the term "radiation" is used to refer to two completely different processes. In one sense (and from ancient times), radiation refers to the step of twisting individual fibers together and pulling them into the yarn. In the production of synthetic fibers, extruding the filaments from the melt into solidified polymer filaments is also referred to as "spinning. &Quot; The difference usually becomes clear in context. Typically, the solidification of the extruded filaments is induced or progressed using a quenching step in which the carefully controlled airflow is directed against the extruded filament.

However, the required properties of the composition that can be melted and radiated in this manner may be independent of, or in combination with, such properties that produce good dyeing characteristics. The properties of the composition that produce a suitable viscosity for the radiation may be completely irrelevant and, in some cases, may be directly contrary to the properties that produced good dyeing characteristics. Thus, designing or adjusting compositions of polymers, copolymers, or copolymer blends to improve the radiation properties may result in less desirable or even unacceptable dyeing properties.

For example, in order to properly "emit ", the molten polymer must have a cohesive (i.e., " watery") viscosity in the spinneret, while avoiding the viscosity too low to accommodate the spinning process for its intended purpose (Viscosity) that allows extrusion to produce liquid filaments (i.e., not separated). Because the viscosity of the polymer melt is proportional to temperature, degree of polymerization and other polymer properties, the spinning temperature must also be appropriate. If stated otherwise, the molten polymer should be capable of performing at the indicated temperature.

In the context of synthetic fibers and their manufacture, the term "melt viscosity" refers to the specific resistance of the molten polymer to deformation or flow under any given condition. The term "inherent viscosity" is used to describe a characteristic that is directly proportional to the average molecular weight of the polymer. The intrinsic viscosity is calculated on the basis of the viscosity of the extrapolated (in solvent) polymer solution to zero concentration. Thus, intrinsic viscosity is a characteristic that affects melt viscosity, but melt viscosity is also related to other factors, especially the temperature of the melt.

As a further factor, since synthetic fibers originate as filaments, such fibers must be cut and textured (not in this order in essence) to obtain other desired properties in the finished yarn, fabric or garment. In most cases, the texturing step requires the synthetic filaments or fibers to be formed mechanically or thermally in a shape other than a straight extruded filament. Thus, the need to texturize the polyester should be responsible for the properties that enhance the polymerization, radiation, or dyeing and add another set of properties that can compete for this property.

Thus, there is a need for a polymer composition that is capable of producing fibers that can be dyed with cotton in a single step.

In one aspect, the present invention is a composition advantageous to textile fibers. In this aspect, the invention relates to a melt of a polyester precursor selected from the group consisting of terephthalic acid, dimethyl terephthalate and ethylene glycol; Adipic acid in an amount sufficient to provide the filaments and fibers made from the melt with a dye that is acceptably similar to the cotton at atmospheric pressure; Pentaerythritol in an amount sufficient to provide a pill resistance to the mixed spinning yarn of fibers and faces prepared from the melt; And polyethylene glycol in an amount sufficient to provide the melt with the elasticity necessary to produce the extruded filaments from the melt. The melt is maintained at a temperature of about 285 DEG C to 295 DEG C (545 DEG F to 563 DEG F) and an intrinsic viscosity of about 0.58 to 0.82.

In another aspect, the present invention is a copolymer composition favorable to textile fibers. In this respect, the present invention relates to polyester copolymers, about 4.5% to 5.5% of adipic acid based on the amount of said copolymer, about 630 to about 730 parts per million (ppm) of pentaerythritol based on the amount of said copolymer ppm and about 3.4% to 4.2% of polyethylene glycol based on the amount of the copolymer.

In another aspect, the present invention is a spinning method of a polyester copolymer filament. The process comprises contacting the terephthalic acid with about 4.5% to 5.5% terephthalic acid, ethylene glycol, adipic acid, about 630 pppm to about 770 ppm pentaerythritol and about 3.4% to 4.2% ethylene glycol, To a copolymer melt containing less than 2% DEG at a temperature of from 295 DEG C (545 DEG F to 563 DEG F); And spinning the resulting polyester copolymer melt into filaments, the proportional amount being based on the amount of polymerized copolymer.

In another aspect, the present invention is a method of coloring a blended yarn from cotton and textured polyester copolymer staple, wherein the yarn is present from about 20% to 80% by weight of cotton. The textured polyester staple comprises from about 4.5% to about 5.5% adipic acid based on the amount of the polyester copolymer, from about 630 ppm to about 770 ppm of pentaerythritol based on the amount of the polyester copolymer, About 3.4% to 4.2% of polyethylene glycol based on the amount of the co-polymer and less than 2% of diethylene glycol based on the amount of the polyester copolymer. The dyeing step is carried out at atmospheric pressure and at temperatures below 212 < 0 > F (100 < 0 > C).

In another aspect, the present invention is a mixed yarn. The spinning yarn contains from about 20% to 80% by weight of cotton, and contains the textured polyester copolymer as the remainder. The textured polyester staple comprises from about 4.5% to about 5.5% adipic acid based on the amount of the polyester copolymer, from about 630 ppm to about 770 ppm of pentaerythritol based on the amount of the polyester copolymer, About 3.4% to 4.2% of polyethylene glycol based on the amount of the co-polymer and less than 2% of diethylene glycol based on the amount of the polyester copolymer.

These and other objects of the invention and the manner in which they are accomplished will become more apparent on the basis of the following detailed description.

Figures 1 to 6 are color photographs of a knitted fabric that is a fabric knit using a control fabric or fibers according to the present invention. The photograph corresponds to the data presented numerically in Tables 3 and 4.
Fig. 7 is an enlarged isolated portion of Fig. 6 showing the difference between a portion of the fabric exposed to light and a portion obscured from the light.
Figure 8 shows a comparison of fabrics made from the present invention using a control fabric and a different leveling agent with the samples of Figures 1-6.

As indicated herein, the object of the present invention is to produce fibers based on polyesters (polyethylene terephthalate) which can be stained with cotton in a single step.

As is well understood in the art, a face is typically dyed with reactive dyes or direct dyes at a temperature of about 66 ° C (150 ° F) (ie, below the boiling point of water) and atmospheric pressure. Polyesters typically and essentially require much higher temperatures (in most cases, greater than 250 DEG F (120 DEG C)), so that pressurized equipment (higher than atmospheric conditions) to penetrate the dye dispersion into the polyester It is dyed with disperse dyes that may be needed. Cotton dyeing tends to be sensitive to pH, while polyester typically requires an additive referred to as a carrier or leveling agent (e.g., a fatty acid derivative) that serves to assist in transferring the dye throughout the substrate material.

In the textile field, terms such as "texturing" and "crimping" are used broadly and specifically. In the broadest sense, texturing and crimping can be performed either mechanically, thermally, or in two ways, such as a synthetic filament, staple fiber or yarn, to have a larger volume than untreated filament, staple or yarn Is used as a synonym to refer to. In a narrower sense, the term crimping is used to describe the fabrication of filaments, fibers or yarns in a two-dimensional tooth orientation, while the term texturing refers to processing to produce looping and curling . The meaning is generally clear in the context. In the specification and claims, the word "texture" is used in a broad sense to include all possibilities for achieving the desired effect in filaments, staple fibers or yarns.

Commonly assigned provisional application serial no. 263, filed March 26, 2014. 61970569 describes compositions comprising adipic acid and diethylene glycol ("DEG") in increased amounts (compared to conventional formulations) to produce a polyester that can be colored with reactive dyes. However, in a further study using the composition, although the '569 composition may accommodate many colors, it will not accept certain colors, examples of which are Huntsman Textile Effects (Charlotte, NC; Dalton, GA; Woodlands, TX) NOVACRON® purple dyes. Thus, although not intending to be bound by any particular theory, a series of comparative tests are performed to determine whether the No. The ingredients in the formulations of the type described in WO98 / 61970569 have been eliminated or alleviated. Based on experience, these tests indicated that higher amounts of diethylene glycol failed to absorb the purple dye in an acceptable amount.

Thus, according to the present invention, it has been unexpectedly found that the presence of more than about 2% of diethylene glycol leads to the problem of dyeing the cotton polyester blend with a predetermined dye color under face-preferential conditions.

Based on the additional test composition and color fastness and color fastness test, 61970569 or other attempts to dye cotton with far better results over a broader range of colors. The improved copolymers maintain adipic acid in an amount of about 4.5% to 5.5%, while maintaining the amount of diethylene glycol (a constant by-product of the esterification of terephthalic acid and ethylene glycol) to less than 2%; Pentaerythritol in an amount of about 630 ppm to 770 ppm; About 3.4% to 4.2% of polyethylene glycol. Each of these amounts is based on their ratio in the finished copolymer.

In the most beneficial compositions to date, adipic acid is present at about 5%, pentaerythritol is present at about 700 ppm, and polyethylene glycol is present at about 3.8%.

(Relatively) higher levels of pentaerythritol increase the reactivity of the polymerization reaction. Thus, conventional expectations are that a lower temperature melt is needed to alleviate this reactivity. However, in the present invention, pentaerythritol and increased reactivity can increase the intrinsic viscosity of the polymer and the total viscosity of the melt. Typically, the intrinsic viscosity of the polyester used in filaments and staple fibers is maintained at about 0.52 to 0.65. Viscous melt tends to be too "watery," and excessively viscous melt tends to separate during extrusion (spinning) from the spinneret.

In the present invention, the intrinsic viscosity is significantly increased, especially about 0.58 to 0.82, with 0.75 being exemplary. Considering that conventional copolymers tend to run at lower intrinsic viscosity, the higher intrinsic viscosity of the present invention is contrary to intuition.

Typically, to properly spin and quench the polymer of lower intrinsic viscosity, the spinning temperature is reduced. In contrast, the composition of the present invention is irradiated at 280 ° C to 290 ° C (536 ° F to 554 ° F) in a higher polymerization reactor at a more common temperature for the polyester produced from the monomers.

Thus, even though the spinning temperature for the copolymer with polyethylene glycol of 4.5% to 5.5% is typically reduced to about 280 ° C (536 ° F), the spinning in the present invention is at the same temperature as the conventional polyester monomer; For example, about 285-290 ° C (545-563 ° F).

The added pentaerythritol reduces the tenacity of the resulting filament, but this feature is advantageous in the present invention because staples made from filaments tend to reduce pilling when blended with cotton.

In particular, the term "peeling" refers to the use of fibers that can occur when the surface of the fabric is worn (including normal wear), as is generally known to those skilled in the art of blending textiles, polyester fibers, It is used to describe small entanglement ("pills"). In cotton-polyester blends, as the strength of the polyester makes it easier for fluffs of the cotton fibers, the fluff formed from the polyester fibers the peeling may be more pronounced because it tends not to allow the peeling of the material to be peeled off, ) Or AATCC Test Methods 124-2014 ("Smoothness Appearance of Fabrics after Repeated Home Laundering").

Table 1 illustrates a number of comparative compositions developed to identify the most advantageous compositions of the present invention. Table 1 contains a series of eight experiments, each of which was designed to produce a 1000 g (1 Kg) batch of polymer. These batches were prepared in a 1 kg NCCATT reactor, after which the filaments were spun on a laboratory scale extruder. These starting materials were polymerized at a temperature of 290 ° C (554 ° F) until a target intrinsic viscosity of 0.620 was reached.

As Table 1 indicates, the starting material included a suitable catalyst and at least one optical brightener (fluorescent whitening agent). Fluorescent luminescent materials are generally well understood in the art and include materials that absorb ultraviolet light (e.g., 360 nm to 380 nm areas) and re-emit blue-purple visible light of longer wavelengths in the visible region of the spectrum ). Such compositions may be selected by those skilled in the art without undue experimentation, provided that the selected luminescent agent does not adversely affect the desired properties of the finished copolymer, fiber or fabric. The starting material also contained small amounts of antimony oxide (0.35 g), 0.02 g of 10% phosphoric acid, and tetramethylammonium hydroxide (0.160 g of 5% aqueous solution).

Table 1 - Preparation of 1000 g batch of copolymer

TA  = Terephthalic acid; EG = ethylene glycol; DEG  = Dai Tilene  Glycol; PEG = polyethylene glycol; OB = fluorescent luminescent agent

Note 1: Esterification  After and before polymerization

The fabric formed from the composition of Table 1 may be dyed according to the following generally conventional manner. The fabric to be dyed is placed in an aqueous solution containing the optional auxiliaries (e. G., Leveling agent and salt), and heated to a dyeing temperature at room temperature for about 25 minutes (e.g., ≪ / RTI > The dye is then added over a period of about 15 minutes (at a liquid ratio of about 10: 1), and then the temperature is allowed to rise to about 90 ° C (195 ° F) for about 30 minutes To move the dye. The temperature is then lowered to about 70 ° C (158 ° F) over an interval of about 10 minutes and held at that temperature for about 35 minutes to fix the dye.

The dyed fabric is then rinsed at about 50 ° C (122 ° F) for about 10 minutes, and potentially rinsed more than once, depending on the overall situation. The fabric is then neutralized using typically weak (e.g., 1% or less) acetic acid at about 71 ° C (160 ° F) for about 10 minutes. The fabric may then be soaked at about 200 DEG F for one cycle or two cycles for 10 minutes, depending on the hardness of the water and the shade of the intended color.

Then rinse the fabric with hot water (about 71 ° C (160 ° F)), rinse with cold water, and rinse for 10 minutes each. The fabric may be treated with a fixative (e.g., a polymeric quaternary ammonium compound is exemplary) and a fabric softener if desired or necessary (e.g., depending on dye hue or other factors).

Of these compositions, PD11 can accommodate high energy dyes at 127-132 DEG C (260-270 DEG F), but will not accept low energy dyes at 96 DEG C (205 DEG F). However, PD12 and PD13 will not accept low energy dyes throughout the fiber. The ability to properly dye with low energy dyes provides significant cost savings because high energy dyes are proportionally more expensive (often 10 times more expensive) than reactive dyes.

Although the present invention is not bound to any particular theory, it is believed that adipic acid provides dye water solubility, pentaerythritol provides pill resistance, and polyethylene glycol provides elasticity to spin the melt into filaments . ≪ / RTI >

Thus, in one aspect, the present invention will be understood to be a composition comprising a polyester, adipic acid, pentaerythritol, polyethylene glycol or a minor amount of diethylene glycol. That is, such a composition can be understood as a polymerized melt, a polyester copolymer filament made from a melt, or a textured filament made from a composition.

Texturing is well known in the art and refers to making filaments that can be textured using the compositions of the present invention so far using conventional steps (e.g., thermosetting, while in a twisted position) It will not be described in detail in detail.

The side of the composition of the present invention may also comprise staple fibers cut from filaments (typically textured filaments), yarns, especially blends of the inventive facets with polyester copolymers, dyed yarns, fabrics, dyed fabrics and garments ≪ / RTI >

In addition, it will be understood that the drying step may be performed on a garment formed from a blended yarn, a fabric formed from blended yards, or even a blended yarn.

In the context of the method, the present invention provides a process for the preparation of a pharmaceutical composition comprising a filling amount of terephthalic acid, ethylene glycol, adipic acid in an amount of about 4.5% to 5.5%, pentaerythritol in an amount of 630 ppm to 770 ppm, polyethylene glycol in an amount of about 3.4% % ≪ / RTI > of diethylene glycol. These amounts are expressed as weight percentages of the components based on the total weight of the finished copolymer.

The filler flows (or until these values are reached) at an intrinsic viscosity of about 0.68 to 0.82 and a temperature of about 285 ° C to 295 ° C (545 ° F to 563 ° F). The melt is spun into filaments in conventional processes.

The filaments produced by this method can be textured, cut into staple fibers, spun with mixed yarns with cotton (typically 5-95 weight percent range), and then dyed as yarns. As another example, a mixed yarn may be weaving or knitting into a fabric, then dyed, and formed into a garment. In some cases, the dyeing step will be performed on the garment, but dyeing of the yarn is probably the most common.

However, those skilled in the art will also appreciate that the filaments can be used as yarns ("filament yarns"), that is, they can be used without being cut with staples or blended with another fiber (eg, cotton). These filament yarns are particularly advantageous for the active industry. In particular, the filament yarns according to the present invention provide the opportunity to use spandex that can be dyed at the dyeing temperature of the present invention (about 96 ° C (205 ° F)) while maintaining all of the desired spandex characteristics. As shown in the background, a variant of spandex that can be stained at high temperatures is available, but it is available at a higher price, and there is no corresponding stretchability or recoverability advantageous for active use purposes.

Because poly-cotton blends are manufactured, sold, and used in varying proportions, a potentially broad range (5-95% cotton) is expressed herein. However, it will be understood that the present invention provides specific advantages to poly-cotton blends that contain a greater proportion (greater than 50%) of polyester, although the present invention clearly provides advantages for high cotton blends.

As already noted, with respect to the composition, in the method step, the best results so far have been achieved using about 5% adipic acid, about 700 ppm pentaerythritol and about 3.8% polyethylene glycol, based on the total weight of the copolymer composition .

In another aspect, the invention can be regarded as a method of dyeing blended yards formed from cotton and textured polyester staples beginning with the compositions described herein. Thus, the dyeing step may comprise from about 5% to 95% by weight of the cotton, together with the polyester comprising adipic acid, pentaerythritol, polyethylene glycol and diethylene glycol in the amounts mentioned in the compositions and methods for the production of filaments Is carried out in the spinning yarn containing.

In another aspect, the present invention is a blended yarn which itself contains about 5-95% by weight of cotton and the remainder of the textured polyester. Textured polyesters have the composition described for other embodiments. For completeness, they contain about 4.5% to 5.5% (e.g., 5%) adipic acid, 630 ppm to 770 ppm (e.g., 700 ppm) pentaerythritol, about 3.4% to 4.2% (e.g., 3.8%) polyethylene glycol, And diethylene glycol by-products less than 2%. These amounts are also based on the weight of the finished copolymer.

As in other embodiments, the yarns may be dyed, formed into fabrics and garments, and dyeing is performed on the blend as opposed to conventional steps of dyeing the surface separately from the polyester.

Thus, using the present invention, the blended fabric can be successfully stained using a single dye. Alternatively, if two dyes are desired, the present invention can be used to maintain all of the two dyes in a single bath so that conventional rinsing or washing between the disperse dyeing step for the polyester and the direct dyeing step for the face the scouring step can be eliminated. That is, the present invention provides the advantage of using less water and producing less waste water.

At manufacture or on a continuing scale, the present invention is expected to be formed and used in a manner that is familiar to those skilled in the art. Thus, as a predicted example, terephthalic acid and ethylene glycol are mixed in a paste (or slurry) at a molar ratio of about 1: 1 to 1.2: 1 (TA: EG). The paste is then transferred to a primary esterification reactor (esterifier) above atmospheric pressure and at a temperature above 250 ° C (typically 260 ° C to 280 ° C). The composition forms esterified monomers, typically representing about 90% esterification. This product can then be transferred to a secondary esterification reactor, where pentaerythritol and adipic acid can be added. The pressure in the secondary esterification reactor is lower than in the primary esterification reactor, but the temperature is slightly higher; For example, from 270 DEG C to 275 DEG C, the esterification reaches (for example) about 94%.

The esterified composition may then be transferred to a low polymerization reactor and, if desired, alternatively, pentaerythritol and adipic acid may be added between the secondary esterification reactor and the low polymerization reactor. The low polymerization reactor is operated at a temperature of about 275 DEG C to 280 DEG C and under vacuum to remove water vapor (polymerization is a condensation reaction), and the monomer reaches a polymerization degree of about 75 to 100. The composition is then transferred to a high polymerization reactor where the polymerization reaches a much higher value, typically about 20,000 units.

The high polymerization reactor typically runs at a temperature of about 270-310 DEG C for a standard PET polymer, and 285-290 DEG C is particularly representative. Conventional copolymers containing polyethylene glycol typically have lower temperatures in this range; For example at about 280 < 0 > C. However, in the present invention, the temperature can be maintained at a higher temperature (e.g., 285-290 ° C) within the standard range, but the intrinsic viscosity will reach about 0.58 to 0.82, and in many cases about 0.75 is preferred.

The intrinsic viscosity is typically measured in a capillary viscometer using a polymer sample dissolved in an appropriate solvent. Alternatively, equipment capable of directly measuring the intrinsic viscosity without the step of dissolving the polymer in a solvent is available. The intrinsic viscosity described herein may be measured, for example, in accordance with ASTM D5225 ("Standard Test Method for Measuring Solution Viscosity of Polymers with a Differential Viscometer") or any test or equipment that provides the same results within acceptable tolerance or error boundaries Can be measured or verified using.

In connection with the present invention (and generally in many cases), color fastness is indicative of the resistance of the dyed color to fading or bleeding under the influence of various types of yarns, fabrics or garments . Exposure to water, light, rubbing, washing and perspiration is typical. The dye fastness test is to confirm the properties of the material in a beneficial and reproducible manner.

In a typical test (AATCC Test Method 61-2013; Colorfastness to Laundering: Accelerated), the fabric color loss due to abrasive action by detergent solution and typical five-hand or household washing with or without chlorine and The surface change is roughly estimated by a one-time test for 45 minutes. The sample is exposed to conditions of abrasion that are expected to result in changes in color due to temperature, detergent, bleaching, and five-hand or home washing. Standard tests were also performed by the Society of Dyers and Colorists (SDC; www.sdc.org.uk; approved on July 24, 2015) and the International Organization for Standardization (ISO; www.iso.org; Approved on July 24, 2015).

Light fastness (i.e., dye fastness under exposure to light) can also be performed using a high energy xenon fade tester under specified conditions of radiation intensity cycle time (contrast) and temperature. AATCC Test Method 169-2009, "Weather Resistance of Textiles: Xenon Lamp Exposure" is a suitable test.

The resulting color difference can be evaluated using standardized gray scale and gray scale test methods (eg, ASTM D2616-12; "Standard Test Method for Evaluation of Visual Color Difference with Gray Scale").

Table 2 provides random Tumble Peeling ("RTP") and Home Laundry ("HL") test results for both the control fabric and the fabric made in the present invention. As shown in Table 2, the PD 13 formulations in Table 1 were used as synthetic constituents representative of the present invention. Testing was performed using ASTM RTP and ASTM D3512 HL (http://www.astm.org/Standards/D3512.htm; approved on March 3, 2016). The test is available on a subscription basis, but typically consists of a standardized rubbing action applied between the sample fabric and the standard fabric. After performing a certain number of rubbing, the sample is inspected to ascertain the number of fluffs formed. Place the fabric on a rectangular block and perform a rubbing motion.

In Table 2, 20/1 is the result of the English cotton count ("Cotton Yarn Count System," Totora). Some fabrics were 50/50 blends of carded sides and synthetic staple fibers and were open ended irradiated and the synthesis was performed according to the invention (PD 13) or the Dupont AKRA control (DuPont-Akra Polyester, LLC, Charlotte, NC 28210, USA). Another fabric was formed from 100% staple or 100% Dupont AKRA polyester (in the case of control) according to the present invention. According to DuPont's Material Safety Data Sheet (MSDS No. DU005415), the composition is a polyethylene terephthalate (CAS number 25038-59-9), a spin finish consisting of about 0.2% to 3% of a lubricant and less than 5% finish).

The third and fourth columns show the test points before the visual inspection, with the grade of the fabric each time, with a higher number being better in the industry.

The home laundry test indicated that the control and the invention were judged to be equivalent from a visual standpoint, or in one case the control was slightly better. However, even if subjective confirmation is granted, the present invention is commercially equivalent to the control group for all practical purposes and provides other advantages as described herein.

The blended fabrics of Figures 3 to 6 were stained using a 1-bath-2-step dyeing process that significantly reduced both the energy and energy. In this dyeing process, water, a disperse dye (for polyester), and a reactive dye (for cotton) were all added together to form a dye solution. In the first step, a weak acid (typically acetic acid) was added to bring the pH to about 5.5 to 6.5. The mixture is then heated to a temperature of about 96 DEG C (205 DEG F); That is, the polyester of the present invention will be dyed but the standard polyester is heated to a temperature at which it will not be dyed.

Salt and caustic (i.e., base, typically sodium hydroxide, NaOH) are added to the same bath so that the reactive cotton dyes And the pH is brought to a basic range (e.g., about pH 8).

This 1-bath-2-step process eliminates the need to empty the dye container ("pot") after the polyester dyeing step and recharge this container for the cotton dyeing step. At a minimum, this provides significant time savings, which becomes progressively more advantageous in the case of repeated dyeing steps. Secondly, since the temperature of the bath can be the same for both cotton and polyester dyeing steps, little heating is required and little time is required for reheating. The result is a fully dyed blend fabric from a single dye bath.

Table 3 and Table 4 are best interpreted as follows. The sample fabric of the table corresponds to the lot number (e.g., "101315A" in FIG. 1) at the upper left corner of FIGS. As a key:

For clarity in the figures, in Figures 1 to 6, respectively, the following reference numerals correspond to the following results: 10-2A washing; 11-3A washing; 12-dry crock; 13-wet crack; 14-cold water bleed; 15-mountain sweat; 16 alkaline sweat; 17-20 hours lightfastness; 18-40 hours lightfastness; 21 acid sweat light fastness; 22 Alkali sweat light fastness; 23 - (FIGS. 3 to 6 in the case of a fabric blend) after removal of the cotton fabric sample color (typically, sulfuric acid, H ₂ SO ₄ by the "combustion (burning)").

Table 3 is a combination of six sub-tables that provide test results for each of the six different fabrics illustrated in Figures 1-6. Thus, the first sub-portion was subjected to a lightfastness test (ISO 105 A05) for 20 hours, then to a lightfastness test for 40 hours, then to an acid stitch test for 20 hours, and then to an alkali stitch test for 10 hours And provides results for.

The second sub-portion of Table 3 corresponds to FIG. 2 (101315B); 3 (101415); 4 (101515); 5 (101615); And Fig. 6 (102215).

In each case, the dEF rating is calculated under ISO 105-A05. In general, ISO 105-A05 is a device test for a series of calculations that evaluates the color change of a test specimen by comparing it to the color change of a control specimen, and then translates the instrument's measurements into a grayscale grade.

The lightfastness test is owned by an international standards body, but is publicly available (ie, not a secret) on a subscription basis. In general, the colorimetry for lightness (L *), chroma (C *), and hue H _AB is measured for control specimens and test specimens, the difference is calculated, To the dEF grayscale level.

Table 4 summarizes similar results for the five types of tests: 2A wash fastness (AATCC 61 CAN / CGSB & ISO 105-C06 Test No BIM), 3A wash fastness (AATCC 61 CAN / CGSB & ISO 105-C06 Test No BIM), cold water bleeding (steeping fabric for a fixed interval in water at 25 ° C), acid sweat fastness: (ISO 105-E04) and alkali sweat fastness (ISO 105-E04).

The sample fabric (corresponding to Figures 1 to 6) is a header row for each of the five sub-tables, including cellulose acetate (CA), cotton (CO), polyester (PES), nylon (PA) Acrylic (PAC) and wool (WO). These are the fabrics of the strip in corresponding parts of the photographs of Figs. 1-6. The results indicate the potential color stability of the fabric when the fabric is formed of one or more of the blends of the present invention and these other types of fibers.

The results of the comparative tests in Table 4 confirm the results in the same way that the photographs illustrate excellent results for (fabric). Values are those obtained from ISO-C06.

Other tests that may be used or used to identify and compare the characteristics of the present invention include one or more of the following.

AATCC 61 is a test developed by the American Association of Textile Chemists and Colorists (Research Triangle Park North Carolina USA). Details of these tests are available from the Association at AATCC.org/test/methods/test-method-61/, approved on March 3, 2016.

These tests evaluate the color fastness with regard to the washing of the textile which is expected to withstand frequent washing. The specimens are tested under conditions of appropriate temperature, detergent solution, bleaching and abrasive action so that the color change is similar to that occurring in the five-hand or home laundry.

The shrinkage test is AATCC 135. In addition, although details thereof are owned, it is generally the case that marking a sample section of the fabric at a selected measuring distance, washing the fabric in a predetermined manner, including drying, and repositioning the mark, As shown in FIG.

Using crocking (AATCC 8), the amount of color transferred from one sample fabric to another by rubbing is checked. The sample fabric to be tested is fixed to a crock meter and rubbed against a white test cloth. This test is performed on both the dry test cloth and then on the wet test cloth. The amount of color transferred to the test cloth is evaluated by comparison with the AATCC chromatic transference scale. Details of the test are owned by AATCC, but are publicly available and well understood by those skilled in the art.

The fabric was also tested under AATCC skewing (skew, skewness) test method 179, which is also owned by AATCC, but is publicly available and well understood by those skilled in the art. These tests confirm the change in skewness in woven and knit fabrics, or twisted garments when treated as a test mimicking repeated automatic washing procedures commonly used in home laundry. These tests define specific cleaning and drying procedures to obtain the measured results. To some extent, the skewness test provides an indication that the course in the fabric or yarn is distorted from their intended manufacturing design.

Color fastness associated with commercial and household hot laundry can also be identified using ISO test number 105-C06. Accurate testing equipment, materials, reagents and procedures are owned by the International Standards Organization (Web address) but are likewise publicly available (subscription or individual purchase costs) and are well understood by those skilled in the art.

Related tests were sweat fastness (ISO 105-E04), water fastness (ISO 105-E01); And light resistance (ISO 105-B02).

Generally, the sweat test is carried out using two standards of simulating sweat, one being weakly acidic (e.g., pH 5.5) and the other being weakly basic (e.g., pH 8.0).

The fabric samples to be tested are brought into contact (often stitched together) with the same non-dyed fabric (often stitched together). This composite sample is then immersed in an acidic or basic solution for about 30 minutes and then held at elevated temperature (e.g., 35-39 DEG C) for about 4 hours under slight pressure.

The complementary test (acid or base) is carried out in exactly the same way. The composite sample can then be separated from the white cloth, dried, and the color change of the sample and dyeing of the white cloth compared to the standardized gray scale.

Figure 8 illustrates the results of a subset of tests performed on dyed fabrics (control and in the present invention) using a leveling agent different from that selected for the samples of Figures 1-6.

In Figure 8, six different fabrics are illustrated (and numbered) according to the top row: Dacron (25) stained with 1% Univadine DLS; (26) stained with 1% Univadine DLS; Dacron (27) stained with 1% Univadine DFM; Inventive (30) stained in 1% Univadine DFM; Dacron (31) stained with 10% Univadine DFM; And the present invention (32) stained with 10% Univadine DFM. Univadine leveling agent is available from Huntsman Textile Effects, 3400 Westinghouse Boulevard Charlotte, NC 28273 USA.

The middle column shows dye residue results based on six non-stained Dacron samples, each of which was placed in a dye bath after the dyeing step. The results are shown in the second column to the extent that the original fabrics 25-27 and 30-32 failed to efficiently absorb the dye. Based on this, less colored results are better than results with paint (or even predominant) color.

They thus show residual dye uptake with corresponding relationships: 25 and 33; 26 and 34; 27 and 35; 30 and 36; 31 and 37; And 32 and 40.

The test sheets 33, 35 and 37 all exhibited an apparent color, indicating that the residual dye remained after the Dacron samples 25, 27 and 31 were stained. The test sheets 34, 36 and 40 are essentially white, indicating much more successful dye absorption by each of the fabric samples 26, 30 and 32 of the present invention.

The bottom row of Figure 8 shows the results of the light resistance test performed on the same fabric for the same comparison purpose. In this column, a relationship exists in each case, and the fabric formed from the composition of the present invention provides excellent results for the Dacron standard.

In the specification, there have been shown preferred embodiments of the invention and, although specific terms have been applied, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being set forth in the claims.

Claims (52)

As a copolymer composition advantageous to textile fibers,
Polyethylene terephthalate copolymers;
Adipic acid;
Pentaerythritol; And
Polyethylene glycol
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Wherein the adipic acid is contained in an amount of 4.5 wt% to 5.5 wt% based on the amount of the copolymer,
The pentaerythritol is contained in an amount of 630 to 770 weight parts based on the amount of the copolymer,
And the polyethylene glycol is present in an amount of from 3.4% by weight to 4.2% by weight, based on the amount of the copolymer. The method according to claim 1,
Diethylene glycol in an amount of less than 2% by weight based on the amount of said copolymer. 3. The method of claim 2,
Wherein the pentaerythritol is present in an amount of 700 weight percent based on the amount of the copolymer. 3. The method of claim 2,
Characterized in that the adipic acid is present in an amount of 5% by weight, based on the amount of the copolymer. The method according to claim 1,
Said polyethylene glycol being present in an amount of 3.8% by weight, based on the weight of said copolymer;
Characterized in that the polyethylene glycol has a molecular weight of 400 grams per mole. 6. A process for preparing the polyethylene terephthalate composition according to any one of claims 1 to 5,
And maintaining the melt at a temperature of 285 DEG C to 295 DEG C and an intrinsic viscosity of 0.58 to 0.82. A textured filament made from the composition according to any one of claims 1 to 5. A yarn made from a blend of cotton fibers and staple fibers cut from textured filaments according to claim 7. As a spinning method of a polyethylene terephthalate copolymer filament,
4.5 wt% to 5.5 wt% of terephthalic acid, ethylene glycol, adipic acid, 630 wt% to 770 wt% of pentaerythritol, and 3.4 wt% to 4.2 wt% of polyethylene glycol with less than 2 wt% diethylene glycol Polymerizing the copolymer melt to form a copolymer melt; And
Spinning the resulting polyester copolymer melt into filaments,
The intrinsic viscosity of the copolymer melt is from 0.58 to 0.82, the temperature is from 285 to 295 占 폚;
Wherein the proportional amount is based on the weight of the polymerized copolymer. 10. The method of claim 9,
Texturing the filament;
Cutting the textured filaments into staple fibers; And
Further comprising the step of spinning the polyester staple with the face to form a blended spun yarn. 11. The method of claim 10,
Further comprising the step of dyeing said blended spun yarn. ≪ Desc / Clms Page number 19 > 10. The method of claim 9,
Terephthalic acid, ethylene glycol, 5 wt.% Adipic acid and pentaerythritol were added to a copolymer melt at an intrinsic viscosity of 0.75 and a copolymerization temperature of 285 DEG C to 295 DEG C, including 3.8 wt.% Polyethylene glycol and less than 2 wt.% Diethylene glycol Wherein the polyester copolymer filament is a polyester film. 17. A method of coloring a yarn, comprising dyeing the yarn according to claim 10 by performing a dyeing step at atmospheric pressure and a temperature lower than 100 < 0 > C. 14. The method of claim 13,
Dyeing the yarn,
Wherein the polyester staple is a polyester staple,
Based on the weight of the polyester copolymer, 5% by weight of adipic acid,
Based on the weight of the polyester copolymer, 700 weight parts of pentaerythritol,
3.8% by weight of polyethylene glycol based on the amount of the polyester copolymer, and
Based on the amount of the polyester copolymer, less than 2% by weight of diethylene glycol
By weight based on the total weight of the yarn. spandex; And
Polyester copolymer filament
The fabric fabric comprising:
In the polyester copolymer filament, the copolymer composition
Polyester copolymers;
4.5 to 5.5% by weight, based on the amount of the copolymer, adipic acid;
Based on the amount of the copolymer, 630 weight parts to 770 weight parts of pentaerythritol; And
Based on the amount of the copolymer, from 3.4% by weight to 4.2% by weight of polyethylene glycol,
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