WO2017010024A1

WO2017010024A1 - Modified polyester fiber, opal finished woven and knitted fabric containing the fiber, and method for producing same

Info

Publication number: WO2017010024A1
Application number: PCT/JP2015/081399
Authority: WO
Inventors: 純哉今北; 弘美西古; 和弘堂前
Original assignee: 三菱レイヨン・テキスタイル株式会社
Priority date: 2015-07-15
Filing date: 2015-11-06
Publication date: 2017-01-19
Also published as: TWI612190B; TW201702444A; EP3323913A4; EP3323913A1; US20180209074A1; JP6515715B2; JP2017020147A

Abstract

Provided is a modified polyester fiber which is used as a fiber having reduced weight, the modified polyester fiber comprising ethylene terephthalate as a primary constituent unit and being obtained by copolymerizing 12-25 mol.% of an aliphatic dicarboxylic acid having 4-8 carbon atoms and 2-5 mol.% of a metal sulfonate group-containing aromatic dicarboxylic acid. This modified polyester fiber has a single fiber fineness of 0.6-3.5 dtex. In a mixed woven and knitted fabric comprising two or more types of fiber consisting of the modified polyester fiber and a regular polyester fiber and, optionally, a polyurethane fiber, good opal finish properties can be achieved by an opal finish agent that contains sodium carbonate and, for example, a Mei printer OP-2 (manufactured by Meisei Chemical Works, Ltd.), which is an opal finish accelerator, and a reduction in strength of non-opal finished parts is also low.

Description

Modified polyester fiber, discharge-processed woven or knitted fabric containing the same, and method for producing the same

[Technical Field] The present invention relates to an alkali-dissolvable polyester fiber having high dischargeability, a discharge-processed woven or knitted fabric containing the fiber, and a method for producing the woven or knitted fabric.

In general, the discharge process is to remove the embrittlement and removal of high-exhaustable fibers by imprinting the extractive paste in a pattern on a woven or knitted fabric consisting of two or more types of fibers, high-extractable fibers and difficult-extractable fibers. It is also called opal processing and is widely known as processing for forming a watermark pattern or a highly stretchable part. The chemical reaction in the removal process varies depending on the type of fiber. For example, a method for removing polyester fibers is also called alkali weight loss, and is alkali hydrolysis using sodium hydroxide, potassium hydroxide, or the like. On the other hand, for removal of cellulosic fibers such as cotton and acetate, acid hydrolysis, carbonization and dissolution with a hot organic solvent are used.

As a discharging process for woven and knitted fabrics made of polyester fibers, we use a pattern to print a discharging paste on woven and knitted fabrics made of modified polyester fibers with high dischargeability and unmodified polyester fibers with low dischargeability. It is known to remove highly modified polyester fibers, and a method is known in which a paste liquid containing sodium hydroxide or potassium hydroxide is printed and heat-treated as a pitting agent.

However, the method using sodium hydroxide or potassium hydroxide, which is used for the removal processing utilizing the difference in hydrolyzability between modified polyester fiber with high pitting property and unmodified polyester fiber with low pitting property, is not yet available. There is a problem that even the modified polyester fiber may be embrittled, leading to a decrease in strength and poor discharge. Moreover, since sodium hydroxide and potassium hydroxide are strong alkaline substances, they are highly toxic and irritating to humans and have a high impact on the aqueous environment.

On the other hand, in order to improve the dyeability of polyethylene terephthalate fibers that are dyed at high pressure and high temperature with disperse dyes and to enable dyeing by atmospheric dyeing using disperse dyes and cationic dyes, 0.1% of 5-sodium sulfoisophthalic acid is added to polyethylene terephthalate. Modified polyester fibers obtained by copolymerizing 4 to 5 mol% and 2 to 15 mol% of adipic acid are disclosed in, for example, JP-A-61-239015 (Patent Document 1) and JP-A-8-269820 (Patent Document 1). Document 2), Japanese Patent Application Laid-Open No. 2013-18802 (Patent Document 3), and the like.

Such modified polyester fibers are used in combination with polyethylene terephthalate fibers with high chemical resistance in opal processing and fibers with low chemical resistance in addition to diversification on the dyed surface due to the spread of applicable dyes. There is also. However, with conventional modified polyester fibers, the removal resistance by alkali at the time of opal processing is still not fully satisfactory, and for the purpose of diversification of opal processed products, more removal removal is performed while maintaining the fiber properties as much as possible. Therefore, there is a demand for a modified polyester fiber that is easy to use.

Further, for example, according to Japanese Patent Laid-Open No. 2000-096439 (Patent Document 4), in the process of removing a modified polyester fiber from a woven or knitted fabric made of a modified polyester fiber and an unmodified polyester fiber, a discharge containing guanidine carbonate is performed. Exhaust processing using a processing agent has been proposed. However, in the erosion processing with guanidine carbonate, the denatured polyester has good pitting property, but there is a problem that the unmodified polyester becomes brittle and causes strength reduction.

Furthermore, for example, in Japanese Patent Application Laid-Open No. 2000-282377 (Patent Document 5), a quaternary ammonium salt is used in the discharge processing of a modified polyester fiber for a woven or knitted fabric containing an atmospheric pressure cationic dyeable polyester fiber as an essential component. There has been proposed a method of printing a paste liquid containing, removing alkali by weight reduction after heat treatment, and removing modified polyester fibers. However, there is a problem that the strength of the modified polyester fiber and the unmodified polyester fiber cannot be maintained because it is an alkali weight reduction process using sodium hydroxide.

Still further, for example, in Japanese Patent Application Laid-Open No. 2008-038332 (Patent Document 6), in the process of discharging a modified polyester fiber to a woven or knitted fabric composed of a modified polyester fiber and an unmodified polyester fiber, guanidine carbonate, caustic soda, caustic potash by inkjet printing is used. It has been proposed to perform a removal process by attaching a removal agent containing at least one. The discharge processing is performed by controlling the amount of the removal agent applied by inkjet printing, but in order to maintain the strength of the unmodified polyester fiber, the fineness of the unmodified polyester fiber is increased, or the core part Is a non-modified polyester fiber, a sheath yarn is a modified polyester fiber composite yarn, and the removal processing agent is attached only to the modified polyester fiber. There is a problem that cannot be prevented. *

Further, for example, according to International Publication No. 2007/086593 (Patent Document 7), the fabric to be subjected to the removal process is composed of non-elastic fibers and elastic fibers, and the non-elastic fibers may be cationically acceptable as a dischargeable fiber. Dyed polyester fiber and non-exhaustable nylon fiber are used, ether-based polyurethane fiber is used for elastic fiber, and if sodium hydroxide is used as an extraction processing agent, it is not subject to extraction. There is a problem that the cationic dyeable polyester fiber and the polyurethane fiber are eroded and the stretchability and strength are lowered.

JP-A 61-239015 JP-A-8-269820 JP 2013-18802 A JP 2000-096439 A JP 2000-282377 A JP 2008-038332 A International Publication No. 2007/086593

One of the objects of the present invention is to provide an easily soluble alkali-modified polyester fiber which is used as a fiber having low chemical resistance in opal processing and can be easily removed by alkali. Although it is a copolymer component that has been known to have an effect of modifying the dyeability of polyethylene terephthalate fiber, the use of a specific amount of aliphatic dicarboxylic acid and metal sulfonate group-containing aromatic dicarboxylic acid improves dyeability. In addition, the present inventors have found that it is possible to obtain an alkali-soluble solubility that is easy to remove and remove while maintaining the quality effect.

In addition, as described above, in the discharging process for discharging the modified polyester fiber, sufficient discharging is not performed unless it is a strong alkali, and conversely, if a strong alkali is used, the strength of the discharged cloth decreases. is there. In view of this situation, one of the other objects of the present invention includes unmodified polyester fibers that can be easily discharged even with a weak alkali, using modified polyester fibers having sufficient discharging performance. It is also an object of the present invention to provide a highly evacuated woven or knitted fabric having a high evacuation property and a method for producing the same, in which a decrease in strength of fibers other than the erosion portion is avoided.

In the prior art, a strong alkaline substance such as sodium hydroxide or potassium hydroxide is used in the removal paste to prevent embrittlement of the unmodified polyester fiber in the removal processing of the woven or knitted fabric of the modified polyester fiber and the unmodified polyester fiber. It has been studied that an alkali weight loss accelerator is heat-treated without printing, and the alkali weight loss of the printed portion is promoted when the alkali weight is reduced after the heat treatment. However, the present inventors have paid attention to further modification of the modified polyester fiber, and as a result of various examinations and experiments, a certain modified polyester fiber is strongly alkaline such as sodium hydroxide or potassium hydroxide. It has been found that alkali weight reduction can be carried out in a specific pH region only with a modified polyester fiber without using a substance and without affecting the strength of unmodified polyester fiber or polyurethane fiber.

The modified polyester fiber of the present invention is a modified polyester fiber having a weight loss rate of 5% to 15% obtained by the following measurement method.
<Method for measuring fiber weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100

The modified polyester fiber of the present invention comprises ethylene terephthalate as a main constituent unit, 12 to 25 mol% of an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and 2 to 5 mol% of a metal sulfonate group-containing aromatic dicarboxylic acid. It is preferably made of a modified polyester copolymerized in an amount of not more than mol%.

In the modified polyester fiber of the present invention, the aliphatic dicarboxylic acid is preferably adipic acid and the metal sulfonate group-containing aromatic dicarboxylic acid is preferably 5-sodium sulfoisophthalic acid.

The modified polyester fiber of the present invention preferably has a diethylene glycol content of 0.5% by mass or more and 3.0% by mass or less.
The modified polyester fiber of the present invention has a single fiber fineness of 0.6 dtex to 3.5 dtex, a fiber strength of 2.0 cN / dtex to 3.5 cN / dtex, and a fiber elongation of 25% to 45%. It is preferable.
In the modified polyester fiber of the present invention, the modified polyester fiber preferably contains lithium acetate and diethylene glycol, and the lithium acetate content is preferably 50 to 120 ppm in terms of the amount of lithium atoms.

The woven or knitted fabric of the present invention comprises a modified polyester fiber having a weight loss rate of 5% to 15% and a non-weight loss fiber having a weight loss rate of 0% to less than 5% obtained by the following measurement method. In the knitted fabric, the content of the modified polyester fiber with respect to the woven or knitted fabric is 5% by mass or more and 50% by mass or less, and the content of the non-reduced fiber is 50% by mass or more and 95% by mass or less.
<Method for measuring fiber weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100

The woven or knitted fabric of the present invention comprises a modified polyester fiber having a weight loss rate of 5% or more and 15% or less obtained by the fiber weight loss rate measuring method and a non-weight loss fiber having a weight loss rate of 0% or more and less than 5%. A woven or knitted fabric having a discharge portion of the modified polyester fiber, wherein the weight loss rate of the modified polyester fiber in the discharge portion is 50 with respect to the modified polyester fiber in the non-discharge portion. It is not less than 100% by mass.
In the woven or knitted fabric of the present invention, it is preferable that the difference between the weight loss rate of the modified polyester fiber and the weight loss rate of the non-exhaust fiber is 5% or more.

In the woven or knitted fabric of the present invention, it is preferable that the burst strength of the woven or knitted fabric in the discharged portion is 250 kPa or more and 900 kPa or less.
In the woven or knitted fabric of the present invention, it is preferable that the strength retention of the rupture strength of the eroded portion of the woven or knitted fabric with respect to the rupture strength of the non-extracted portion of the woven or knitted fabric is 50% or more.

In the woven or knitted fabric of the present invention, the modified polyester fiber has ethylene terephthalate as a main constituent unit, an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and an aromatic dicarboxylic acid containing a metal sulfonate group. The modified polyester is preferably copolymerized in an amount of 2 mol% or more and 5 mol% or less.

In the woven or knitted fabric of the present invention, the non-reducing fiber preferably contains 50% by mass or more and 95% by mass or less of synthetic fiber.
In the woven or knitted fabric of the present invention, the synthetic fiber is preferably any one or more of regular polyester fiber, polyamide fiber, elastic fiber, polyolefin fiber, and acrylic fiber.

In the woven or knitted fabric of the present invention, the single fiber fineness of the modified polyester fiber is preferably 0.6 dtex or more and 3.5 dtex or less.
In the woven or knitted fabric of the present invention, the elastic fiber is preferably made of any one of polyurethane fiber, polytrimethylene terephthalate fiber, and polybutylene terephthalate fiber.

The method for producing a woven or knitted fabric according to the present invention is a method for removing a weight loss from a fiber containing a modified polyester fiber having a weight loss rate of 5% to 15% and a non-weight loss fiber obtained by the fiber weight loss rate measuring method. Is a method of manufacturing a knitted or knitted fabric that is subjected to weight loss processing by applying superheated steam to a portion printed with a removal processing agent, wherein the pH of the removal processing agent is 8 or more and 13 or less, and the heating method is The superheated steam at 150 ° C. or more and 200 ° C. or less, and the heating time is preferably 5 minutes or more and 15 minutes or less.

According to the present invention, in the removal processing of a woven or knitted fabric containing a modified polyester fiber, the strength of the modified polyester fiber other than the discharged portion does not decrease, and the woven or knitted fabric containing a fiber other than the modified polyester fiber is removed. It is possible not to cause a decrease in strength of the extracted portion, and at the same time, a good discharging effect can be obtained. According to the present invention, it is possible to obtain a discharge-processed product in which the modified polyester fiber is excellently discharged and the strength is not reduced.

If the weight loss ratio of the modified polyester fiber of the present invention is 5% or more, the weight can be easily reduced with an alkali, and the deterioration of the physical properties of the non-weight loss fiber can be reduced. Moreover, if the said weight loss rate is 15% or less, there will be little intensity | strength fall of the modified polyester fiber of this invention, and it can reduce thread breakage in the manufacturing process of a woven / knitted fabric.
From the above viewpoint, the fiber weight loss rate is more preferably 7% or more and 13% or less, and further preferably 8% or more and 11% or less.

The modified polyester fiber of the present invention comprises ethylene terephthalate as a main constituent unit, 12 to 25 mol% of an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and 2 to 5 mol% of a metal sulfonate group-containing aromatic dicarboxylic acid. It is preferably made of a modified polyester copolymerized in an amount of not more than mol%.
In the modified polyester fiber of the present invention, the aliphatic dicarboxylic acid is preferably adipic acid and the metal sulfonate group-containing aromatic dicarboxylic acid is preferably 5-sodium sulfoisophthalic acid.

The aliphatic dicarboxylic acid having 4 to 8 carbon atoms, which is a copolymerization component, increases the alkali solubility of the polyester fiber by disturbing the amorphous structure of the fiber. Examples of the aliphatic dicarboxylic acid having 4 to 8 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid, with adipic acid being particularly preferred.

The copolymerization amount of the aliphatic dicarboxylic acid having 4 to 8 carbon atoms is 16 mol% or more and 25 mol% or less, preferably 18 mol% or more and 20 mol% or less. By suppressing the remarkable deterioration of the characteristics and disturbing the amorphous structure of the fiber, not only contributes to the improvement of the dyeability by the disperse dye and the cationic dye, but also significantly increases the alkali solubility of the fiber. If the aliphatic dicarboxylic acid having 4 to 8 carbon atoms is 16 mol% or more, it is easy to obtain alkali-soluble solubility suitable for opal processing, and if it is 25 mol% or less, it is necessary for use as a fiber. Thermal properties such as fiber properties, fastness and heat resistance are easily maintained.

The metal sulfonate group-containing aromatic dicarboxylic acid, which is the other copolymerization component, introduces a metal sulfonate group into the fiber to serve as a dyeing seat for the cationic dye, and allows the polyethylene terephthalate fiber to be dyed at atmospheric pressure with the cationic dye. It is a component. In addition, the metal sulfonate group is introduced into the fiber together with the aromatic ring, so that the dyeing property for the disperse dye is improved and the dyeing temperature can be lowered. Furthermore, it contributes to the improvement of the alkali solubility of the fiber. Examples of the metal sulfonate group-containing aromatic dicarboxylic acid include 5-sodium sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium sulfonaphthalenedicarboxylic acid, and the like. Particularly preferred is 5-sodium sulfoisophthalic acid.

The copolymerization amount of the metal sulfonate group-containing aromatic dicarboxylic acid is 2 mol% or more and 5 mol% or less, and if it is 2 mol% or more, sufficient dyeability with a cationic dye can be easily obtained, and dyeing with a disperse dye When the temperature is less than 5 mol%, yarn breakage and fluff generation during spinning are likely to be reduced.

The production of the modified polyester in the present invention can be obtained by a known method similar to the production of polyethylene terephthalate. That is, when terephthalic acid is used, an esterification reaction with ethylene glycol as the acid is used, or when terephthalic acid dimethyl ester is used, a method of polycondensation is performed after an ester exchange reaction with ethylene glycol.

The aliphatic dicarboxylic acid having 4 to 8 carbon atoms as a copolymerization component can be added at any stage before the completion of polycondensation, for example, as an ethylene glycol slurry at the start of the esterification reaction of terephthalic acid and ethylene glycol. The bis (β-hydroxylethyl) terephthalate produced by the esterification reaction of terephthalic acid and ethylene glycol is added as an ethylene glycol dispersion or solution of an aliphatic dicarboxylic acid or bishydroxydicarbonate. In the production of the modified polyester, a matting agent, an antistatic agent, a flame retardant, a pigment, and the like can be added at any stage before the completion of polycondensation.

Similarly, the metal sulfonate group-containing aromatic dicarboxylic acid as a copolymerization component in the production of the modified polyester can be added at any stage before the completion of the polycondensation, for example, an ester of terephthalic acid and ethylene glycol. Bis (β-hydroxylethyl) terephthalate produced by esterification reaction of terephthalic acid and ethylene glycol, added as an ethylene glycol slurry at the start of the conversion reaction, dimethyl ester of dicarboxylic acid containing metal sulfonate group or ethylene of diglycol ester Add as glycol dispersion or solution.

The modified polyester fiber of the present invention preferably has a diethylene glycol content of 0.5% by mass or more and 3.0% by mass or less.
When the modified polyester is produced, particularly by the method of direct esterification, ethylene glycol is dehydrated to dimerize diethylene glycol, which remains as a by-product in the subsequent polycondensation reaction system.
If the content of diethylene glycol in the modified polyester fiber of the present invention is 3.0% by mass or less, the decrease in fiber strength can be reduced. From the said viewpoint, 2.5 mass% or less is more preferable, and 2.0 mass% or less is further more preferable.

As a method for suppressing the by-production of diethylene glycol, it is preferable to add a weak acid salt or hydroxide of an alkali metal or alkaline earth metal to the reaction system during the esterification reaction, particularly sodium hydroxide, sodium acetate, lithium acetate, etc. Is effective in suppressing the by-production of diethylene glycol, and is preferably used when the dicarboxylic acid of the copolymer component is 10 mol% or more. In the present invention, lithium acetate is more preferably used.

The modified polyester fiber of the present invention preferably contains lithium acetate, and the lithium acetate content is preferably 50 to 120 ppm in terms of lithium atoms.
The lithium acetate content is preferably 50 to 150 ppm, more preferably 100 to 150 ppm, and still more preferably 120 to 150 ppm in terms of lithium atoms based on the polymer composition. By containing, the modified polyester whose ethylene glycol content is 0.5 mass% or more and 3.0 mass% or less can be obtained.

The modified polyester fiber of the present invention has a single fiber fineness of 0.6 dtex or more and 3.5 dtex or less, a fiber strength of 2 cN / dtex or more and 3.5 cN / dtex or less, and a fiber elongation of 25% or more and 45% or less. Is preferred.

If the single fiber fineness of the modified polyester fiber of the present invention is 0.6 dtex or more, it is preferable because fiber strength can be maintained and the knitting property is good, and if it is 3.5 dtex or less, the weight loss processability is good. This is preferable. From the above viewpoint, the single fiber fineness is more preferably 1 dtex or more and 3 dtex or less, and further preferably 1.3 dtex or more and 2.5 dtex or less. *

If the fiber strength of the modified polyester fiber of the present invention is 2 cN / dtex or more and 3.5 cN / dtex or less, there is no problem in the knitting property, and 2.3 cN / dtex or more and 3 cN / dtex or less is more preferable. Further, if the elongation of the modified polyester fiber of the present invention is 25% or more and 45% or less, it is preferable because the knitting property is good, and more preferably 30% or more and 40% or less.

The modified polyester in the present invention is produced, for example, through the following production process.
A slurry of terephthalic acid and ethylene glycol is supplied to an esterification reactor in which bis (β-hydroxylethyl) terephthalate and its oligomer are present, and the esterification is carried out at a temperature of about 250 ° C. for 3 to 8 hours to achieve an esterification rate of 95%. The process of making the above reactants, this esterification reaction product is transferred to a polymerization can, and aliphatic dicarboxylic acid of copolymerization component, metal sulfonate group-containing aromatic dicarboxylic acid, lithium acetate, magnesium acetate, triethyl phosphate, germanium dioxide, respectively. After addition as an ethylene glycol solution or dispersion, the polymerization catalyst antimony trioxide is added as an ethylene glycol dispersion, and the temperature is raised and a polycondensation reaction is performed under a reduced pressure of around 270 ° C. until polycondensation is achieved until a predetermined intrinsic viscosity is reached. After passing through the process, the polycondensate is taken out and the strand And, to a chip.

The modified polyester fiber of the present invention can be obtained by a known melt spinning method similar to the production of polyethylene terephthalate fiber, and includes spinning for discharging the modified polyester chip from the spinning hole of the spinneret and subsequent stretching. A known method can be applied to the yarn production method. For example, in the production of the modified polyester fiber, the spinning temperature is 240 to 300 ° C., the spinning speed is 1000 to 2000 m / min, the stretching temperature is 60 to 90 ° C., the stretching speed is 400 to 1000 m / min, and the draw ratio is 1. Conditions of 8 to 3.5 times, a draw ratio of 0.65 to 0.80 times the maximum draw ratio, and a heat setting temperature of 110 to 160 ° C. are used. Here, the maximum draw ratio refers to the ratio when the undrawn yarn is drawn until it is cut at a drawing temperature of 80 ° C., a heat setting temperature of 145 ° C., and a drawing speed of 600 m / min.

In the spinning process, the spun unstretched yarn is wound once and then stretched, the spun unstretched yarn is stretched without being wound, and the spun speed is wound as a semi-unstretched yarn by high speed spinning of 2000 m / min or more. Alternatively, a method such as spinning at high speed and drawing without winding is used.

Since the modified polyester fiber of the present invention is suitably used for opal processing in which a part of the composition fiber of the woven or knitted fabric is removed by discharge, the single fiber fineness of the modified polyester fiber is a filament yarn. If it exists, it is preferable that the single yarn fineness is 0.6 dtex or more and 3.5 dtex or less which is easy for the fiber to remove and remove. The cross-sectional shape of the modified polyester fiber may be any shape such as a circle, a flat shape, a triangle, a Y shape, and a multi-leaf shape. The modified polyester fiber may be either a short fiber or a filament, and when the fiber is a filament, the filament yarn can be crimped or false twisted.

The modified polyester fiber of the present invention has an easily dyeable and easily dissolvable alkali-dissolving property while being easily dyeable at normal pressure with a disperse dye and dyeable at normal pressure with a cationic dye. It is a combination of other highly chemical-resistant fibers to make a mixed woven or knitted fabric by cross knitting or knitting, and when this mixed woven knitted fabric is opal processed, it is a discharge paste or discharge accelerator that is printed. Opal processed products with various colors and tones can be obtained by adding disperse dyes or cationic dyes to the contained paste. As the fiber having high chemical resistance, polyethylene terephthalate fiber is particularly preferably used. Therefore, the modified polyester fiber of the present invention can be combined with polyethylene terephthalate fiber to obtain an opal processed product of a mixed woven or knitted fabric made only of polyester fibers. Further, the modified polyester fiber of the present invention is not only a fiber having high chemical resistance but also other low or different chemical resistance fibers as required, such as wool, silk, cotton, rayon, acetate fiber. It can also be mixed with polyamide fibers and the like, and an opal processed product with various colors, colors and textures can be obtained by adding a dye suitable for the mixed fiber to the discharge paste.

In addition, the modified polyester fiber of the present invention is modified without causing embrittlement of the polyurethane fiber by opalizing the polyethylene terephthalate fiber and the polyurethane fiber under mild alkali treatment conditions due to its alkali solubility. This makes it possible to obtain a stretchable opal processed product by forming a highly stretchable part from which only the high quality polyester fiber is removed. The polyurethane fiber used may be either a polyether-based polyurethane fiber or a polyester-based polyurethane fiber.

The opal processing performed on the mixed woven or knitted fabric obtained by combining or knitting with the modified polyester fiber of the present invention combined with polyethylene terephthalate fiber or polyurethane fiber is a woven / knitted structure, mixed fiber ratio, discharge pattern, usage, etc. Depending on the conditions, for example, a method consisting of a printing process of an extraction paste containing caustic soda as an extraction agent, a drying process, an extraction treatment process by wet heat or dry heat, a soaping / washing process, or an acceleration of extraction A method comprising an agent-containing paste printing process, a drying / heat treatment process, a soaping / washing process, and an alkali weight reduction process (discharge process) with caustic soda is employed. In the case of opal processing of a mixed woven or knitted fabric of the modified polyester fiber of the present invention and polyethylene terephthalate fiber or further polyurethane fiber, the alkali weight loss treatment (discharge process) in the latter method is generally applied to the woven or knitted fabric of polyester fiber. Alkali weight loss processing may be performed, and the latter method is preferably employed. During opal processing, dyes can be added appropriately to the extraction paste or extraction accelerator-containing paste, and the non-extraction fibers can be colored simultaneously with the extraction, and dyeing before or after the opal processing. Combined with this, combined with the variety of colors and fine single fiber fineness, a high-quality opal processed product can be obtained.

As the opal processed product of the mixed woven or knitted fabric using the modified polyester fiber of the present invention, outerwear such as embroidery lace, lingerie, foundation, swimsuit, sports inner, body suit, leotard, sports tights, girdle, Inner wear is listed.

The woven or knitted fabric of the present invention comprises a modified polyester fiber having a weight loss rate of 5% to 15% and a non-weight loss fiber having a weight loss rate of 0% to less than 5% obtained by the following measurement method. A knitted fabric, wherein the content of the modified polyester fiber relative to the woven fabric is 5% by mass to 50% by mass, and the content of the non-reduced fiber is 50% by mass to 95% by mass.
<Method for measuring fiber weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100

By containing the non-weight-reducing fiber whose weight loss rate is 0% or more and less than 5%, even when the modified polyester fiber of the present invention is weight-reduced with an alkali, the non-weight-reducing fiber remains and can be discharged.
From the above viewpoint, the weight loss rate of the non-weight-reducing fiber is more preferably 4% or less, and further preferably 3% or less.

Further, if the content of the modified polyester fiber with respect to the woven or knitted fabric is 5% by mass or more, the effect of the discharge process is likely to occur, and if it is 50% by mass or less, the non-exhaust fibers remain sufficiently. The strength of the knitted fabric can be sufficiently maintained.
From such a viewpoint, the content of the modified polyester fiber with respect to the woven or knitted fabric is more preferably 10% by mass or more and 40% by mass or less, and further preferably 15% by mass or more and 30% by mass or less.

The woven or knitted fabric of the present invention contains a modified polyester fiber having a weight loss rate of 5% to 15% and a non-weight loss fiber having a weight loss rate of 0% to less than 5% obtained by the following measurement method, A knitted or knitted fabric having a portion to which the modified polyester fiber is removed, wherein the weight loss rate of the modified polyester fiber in the portion to be removed is 50% by mass or more and 100% by mass with respect to the polyester fiber in the non-exhausted portion It is the following woven or knitted fabric.
<Method for measuring fiber weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100

In the woven or knitted fabric of the present invention having an extracted portion, the weight loss rate of the modified polyester fiber in the extracted portion is 50% by mass to 100% by mass with respect to the modified polyester fiber in the non-extracted portion. is there.
If the weight loss rate is 50%, the effect of weight loss processing on the fabric is sufficient. That the weight loss rate is 100% means that the modified polyester fiber in the portion to be removed has disappeared, and this state is preferable. However, in view of the design effect of the woven or knitted fabric, it is preferable to leave a part of the modified polyester in the removed portion.

In the woven or knitted fabric of the present invention, it is preferable that the burst strength of the woven or knitted fabric in the discharged portion is 250 kPa or more and 900 kPa or less.
When the burst strength is 250 kPa or more, the strength is satisfactory for use as a product. Moreover, if it is 900 kPa, it is intensity | strength sufficient on use.
From the above viewpoint, the burst strength is preferably 400 kPa or more, and more preferably 600 kPa or more.

In the woven or knitted fabric of the present invention, it is preferable that the strength retention of the rupture strength of the eroded portion of the woven or knitted fabric with respect to the rupture strength of the non-extracted portion of the woven or knitted fabric is 50% or more.
If the strength retention of the burst strength is 50% or more, it is possible to reduce the fact that the stress is excessively concentrated on the removed portion and the woven or knitted fabric breaks.
From the above viewpoint, the strength retention is more preferably 70% or more, and further preferably 85% or more.

In the woven or knitted fabric of the present invention, the modified polyester fiber has ethylene terephthalate as a main constituent unit, an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and an aromatic dicarboxylic acid containing a metal sulfonate group. It is preferable that the modified polyester fiber is copolymerized in an amount of 2 mol% or more and 5 mol% or less.

If the amount of the copolymerized aliphatic dicarboxylic acid having 4 to 8 carbon atoms is 16 mol% or more, the modified polyester fiber can be easily reduced in the range of pH 9 to 13, and if it is 25 mol% or less, Yarn breakage during spinning of the fibers can be reduced, and productivity is improved.
From the above viewpoint, the copolymerization amount of the aliphatic dicarboxylic acid having 4 to 8 carbon atoms is more preferably 20 mol% or less.

In the woven or knitted fabric of the present invention, the non-reducing fiber preferably contains 50% by mass to 95% by mass of synthetic fiber.
When the content of the synthetic fiber with respect to the woven or knitted fabric is 50% by mass or more, a decrease in the burst strength of the discharged portion can be reduced. Moreover, if content of the said synthetic fiber is 95 mass% or less, a removal fiber can be included and it can be easy to produce the effect of a removal process. From the above viewpoint, the content of the synthetic fiber is more preferably 60% by mass or more and 80% by mass or less.

In the woven or knitted fabric of the present invention, the synthetic fiber is preferably any one or more of regular polyester fiber, polyamide fiber, elastic fiber, polyolefin fiber, and acrylic fiber.
Among these, regular polyester fibers are preferable in terms of strength, and elastic fibers are preferable from the viewpoint of exerting stretch properties.

In the woven or knitted fabric of the present invention, the single fiber fineness of the modified polyester fiber is preferably 0.6 dtex or more and 3.5 dtex or less.
If the single fiber fineness is 0.6 dtex or more, the strength of the woven or knitted fabric can be increased, and if it is 3.5 dtex or less, the pitting property becomes good and the texture of the woven or knitted fabric can be made soft easily.
From the viewpoint, the single fiber fineness is more preferably 0.9 dtex or more and 2.5 dtex or less.

In the woven or knitted fabric of the present invention, it is preferable that the elastic fiber is any one of polyurethane fiber, polytrimethylene terephthalate fiber, and polybutylene terephthalate fiber as described above.

The woven or knitted fabric of the present invention is preferably composed of a modified polyester fiber, a regular polyester fiber and a polyurethane fiber. If it is the said structure, it has stretch property, is high intensity | strength, and can obtain the soft texture woven or knitted fabric.

The method for producing a woven or knitted fabric according to the present invention comprises printing a discharging agent on a fabric containing a modified polyester fiber and a non-reducing fiber that are reduced in weight under a pH of 8 or more and 13 or less. A method of manufacturing a knitted or knitted fabric that is subjected to weight reduction processing by applying superheated steam to the part, wherein the pH of the removal processing agent is 8 or more and 13 or less, and the heating method is 150 ° C or more and 200 ° C or less of superheated steam. The heating time is 5 minutes or more and 15 minutes or less.

In the heating method, overheated steam of 150 ° C. or higher and 200 ° C. or lower is applied to the portion where the removal processing agent is printed. When the temperature of the superheated steam is 150 ° C. or higher, the pitting property is good, and when it is 200 ° C. or lower, it is possible to reduce the texture of the polyester fiber becoming hard.

The heating time is preferably 5 minutes or more and 15 minutes or less.
If the heating time is 5 minutes or more, the dischargeability is good, and if the heating time is 15 minutes or less, the strength reduction of the non-extraction portion can be reduced.

The discharge processing agent is characterized by containing a paste and a component having a discharging action in a specific pH range (pH 8 to 13) excluding guanidine carbonate. As said component which has a pitting action, 1 type or 2 types of sodium carbonate or potassium carbonate is preferable, and 1 type of sodium carbonate is more preferable. The amount of sodium carbonate or potassium carbonate may be adjusted according to the mass of the modified polyester fiber to be removed, but is generally used in the range of 5 to 15% by mass with respect to the removal processing agent. It is preferable. The removal processing agent may contain a removal promotion agent as necessary. The extraction accelerator is not particularly limited, and a commercially available one can be used. For example, May printer OP-2 manufactured by Meisei Chemical Industry Co., Ltd. is preferable.

As paste contained in the extraction processing agent, locust bean gum, starch, dextrin, crystal gum, tragacanth gum, cellulose, carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, natural, processed, Semi-synthetic and synthetic pastes can be used alone or in combination of two or more. The ratio of the paste is not particularly limited as long as it can maintain the appropriate viscosity for printing and performing heat treatment, but for example, it is contained in an amount of 1% by mass or more and 10% by mass or less with respect to the extraction processing agent. It is preferable.
In addition, other compounds such as dyes can be added to the removal processing agent.

A discharging process using the above-described discharging agent will be described.
The above-mentioned removal processing agent is preferably applied to woven or knitted fabrics containing modified polyester fibers.
The fiber used in combination with the modified polyester fiber is not particularly limited as long as it is a non-weight loss fiber different from the modified polyester fiber. For example, unmodified polyester fiber (made of unmodified polyethylene terephthalate, also called regular polyester fiber) Polyamide fiber, polytrimethylene terephthalate fiber, polybutylene terephthalate fiber, polypropylene fiber, polyethylene fiber, polyurethane fiber, and the like can be used. The woven or knitted fabric composed of yarns, staple yarns, and the like in which the modified polyester fibers and these fibers are combined by any method such as blending, blending, and twisting is subjected to a discharge process. The woven or knitted fabric may be a fabric dyed as necessary. As the dyeing, all or part of the fabric is performed by plain dyeing or printing by any known method.

The removal process can be performed generally using the above-described removal process agent according to known processes such as printing, heat treatment, and washing. In the printing process, a discharging agent is printed on the woven or knitted fabric containing the modified polyester fiber in a shape corresponding to a desired pattern. A printing method, a spray method, etc. are used for the printing of the discharge processing agent. The printing method is not particularly limited, and a form printing method, a flat screen method, a rotary screen method, a roller method, and the like are used. The amount of the removal processing agent attached to the woven or knitted fabric can be arbitrarily determined depending on the printing method, the woven or knitted structure of the fabric, and the desired pattern.

For example, in the case of the flat screen method, the viscosity of the removal processing agent, the hardness of the rubber squeegee, the printing of the removal processing agent is performed with a woven or knitted structure that performs printing, a mesh of a formwork that prints a desired pattern, or the like. The rubber squeegee pressure and the printing speed of the squeegee are determined, and the discharging agent is uniformly applied to the fabric in a desired pattern. To check whether the fabric is evenly adhered, check that there is no blurring of the printed part visually, there is no difference in the pattern on the left and right of the rubber squeegee, and the removal processing agent penetrates uniformly into the back of the printed part. It is done by confirming whether it is. Moreover, you may print the shape according to a desired pattern with the dyeing glue which does not contain a removal processing agent in parts other than the adhesion part of a removal processing agent. The printing method of the dyeing paste is not particularly limited, and printing is performed in the same manner as the discharge processing agent. After the discharge processing agent and the dyeing paste are printed on the woven or knitted fabric, the fabric is appropriately dried and subsequently heat-treated.

Examples of the heat treatment method include a baking method, a steam method, and an HT steam method, and the HT steam method is more preferable.

After the heat treatment process, removal of embrittled modified polyester fibers in the printed part, removal of unfixed dyes on the fibers of the dye used in combination with the removal processing agent, and dyeing paste used for areas other than the attachment portion of the removal processing agent Cleaning of adhesives and unfixed dyes on fibers is performed. The cleaning method is not particularly limited, and cleaning is performed by a known process. For example, cleaning with 2 g / L of surfactant, 2 g / L of surfactant, alkali cleaning with 2 g / L of soda ash, 2 g / L of surfactant, acidic cleaning with 2 g / L of acetic acid (90%), interface Activator 2g / L, soda ash 2g / L, hydrosulfite or thiourea dioxide 2g / L alkali reduction cleaning, surfactant 2g / L, acetic acid (90%) 2g / L, Rongalite 4g / L There is acid reduction cleaning. The washing temperature is preferably 60 ° C. or more and 100 ° C. or less, and the washing time is preferably 5 minutes or more and 30 minutes or less. Thereafter, washing, dehydration and drying are performed.

Examples of the surfactant used for washing include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and these can be used alone or in admixture of two or more.

Examples of nonionic surfactants include ether type non-alkylating agents such as higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, styrenated alkylphenol alkylene oxide adducts, styrenated phenol alkylene oxide adducts, and higher alkylamine alkylene oxide adducts. Ionic surfactants; Ether ester type nonionic surfactants such as fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and fatty acid alkylene oxide adducts; polypropylene glycol ethylene oxide Polyalkylene glycol type nonionic surfactants such as adducts; fatty acid esters of glycerol, pentaerythritol Ester-type nonionic surfactants such as fatty acid esters, fatty acid esters of sorbitol, fatty acid esters of sorbitan, fatty acid esters of sucrose; other nonionic interfaces such as alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines Mention may be made of activators. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The addition form of the alkylene oxide may be random addition of two or more kinds or block addition.

Anionic surfactants include anionic surfactants of carboxylates such as fatty acid soaps; higher alcohol sulfates, higher alcohol alkylene oxide adduct sulfates, polyoxyalkylene ether sulfates, phenol alkylene oxide adducts sulfuric acid Ester salt, alkylphenol alkylene oxide adduct sulfate ester, styrenated alkylphenol alkylene oxide adduct sulfate ester, styrenated phenol alkylene oxide adduct sulfate ester, polyhydric alcohol alkylene oxide adduct sulfate ester, sulfated oil, sulfuric acid Sulfate esters such as sulfated fatty acid esters, sulfated fatty acids, sulfated olefins; alkylbenzenesulfonates, alkylnaphthalenesulfonates, naphthalene Anionic surfactants of sulfonate salts such as formalin condensates such as sulfonic acid, sulfonates such as α-olefin sulfonate, paraffin sulfonate, sulfosuccinate diester salt; oleoyl methyl taurine sodium salt, higher alcohol Phosphate ester salt, polyoxyalkylene ether phosphate ester salt, phenol alkylene oxide adduct phosphate ester salt, alkylphenol alkylene oxide adduct phosphate ester salt, styrenated alkylphenol alkylene oxide adduct phosphate ester salt, styrenated phenol alkylene Phosphate ester salts such as oxide adduct phosphate salts, polyhydric alcohol alkylene oxide adduct phosphate ester salts; N-methyl taurine oleate, N-methyl Other anionic surfactants such as taurine stearate can be mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The addition form of the alkylene oxide may be random addition of two or more kinds or block addition. Examples of the salt include alkali metal salts such as lithium, sodium and potassium; primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine and allylamine; 2 such as dimethylamine, diethylamine, dipropylamine, dibutylamine and diallylamine Examples include tertiary amines; tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; amine salts such as alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

Examples of cationic surfactants include alkyl ether quaternary ammonium salts, alkylamide quaternary ammonium salts, dialkyl ester quaternary ammonium salts, dialkylimidazoline quaternary ammonium salts, alkylamidoamines, alkyl etheramines, alkylamidoguanidines, and arginine derivatives. be able to.

Examples of amphoteric surfactants include alkyl betaine surfactants, amidopropyl betaine surfactants, and imidazolinium betaine surfactants.

By the above processing method, it is possible to obtain an extraction processed product in which the modified polyester fiber in the portion where the extraction processing agent is printed is dropped. The obtained extracted processed product is subjected to known processes such as dyeing and finishing as necessary.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In addition, the measurement of various characteristic values in an Example and the evaluation method are as follows.

(Intrinsic viscosity [η])
The modified polyester was adjusted to 20 ° C. in a mixed solvent of phenol / ethane tetrachloride = 1/1 and measured by the Ubbelohde method.

(Diethylene glycol (hereinafter abbreviated as DEG) content)
The resulting modified polyester was hydrolyzed with alkali, and then the number of moles of ethylene glycol and DEG was quantified using a gas chromatograph GC-9A manufactured by Shimadzu Corporation. The number of moles of DEG relative to the total number of moles of ethylene glycol and DEG It calculated | required in the ratio (%).

(Glass transition temperature Tg)
The Tg (° C.) of the modified polyester was measured at a heating rate of 10 ° C./min using a differential thermal analyzer DSC220 manufactured by Seiko Denshi Kogyo.

(Strength / Elongation)
In accordance with JIS L1013, strength (cN / dtex) and elongation (%) were measured using a tensile tester Tensilon UTM-4-100 manufactured by Orientec.

(Alkaline weight loss rate)
The weight loss rate (%) was calculated from the weight loss rate of the fiber subjected to alkali weight loss from the mass of the fiber before and after the treatment according to the following formula.
Weight loss rate (%) = {(mass of fiber before treatment−mass of fiber after treatment) / mass of fiber before treatment} × 100
It is preferable from the viewpoint of handleability that the fiber is reduced in alkali in the form of a knitted fabric.

(Burst strength)
The measurement was performed according to the MU Len method of JIS L 1018.

(Burst strength retention)
Rupture strength retention rate = {rupture strength of the eroded portion after the woven / knitted fabric's erosion process / burst strength of the non-exhausted portion after the woven / knitted fabric's eradicating processing} × 100 (%)

(Example 1)
A molar ratio of terephthalic acid (hereinafter abbreviated as TPA) to ethylene glycol (hereinafter abbreviated as EG) is 1/1 in an esterification reaction vessel in which bis (β-hydroxyethyl) terephthalate and its oligomer exist. .6 slurry was continuously supplied, and the esterification reaction was performed under the conditions of a temperature of 250 ° C., a pressure of 0.1 Pa, and a residence time of 8 hours. Next, 15.4 kg of the obtained esterification reaction product was transferred to a polycondensation reaction can, and 4.6 kg of an EG dispersion whose concentration of adipic acid (hereinafter abbreviated as ADA) was adjusted to 50% by mass was added. Moreover, lithium acetate was added so that the amount of lithium atoms was 120 ppm in order to suppress DEG by-product. Then, after stirring and mixing at 230 ° C. for 5 minutes, magnesium acetate as a stabilizer was added in an amount of 120 ppm of magnesium atoms, triethyl phosphate was added in an amount of 140 ppm of phosphorus atoms, germanium dioxide was added in an amount of 30 ppm of germanium atoms, and 5-sodium sulfo 2.6 kg of SIP EG solution in which the concentration of EG ester of isophthalic acid (hereinafter abbreviated as SIP) was adjusted to 35% by mass was added, and the mixture was stirred and mixed at a temperature of 230 ° C. Next, after adding 400 ppm of antimony trioxide as a polycondensation catalyst, the pressure is gradually reduced, and after 60 minutes, the pressure is reduced to 1.2 hPa or less, stirring and mixing are performed, and then the temperature is raised to 270 ° C. A polycondensation reaction is performed until a predetermined intrinsic viscosity [η] is obtained, and a modified polyester having an ADA copolymerization amount of 18 mol% and a SIP copolymerization amount of 2.5 mol% is obtained, and this is converted into a chip. did. The polymer properties of the modified polyester are shown in Table 1.

The resulting modified polyester chip was spun at a spinning temperature of 255 ° C. and a spinning speed of 1800 m / min with a spinneret having a circular hole shape and a hole number of 24, and this undrawn yarn was drawn at a drawing temperature of 65 ° C. and a draw ratio. 2.28 times, the ratio of the draw ratio to the maximum draw ratio (MDR ratio) is 0.72 times, and heat-set at 150 ° C. to obtain a modified polyester fiber of 84 dtex / 24f (single yarn fineness 3.5 dtex). It was.

A flat knitted fabric of the modified polyester fiber was prepared, 10 g of the knitted fabric was immersed in 1 L of an aqueous solution having a caustic soda concentration of 10 g / L and a temperature of 98 ° C. for 20 minutes, and then washed with water, dehydrated and dried. The weight loss rate was measured by the formula.
Weight loss rate (%) = {(mass of flat knitted fabric before alkali weight loss processing−mass of processed knitted fabric after alkali weight loss processing) / mass of flat knitted fabric before alkali weight loss processing} × 100
The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Example 2)
Using the modified polyester chip obtained in Example 1, spinning and drawing were carried out in the same manner as in Example 1 except that the polymer discharge rate during spinning was changed to 2/5 in Example 1, and 33 dtex / A modified polyester filament yarn having 24f (single yarn fineness of 1.38 dtex) was obtained. The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Example 3)
In Example 1, 15.9 kg of the obtained esterification reaction product was transferred to a polycondensation reactor, and the addition amount of ADA EG dispersion was changed to 4.1 kg and the addition amount of SIP EG solution to 2.4 kg. Except for the above, a modified polyester obtained by copolymerizing ADA 16 mol% and SIP 2.25 mol% was obtained in the same manner as in Example 1 to obtain chips. Table 1 shows the polymer physical properties of the modified polyester. Using the resulting modified polyester chip, spinning and drawing were carried out in the same manner as in Example 1 except that the spinning speed at the time of spinning was 1200 m / min, and a modification of 84 dtex / 24f (single yarn fineness of 3.5 dtex) was made. A polyester filament yarn was obtained. The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Comparative Example 1)
In Example 1, 16.4 kg of the obtained esterification reaction product was transferred to a polycondensation reactor, and the addition amount of the ADA EG dispersion was changed to 3.6 kg and the addition amount of the SIP EG solution was changed to 2.1 kg. Except that, a modified polyester obtained by copolymerizing ADA 14 mol% and SIP 2.0 mol% was obtained in the same manner as in Example 1 to obtain chips. The polymer properties of the modified polyester are shown in Table 1. Using the obtained modified polyester chip, spinning and drawing were performed under the spinning conditions and drawing conditions shown in Table 1 to obtain a modified polyester filament yarn of 84 dtex / 24f (single yarn fineness 3.5 dtex). The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Comparative Example 2)
In Example 1, 16.9 kg of the obtained esterification reaction product was transferred to a polycondensation reactor, and the addition amount of ADA EG dispersion was changed to 2.6 kg and the addition amount of SIP EG solution to 2.1 kg. Except for the above, a modified polyester obtained by copolymerizing 10 mol% of ADA and 2.0 mol% of SIP was obtained in the same manner as in Example 1 to obtain chips. The polymer properties of the modified polyester are shown in Table 1. Using the obtained modified polyester chip, spinning and drawing were performed under the spinning conditions and drawing conditions shown in Table 1 to obtain a modified polyester filament yarn of 84 dtex / 24f (single yarn fineness 3.5 dtex). The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Comparative Example 3)
In Example 1, 17.6 kg of the obtained esterification reaction product was transferred to a polycondensation reaction can, and the addition amount of ADA EG dispersion was changed to 1.3 kg and the addition amount of SIP EG solution was changed to 2.3 kg. Except that, a modified polyester obtained by copolymerizing ADA 5 mol% and SIP 2.25 mol% was obtained in the same manner as in Example 1 to obtain chips. The polymer properties of the modified polyester are shown in Table 1. Using the obtained modified polyester chip, spinning and drawing were performed under the spinning conditions and drawing conditions shown in Table 1 to obtain a modified polyester filament yarn of 84 dtex / 24f (single yarn fineness 3.5 dtex).
The fiber is a copolymer component of atmospheric pressure cationic dyeable polyester fiber that is generally used in the market.
The physical properties of the obtained modified polyester filament yarn are shown in Table 1.

(Example 4)
A modified polyester fiber having a fineness of 84 dtex and 48 filaments, composed of a modified polyester resin in which ethylene terephthalate is the main constituent unit and 16 mol% of ADA and 2.5 mol% of SIP is copolymerized, Produced.
Using a mini-color dyeing machine (manufactured by Teksam Giken Co., Ltd., a multicolor rotating pot dyeing tester), 100 g of the weft knitted fabric is 40 g / L in sodium carbonate concentration, The weight ratio was 1:20, and the aqueous solution temperature was reduced to 100 ° C. for 30 minutes by alkali reduction, washed with water, dehydrated, and dried at 80 ° C. for 60 minutes to obtain a processed knitted fabric.
Further, in place of sodium carbonate, alkaline weight reduction processing was similarly performed with an aqueous solution of potassium carbonate and sodium hydroxide to obtain a processed knitted fabric.
Table 2 shows the pH of each aqueous solution and the weight loss rate of the modified polyester fiber.
Weight loss rate (%) = {(mass of weft knitted fabric before alkali weight loss processing-mass of processed knitted fabric after alkali weight loss processing) / mass of weft knitted fabric before alkali weight loss processing} × 100

(Comparative Example 4)
The yarn used for the weft knitted fabric is composed of a polyester resin in which ethylene terephthalate is the main structural unit and copolymerized with 5 mol% of ADA and 2.3 mol% of SIP, and has a fineness of 84 dtex and a 48 filament cationic dyeable polyester fiber. Except for the above, a processed knitted fabric was obtained in the same manner as in Example 4.
Table 2 shows the weight loss rate.

(Comparative Example 5)
The yarn used for the weft knitted fabric was made of polyethylene terephthalate fiber (yarn made of unmodified polyethylene terephthalate; hereinafter also referred to as “regular polyester fiber”). This yarn made of regular polyester fiber was manufactured by Teijin Limited. A processed knitted fabric was obtained in the same manner as in Example 4 except that a yarn having a fineness of 84 dtex and 36 filament was used.
Table 2 shows the weight loss rate.

As shown in Table 2, when alkali weight reduction was performed with sodium carbonate, the modified polyester fiber of Example 4 resulted in a higher weight loss rate than the general cationic dyeable polyester fiber of Comparative Example 4, and Comparative Example The regular polyester fiber No. 5 was not able to lose weight with sodium carbonate. Moreover, when alkali weight reduction was performed with potassium carbonate, the modified polyester fiber of Example 4 resulted in a higher weight loss rate than the general cationic dyeable polyester fiber of Comparative Example 4, and the general cation of Comparative Example 4 As shown in Table 2, the dyeable polyester fiber had a low weight loss rate of 2% with potassium carbonate. When alkali weight reduction was performed with caustic soda, the modified polyester fiber of Example 4 had a higher weight loss rate than the general cationic dyeable polyester fiber of Comparative Example 4 and the regular polyester fiber of Comparative Example 5.

(Example 5)
Using the warp knitted fabric (modified polyester fiber = 16.7%, regular polyester fiber = 83.4%) using the modified polyester fiber used in Example 4 and the regular polyester fiber used in Comparative Example 5, As the removal processing agent, a removal processing agent having the following composition was used, and a removal processing for dissolving the modified polyester fiber was performed. Table 3 shows the composition of the removal processing agent.
・ Sorbitose C-5 (10% aqueous solution) (Avebe) 50% by mass
・ Sodium carbonate (trade name: Soda ash, manufactured by Tokuyama Corporation) 10% by mass
・ Water 40% by mass
A square pattern was printed on the treated knitted fabric with the above-described discharge processing agent and dried at 110 ° C. for 2 minutes. Subsequently, the superheated steam process was performed for 180 degreeC x 8 minutes using the HT steamer. After that, after washing in a soap bath of 2g / L of Rakkor ISF (manufactured by Meisei Chemical Industry Co., Ltd.) at 80 ° C for 20 minutes, it is washed with water, dehydrated and dried to obtain a processed warp knitted fabric. It was.

Evaluation: The pitting property was visually evaluated. As shown in Table 3, the evaluation criteria are as follows. For the removal property, the fiber that has been removed from the printed part cannot be visually confirmed as ◎, and a small amount of residue can be visually confirmed, but the removal is performed. In addition, a product that can be judged as usable as a product was rated as “good”, and a residue that could be visually confirmed was not removed. Further, the burst strength of the removed portion was measured according to JIS L 1018 Murren method. The results are shown in Table 3. The burst strength of the processed knitted fabric of the non-exhausted portion was 755 kPa.

(Example 6)
As shown in Table 3, an extraction knitted fabric was obtained in the same manner as in Example 5 except that an extraction accelerator (Maysei Chemical Industries, May Printer OP-2) was used. Table 3 shows the evaluation of the dischargeability.
By using the above-mentioned removal accelerator, the removal property was the same as that when a strong alkali was used. On the other hand, there was little decrease in burst strength.

(Comparative Examples 6 and 7)
Exhaust processing was conducted in the same manner as in Example 5 except that the composition and conditions shown in Table 3 were used as the discharge processing agent, and the resulting discharge processed knitted fabric was evaluated. The results are shown in Table 3.
Since the alkalinity is strong, the biting property was good, but the burst strength was greatly reduced.

As shown in Table 3, Example 5 containing only sodium carbonate was able to perform the discharge process, and there was little decrease in the strength of the extracted part. On the other hand, in Comparative Example 6 using guanidine carbonate and Comparative Example 7 using sodium hydroxide, the excavability of the excised part was good, but an extreme decrease in strength of the excised part was observed.
The processing agent using guanidine carbonate has a pH of 11.8. However, it is known that guanidine carbonate becomes a strong alkali when heated, so that the decrease in burst strength is large.
Further, in Example 6 containing Mayprinter OP-2, which is a discharge accelerator, and sodium carbonate, good dischargeability was obtained, and there was little decrease in strength of the discharged portion.

(Example 7)
A knitted fabric (modified polyester fiber 50% / regular polyester fiber) using the same modified polyester fiber as in Example 4 and the same regular polyester fiber as in Comparative Example 5 (84 dtex, manufactured by Teijin Ltd.). Exhaust processing was performed in the same manner as in Example 6 except that 50%) was used, and an excavation knitted fabric was obtained. Table 4 shows the evaluation of the dischargeability. The evaluation of the biting property was evaluated as “◎” because the fiber that had been discharged on the printed part could not be visually confirmed.

(Comparative Examples 8 to 11)
Exfoliated fabric was obtained in the same manner as in Example 5 except that the modified polyester fiber of Example 5 was changed to the polyester fiber described in Table 4. Table 4 shows the evaluation of the dischargeability.

According to the present invention, by using the modified polyester fiber as the modified polyester fiber, only the modified polyester fiber in the printed part is obtained without performing alkali weight loss on the woven or knitted fabric composed of the modified polyester fiber and the unmodified polyester fiber. It is possible to obtain an exfoliation processed cloth with good exfoliation property of the modified polyester fiber that does not cause embrittlement of the unmodified polyester fiber, and a strong alkaline substance that is highly harmful to humans can be obtained. Since it is not used, it is possible to perform a discharge process with high safety in operation.

Claims

A modified polyester fiber having a weight loss rate of 5% to 15% in the following measurement.
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100
The main structural unit is ethylene terephthalate, and 12 to 25 mol% of an aliphatic dicarboxylic acid having 4 to 8 carbon atoms and 2 to 5 mol% of a metal sulfonate group-containing aromatic dicarboxylic acid are copolymerized. The modified polyester fiber according to claim 1, comprising a modified polyester.
The modified polyester fiber according to claim 2, wherein the aliphatic dicarboxylic acid is adipic acid, and the metal sulfonate group-containing aromatic dicarboxylic acid is 5-sodium sulfoisophthalic acid.
The modified polyester fiber according to any one of claims 1 to 3, wherein the content of diethylene glycol is 0.5 mass% or more and 3.0 mass% or less.
The single fiber fineness is 0.6 dtex or more and 3.5 dtex or less, the fiber strength is 2.0 cN / dtex or more and 3.5 cN / dtex or less, and the fiber elongation is 25% or more and 45% or less. The modified polyester fiber according to Item.
The modified polyester fiber according to any one of claims 1 to 5, wherein the modified polyester fiber contains lithium acetate, and the content of the lithium acetate is 50 to 120 ppm in terms of lithium atoms.
A knitted or knitted fabric containing a modified polyester fiber having a weight loss rate of 5% or more and 15% or less and non-weight loss fiber having a weight loss rate of 0% or more and less than 5% in the following measurement, A woven or knitted fabric in which the content of the quality polyester fiber is 5% by mass or more and 50% by mass or less, and the content of the non-reduced fiber is 50% by mass or more and 95% by mass or less.
<Method for measuring weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and the fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100
A modified polyester fiber having a weight loss rate of 5% or more and 15% or less in the following measurement and a non-weight loss fiber having a weight loss rate of 0% or more and less than 5%, A woven or knitted fabric having a weight loss rate of 50% by mass or more and 100% by mass or less of the modified polyester fiber in the extracted portion with respect to the modified polyester fiber in the non-extracted portion.
<Method for measuring weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and the fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100
The woven or knitted fabric according to claim 7 or 8, wherein a difference between the weight loss ratio of the modified polyester fiber and the weight loss ratio of the non-exhaust fiber is 5% or more.
The woven or knitted fabric according to claim 8 or 9, wherein the burst strength of the woven or knitted fabric in the discharged portion is 250 kPa or more and 900 kPa or less.
The woven or knitted fabric according to any one of claims 8 to 10, wherein the strength retention of the rupture strength of the eroded portion of the woven or knitted fabric relative to the rupture strength of the non-exhausted portion of the woven or knitted fabric is 50% or more.
The modified polyester fiber has ethylene terephthalate as a main constituent unit, an aliphatic dicarboxylic acid having 4 to 8 carbon atoms in an amount of 16 mol% to 25 mol%, and a metal sulfonate group-containing aromatic dicarboxylic acid in an amount of 2 mol% to 5 mol. The woven or knitted fabric according to any one of claims 8 to 11, wherein the woven or knitted fabric is a modified polyester copolymerized in an amount of 1% or less.
The woven or knitted fabric according to any one of claims 8 to 12, wherein the non-weight-reducing fiber contains 50% by mass or more and 95% by mass or less of a synthetic fiber.
The woven or knitted fabric according to claim 13, wherein the synthetic fiber is at least one of regular polyester fiber, polyamide fiber, elastic fiber, polyolefin fiber, and acrylic fiber.
The woven or knitted fabric according to any one of claims 8 to 14, wherein a single fiber fineness of the modified polyester fiber is 0.6 dtex or more and 3.5 dtex or less.
The woven or knitted fabric according to claim 14 or 15, wherein the elastic fiber is any one of polyurethane fiber, polytrimethylene terephthalate fiber, and polybutylene terephthalate fiber.
In the following measurement, the removal processing agent is printed on the fabric containing the modified polyester fiber and the non-reduction fiber with a weight loss rate of 5% or more and 15% or less, and superheated steam is applied to the portion where the removal processing agent is printed. Is a method for producing a woven or knitted fabric for weight reduction processing, wherein the pH of the removal processing agent is 8 or more and 13 or less, the heating method is 150 ° C. or more and 200 ° C. or less superheated steam, and the heating time is 5 A method for producing a woven or knitted fabric that is not shorter than 15 minutes and not longer than 15 minutes.
<Method for measuring weight loss>
100 g of fiber is put into 2 L of sodium carbonate 40 g / L aqueous solution, heated at 100 ° C. for 30 minutes, and the fiber mass Ag after drying at 80 ° C. for 60 minutes is measured.
Weight loss rate (%) = {(100−A) / 100} × 100