TW444030B - Novel materials for improved the dyeability of conjugated fibers - Google Patents

Abstract

The core/sheath type and islands in sea type conjugated fibers have been used PET as core's or island's materials, and hot base water soluble copolyesters as sheath's or sea's materials. The dyeability of conjugated fibers used PET as island's or core's material was not so good. We have used copolyester (prepared from terephthalate glycol, polyethylene glycol and pentaerythritol as raw material) as island's or core's materials have been improved island's and core's dyeability in our innovation.

Description

__Case No. 88106612__} η Ο -------- 5. Description of the invention (1) In the case of composite spinning, when poly-para-xylylene is used as an island or Lai material, it is soluble in hot alkaline aqueous solution When the copolyester is a sea or core material, after composite spinning and weight reduction, the dyeability is not bad after weaving into a cloth (the color is not deep enough and fresh). The present invention uses terephthalic acid (or terephthalic acid Methyl ester), 6 diol, tri- or tetraol (or acid) functional groups and polyethylene glycol as raw materials to synthesize copolyesters as island or sheath materials. After composite spinning, weaving into fabrics and dyeing, the depth of dyeing And the color brightness is better than using polyethylene terephthalate as an island or sheath material. The sheath fine type and the sea-island type ultra-fine weaving dimension spun out of the present invention can have a fineness of less than 0.1 denier, or even superfine fibers such as 0.00 OOO denier. At present, this type of product includes silk fabrics such as suede, silk, peach, and rose. In the patent literature, 'improving the dyeing method of poly (p-phenylene terephthalate) is generally used 3, 5-di ( Sodium methoxycarbonyl) benzenesulfonate, 3,5-di-hydroxyethylcarbonyl) benzenebenzenesulfonate or sodium isophthalate sulfonate, etc., and / or alcohol (polyethylene glycol) or isophthalic acid, etc. should be changed to 5 When synthesizing poly (ethylene terephthalate), a synthetic copolyester (shovel; called cationic dyeable polysleep) is added. If cationic dyeability is used, it can improve the dyeing of the island after the reduction of composite spinning. In the process of weight reduction, some cations can be removed in the process of weight reduction, so that the surface of the fiber exhibits uneven physical properties. The patent literature in this regard is representative of the '/ Affecting Fiber No. 18128 (published in 1 998) published in the specification to Kaiping 10-3, 5-bis (m-Ethoxyethoxyl) sodium sulfonate and benzene Two: acid and (or dimethyl terephthalate) and ethylene glycol manganese

…two................................................ ........................................ ........................................ ........................................ ........................................ .......... ... IιΑ copolyester is an island material, heart 0 from __ 索 号 .881Q6612 to fight for $? a A.t_ V. Description of the invention (2) To improve the problem of island fabric dyeing after composite spinning reduction, (2) Japanese Unexamined Patent Publication No. 9-2794 18 (published in 1997) uses terephthalic acid and ethyl acetate. Diacid was added with polyethylene glycol and sodium 3,5-bis (methoxycarbonyl) benzenesulfonate as raw materials to synthesize the copolyester as an island material, which is used to improve the composite yarn access and reduce the dyeability of island fibers after weight reduction. In addition, 'Some patents have different weight loss conditions to improve the dyeing properties of the island after the composite spinning weight loss. For example, (1) Japanese Patent Application No. 4_281075 (published in 1992) mentions the use of sodium tripolyphosphate. ) Improving the dyeing properties of Shimori fabrics by soaking poly-ethylene terephthalate fibers in aqueous solution, (2) Japanese Unexamined Patent Publication No. 4-281076 (published in 1992) mentions the use of poly-terephthalic acid. The diethyl island weave was immersed in sodium argon oxide, hydrosulfite, and nonionic surfactant, which improved the dyeability of the island weave. The invention uses terephthalic acid (or dimethyl terephthalate), adipic acid, pentaerythritol and polyethanol as raw materials to synthesize a copolyester as an island material, which is used to improve the dyeability of the island weave. The fiber will not be partially dissolved by sodium argonate during weight reduction. 0 _ The sea or core material of the present invention can be used to synthesize 1,4-bis (hydroxyl) with terephthalic acid (or dimethyl terephthalate) and ethylene glycol. Ethoxycarbonyl) benzene, or diethyl p-benzylate, ethylene glycol, or comonomers (such as bisacids, bis, dianhydrides, bisols, polyetherols, bisacids, bis Copolyester synthesized from raw materials such as esters and acid salts. The (1) diacid mentioned above may be isophthali (acid), phthanc acid, 1,4-cyclohexyl diψ acid ζ Λ Λ _ ^, 1 '4 ~ cyc 1 ohexane di carboxy 1 ic acid), adipic acid

444 030 _ cable number 88106612 amended on the day of the month _ V. Description of the invention (3) (adipic acid), 2,6-diphthalic acid (2,6-naphthalene dicarboxylic acid), etc. (2) The diester can be Dimethyl isophthalate, dimethyl phthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl adipate, dimethyl 2,6-dicarboxylate, etc. (3) Diester anhydride may be phthalic anhydride, etc., (4) Diol may be diethylene glycol, triethylene glycol, 1,4-cyclohexanediol ( 1,4-cyclohexane dimethanol), propylene glycol, 2-methyl-1,5-pentanediol, neoglutarase, xylene glycol, etc. (5) Polyol can be Polyacetic acid, polypropylene glycol, polytetramethylene glycol, or a copolymer thereof, etc. (6) The diacid sulfonate may be sodium salt of sulfoisophthalic acid ), Isophthalic acid, lithium isophthalate sulfonate, magnesium isophthalate sulfonate, sodium 2, 6-dicarboxylic acid-4-sulfonate (2,6-dicarboxylic acid naphthalene-4-sulfonic acid), 3,5-cyclohexane dicarboxyl i c acid-4-sulfonic acid, (7) diesters can be 3, 5 -Sodium bis (methylcarbonyl) benzenesulfonate, Potassium 3,5-bis (methylcarbonyl) benzenesulfonate, Lithium 3,5-bis (methylcarbonyl) benzenesulfonate, 3,5-Di (fluorenyl) Carbonyl) magnesium benzenesulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) sodium benzenesulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 3, 5-di (M-Hydroxyethoxycarbonyl) lithium benzenesulfonate, 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 3,5-bis (m-hydroxyethoxycarbonyl) benzoic acid Tetrabutyl vinegar

4 A4 Ο 3 Ο _ case number 88106612 $ month? Amendment _ V. Description of the invention (4) phosphonium-3,5-di (beta-hydroxyethoxycarbony 1) benzene sulfonate], 3,5-bis (methoxythionyl) phenylphosphonic acid tetra-butyl vinegar [tetrabutyl phosphonium -3,5-di (carbomethoxy) benzene sulfonate], 3,5-di (methoxybothyl) cyclohexyl sodium sulfonate (sodium salt of 3,5-dicarbomethoxy cyclohexane sulfonic acid), 3, 5-di ( Sodium salt of 3,5-di (beta-hydroxyethoxycarbony 1) cyclohexane sulfonic acid, 3,5-di (methoxycarbonyl) cyclohexanesulfonic acid Tetra butyl phosphonium-3,5-di (carbomethoxy) cyclohexane sulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) cyclohexanesulfonic acid Ester [VII 61; ^ 1) 11171 卩} 108-port 11011111111- (beta-hydroxyethoxycarbonyl) cyclohexane sulfonate] and the like. The invention uses terephthalic acid (or dimethyl terephthalate), ethylene glycol, tri or tetraol (or acid) functional groups and polyethylene glycol as raw materials to synthesize a copolyester as an island or sheath material. In order to improve the dyeing property of the composite spinning weight-loss fabric. The molecular weight of polyethylene glycol mentioned in the present invention is 200 to 20,000, and a molecular weight of 200 to 4,000 is a better molecular weight of polyethanol. In addition, the tri- or tetra-ol (or acid) functional group of the present invention may be glycerol, tr i me thy 1 e 1 e thane, tetra-methanol or pentaerythritol, heptamate ( 1: rime 1 1 iticanhydride) and so on. A few examples are described below, the examples are only for the present invention 4, d4 March 2003? Said __ _ cable number 88106612 V. Description of the invention (5) General illustration of the method 'is not intended to limit the scope of the invention, so it is stated here that the embodiment of the invention is divided into (1) island synthesis, (2) sea Synthetic, (3) Composite spinning 'woven into socks tube and reduced dyeing parts. The descriptions are as follows: (1) Example 1 of the island synthesis part Put reactants such as terephthalic acid and ethylene glycol (terephthalic acid / ethylene glycol molar ratio 1 / 1.3) into a 2000 liter reaction tank. After the reaction degree of stearic acid and ethylene glycol reaches 96¾ or more, polyethylene glycol (molecular Dong 400) 2 5 weight percent (based on the weight of the synthetic copolymer) and pentaerythritol are added. pentaerythritol) weight 520 ppm (based on the weight of paraben dicarboxylic acid) 'added antimony trioxide / manganese acetate / acetic acid / sodium acetate / triphenyl phosphoric acid (the amount is 300ppm / 20 0ppm / 200ppm / 20 0ppm / 30 0ppm 'Based on the weight of terephthalic acid), etc., the temperature rises to 265 C' After a suitable time ', the vacuum is lowered, and the vacuum degree is reduced by 10 cmHg every 6 minutes' until the vacuum degree reaches 6 torn In the following case, the high vacuum motor is started and the temperature in the reaction tank is increased to 285 ° C. Maintain this temperature until the stirring torque rises to the normal torsional value of synthetic polyethylene terephthalate, then use nitrogen to break the vacuum and pressurize the material. The pelletized copolyester particles are tested after dehydration, cooling and drying. The V. value is 066 dl / g. * The method for measuring IV is based on the weight ratio of tetragas ethane / phenol 40/60 as the solvent, in which the sample concentration is 0.5g / dl, 0.33 g / dl, 0.213 g / dl and 0_125 g / dl. Test the sample solution at ° C using Cannon-1 50 viscosity tube

Page 9 • 'Xin 4403005. Explanation of the invention (6) and the time for the solvent to flow through the viscosity tube, the IV value is calculated and calculated (及. V. The test is measured at 30 ° C) ^

(2) Example 2 of the synthesis of marine material A A terephthalic acid, ethylene glycol (terephthalic acid / ethylene glycol molar ratio of 1 / 1.3), and methanedicarboxylic acid, ethylene glycol (pure The molar ratio of phthalic acid / isophthalic acid is 100/15, and the molar ratio of isophthalic acid / ethanedionate is 1 / κ5) and other reactants are put into a 200 liter reaction tank, and the degree of esterification reaction is greater than 9 63 (; hours, then add 3'5-bis (m-hydroxyethoxycarbonyl) benzene sulfonate (40% ethylene glycol solution) 'of which 3,5-bis (m-hydroxyethyl Carbonyl) sodium benzenesulfonate / mole terephthalate ratio 1/1. Add antimony trioxide / manganese acetate / zinc acetate / sodium fumarate / triphenyl phosphate (the amount is 300ppm / 2. 〇ppm / 200ppm / 200ppin / 300ppm, based on the weight of terephthalic acid) etc. When the temperature rises to 265 ° C, after a suitable time, the vacuum is lowered, and the vacuum degree is adjusted down by 10cmHg every 10 minutes. When the vacuum reaches below 6 t or r, start the high-vacuum motor and start the high-vacuum. The temperature in the reaction tank rises to around 280 ° C. Maintain this temperature until the stirring torque reaches the normal synthetic polyparaphenylene. After the stirring torque value of diethyl diformate, nitrogen was used to break the vacuum, cut off the material under pressure, and pelletize the obtained copolyester. After dehydration, cooling, drying, and recrystallization, solidification was performed. Its solidification conditions were 60 eC (after 6 hours) '6 hours after heating to 7 5 ° C, and then 90 ° C, after 6 hours, it rises to 100 ° C, and after 6 hours, it rises to 1 3 5 ° C After 8 hours, the temperature is raised to 1 60 ° C (the above-mentioned solidification temperature refers to the external temperature), and the ester particles are obtained after tens of hours of solidification. After analyzing the I, V · values, the value is 0.62 dl / g.

Page 10 ί; / 14 〇3 Ο __ Case No. 88106612 g *) Car j month? Day amendment _ V. Description of invention (7)

Example 2 B Polyethylene terephthalate was prepared from isophthalic acid and ethylene glycol (the isophthalic acid / ethylene glycol molar ratio is 1 / 1_5), and 3,5 -di (methanol -Hydroxyethoxycarbonyl) sodium benzoate (40% ethanedase solution), in which polyethylene terephthalate / isophthalic acid / 3, 5-bis (m-hydroxyethoxycarbonyl) The molar ratio of sodium benzenesulfonate is 100/15/10) and other reactants are put into a 200 liter reaction tank to react until the degree of isophthalic acid is greater than 96¾, and then add antimony dioxide / manganese acetate / acetic acid. / Sodium acetate / triphenyl phosphate (the dosage is 300 ppm / 200ppra / 200ppm / 200ppm / 300ppm, based on polyethylene terephthalate), etc., the temperature rises to 265 ℃, after a suitable time, Start to lower the vacuum, and the vacuum degree will be adjusted down by 10 cmHg every 10 minutes 'Until the vacuum reaches 6 torr, start the high vacuum motor' to start high vacuum, and the temperature in the reaction tank will rise to 28 ° C Nearby 'maintain this temperature until the mixing torque reaches the stirring torque value of synthetic polyethylene terephthalate', break the vacuum with nitrogen, cut the material under pressure, cut The resulting copolyester 'dehydrated and air dried, after recrystallization and drying, subjected to solid polymerization. The solidification conditions are 60 ° C (after 6 hours), and the temperature is raised to 75 eC. After 6 hours, the temperature is increased to 90 ° C. After 6 hours, the temperature is increased to 1000c. After 6 hours, the temperature is increased again. To 1 3 5 ° C 'After 8 hours, then increase the temperature to 160 ° C (the above-mentioned solidification temperature refers to the external temperature)' After solidification for tens of hours, ester particles were obtained. After IV analysis, the IV was measured. The value was 0.6 4 d 1 / g.

(3) Composite spinning, weaving into a sock tube, dyeing analysis Example 3 A sea-island type ultra-fine fiber composite spinning, using PET (I. V. is 0.64

444 03 Ο ___Case No. 88106612 ”Car ^ a Today __ V. Description of the invention (8)) or the copolyester synthesized in Example 1 is an island, and the synthetic copolyester in Example 2 is used as a marine material for composite spinning The composite spinning conditions are as follows: there are 60 spinning holes (spindles) on the spinet, and there are 20 island monofilaments (fi 1 ament) in each single bundle of composite spinning. The ratio is 80/20. In addition, its spinning temperature is 287 ° C, and its spinning speed is 9 00 m / min. The spun composite yarn is stretched 4 times at 2 ° C. The analysis results are shown in Table 1 * The method of measuring the single-strength and elongation of composite spinning is tested according to JIS-l-1 0 1 7 Method "* The reduction of composite spinning is performed after boiling for 60 minutes in a 2% aqueous solution of argon sodium. Dissolve the sea, get the island weaving, and measure its fineness. In addition, the sea argon oxide solubility is measured as the fiber weight after the reduction divided by the weight of the fiber before the reduction multiplied by 100 percent.

Example 3 B The ultra-fine fibers from Example 3A were woven into a sock tube, and the results of dyeing were shown in Table 2. The dyeing and finishing conditions are as follows: (1) Dyeing: Disperse dye is Palanil Red 3BE 150% ( BASF Co., Ltd.) Swelling agent o-phenyiphenol 20% bath ratio is 1/20 Dyeing temperature and time is 130 ° c, 60 minutes. (2) Drying_f110 ° C After drying, dry heat treatment is performed, the temperature is 190 ° C, and the treatment is 60

Page 12 ΛΑΛ 03 Ο

(3) Soaking treatment: solution concentration sodium hydroxide aqueous solution of sulfuric acid (hydrosulfite) non-ionic surfactant bath ratio: 1/20 soaking temperature is 80 ° C, soaking time is 25 minutes (4) after soaking in 1 1 Dry at 0 ° c. After the above treatment, the socks are dried and the secret value is measured. The dyeing fastness test is the first m; its color development is π T now lacking Ίιΐ Θ females are called, and the test is washed and filled (according to JIS-L0844 test method) Test) ^ t,, Japan > Shitutomu I 丨 4, helmet and light resistance test (tested according to JIS-L0841 test method) mainly, the results of β Α see Table 2 »

Ο 3 Ο _ Cable No. 88106612 Sept. I. 5. Description of the invention () 0) Table 1. Physical properties and reduction analysis results of composite spinning No. Island composition Sea composition Island / Hyper single bundle island filament number Single bundle island strength (Denny / gram) Single bundle elongation (%) Island monofilament fineness UM) Decrease percentage (%) 31 PET example 2A 80/20 20 3.4 40 0.1 80 32 PET example 2B 80/20 20 3.5 38 0.1 80 33 Example 1 Example 2A 80/20 20 3.7 42 0.08 80 34 Example 1 Example 2B 80/20 20 3.8 43 0.07 80 Table 2. Offshore ultrafine fiber woven into socks for implementation 3 A The results of post-tube staining analysis are as follows: Chromogenicity L value Dyeing fastness Judging by the naked eye 31 22.1 5 5 〇32 22.4 5 5 〇33 25.1 7 8 ◎ 34 26.0 8 7 ◎ Recently, the dyeing depth of one round is lighter than that of two rounds. 1H · Page 14

Claims (1)

Bulletin An island or sheath material for improving composite spinning and dyeing, which is composed of terephthalic acid or dimethyl terephthalate, ethylene glycol, and (1) 3 alcohols or 3 g-energy-based compounds, or 3 The amount of acid or three or more acid functional groups is ⑽ by weight (using synthetic copolymerization and (2) polyacetic acid as raw materials, and the amount is from 1 to η by weight (using t as the weight of the copolyester as Benchmark) Synthetic copolyester, as an island or sheath material of sea-island type or sheath 'resistant microfiber. 2. An improved composite spinning two-color island or sheath material as described in the first item of the scope of patent application, Among them, three yeasts or more than three enzyme functional groups are combined, or three acids or three or more acid functional compounds are compounded, and the preferred amount is from 5% to 5% (based on the weight of the synthetic copolyester). An island or sheath material for improving composite spinning as described in the first item of the patent application scope, wherein three alcohols or three enzyme functional groups are combined, or three acids or three acid functional compounds are glycerol Triolethane, pentaerythritol, trimellitic anhydride. 6 As described in the first item of the scope of patent application An island or le material that improves the composite spinning β 'wherein the amount of polyethylene glycol is preferably from 1 to 5 weight percent (based on the weight of 10% of copolymerization), as described in the first item of the scope of patent application An improved composite spinning ', island or Lai material, wherein the molecular weight of the polyethanol is 2000 to 20,000. The year on page 15? Month & Day Correction: Ψ Μβ%: φ, > 1 丨 Case No. 88106612 Category: (The above columns are filled by this bureau) Invention Patent Specification 444030 Chinese Island or Sheath Material for Improving Composite Fiber Dyeing, Name of Invention Novel Materials for Improved the Dyeability of Conjugated Fibers Name (Chinese) 1. You Wubin 2. Zheng Mengsong Inventor Name (English) 1. Yuo Wu Bin 2. Cheng Meng Song Nationality 1. Republic of China 2. Chinese people trapped, Residence 1. 1st, 7th Floor, 105 Southeast Street, Hsinchu City 2. 14th Floor, 105 Changlu Road, Changhua City Name (Name) (Chinese) 1. You Wubin 2. Zheng Mengsong Name (Name) (English) 1. Yuo Wu Bin 2. Cheng Meng Song Nationality 1. Republic of China 2. Residence, domicile (office) of the Republic of China applicant 1. 1st, 7th floor, 105 Dongnan Street, Hsinchu City 2. Representative, 14th floor, 105 Changlu Road, Changhua City Name of the person (Chinese) 1. 2. Name of the representative (English) 1. 2. Page 1 __Case No. 88106612__} η Ο -------- V. Description of the invention (1) In the case of composite spinning, when using polyparaxylylene as the island or Lai material, heat is used. When the alkali-soluble soluble copolyester is a sea or core material, after composite spinning and weight reduction, the dyeability is not bad after weaving into a cloth (the color is not deep enough and fresh). The present invention uses terephthalic acid (or p-benzene Dimethyl diformate), 6 diol, tri- or tetra-ol (or acid) functional groups and polyethylene glycol as raw materials to synthesize copolyesters as island or sheath materials. After composite spinning, weaving into fabrics and dyeing. The depth of dyeing and the brightness of color are better than using polyethylene terephthalate as an island or sheath material. The sheath fine type and the sea-island type ultra-fine weaving dimension spun out of the present invention can have a fineness of less than 0.1 denier, or even superfine fibers such as 0.00 OOO denier. At present, this type of product includes silk fabrics such as suede, silk, peach, and rose. In the patent literature, 'improving the dyeing method of poly (p-phenylene terephthalate) is generally used 3, 5-di ( Sodium methoxycarbonyl) benzenesulfonate, 3,5-di-hydroxyethylcarbonyl) benzenebenzenesulfonate or sodium isophthalate sulfonate, etc., and / or alcohol (polyethylene glycol) or isophthalic acid, etc. should be changed to 5 When synthesizing poly (ethylene terephthalate), a synthetic copolyester (shovel; called cationic dyeable polysleep) is added. If cationic dyeability is used, it can improve the dyeing of the island after the reduction of composite spinning. In the process of weight reduction, some cations can be removed in the process of weight reduction, so that the surface of the fiber exhibits uneven physical properties. The patent literature in this regard is representative of the '/ Affecting Fiber No. 18128 (published in 1 998) published in the specification to Kaiping 10-3, 5-bis (m-Ethoxyethoxyl) sodium sulfonate and benzene Two: acid and (or dimethyl terephthalate) and ethylene glycol manganese …two................................................ ........................................ ........................................ ........................................ ........................................ .......... ... IιΑ copolyester is an island material, heart 0 from __ 索 号 .881Q6612 to fight for $? a A.t_ V. Description of the invention (2) To improve the problem of island fabric dyeing after composite spinning reduction, (2) Japanese Unexamined Patent Publication No. 9-2794 18 (published in 1997) uses terephthalic acid and ethyl acetate. Diacid was added with polyethylene glycol and sodium 3,5-bis (methoxycarbonyl) benzenesulfonate as raw materials to synthesize the copolyester as an island material, which is used to improve the composite yarn access and reduce the dyeability of island fibers after weight reduction. In addition, 'Some patents have different weight loss conditions to improve the dyeing properties of the island after the composite spinning weight loss. For example, (1) Japanese Patent Application No. 4_281075 (published in 1992) mentions the use of sodium tripolyphosphate. ) Improving the dyeing properties of Shimori fabrics by soaking poly-ethylene terephthalate fibers in aqueous solution, (2) Japanese Unexamined Patent Publication No. 4-281076 (published in 1992) mentions the use of poly-terephthalic acid. The diethyl island weave was immersed in sodium argon oxide, hydrosulfite, and nonionic surfactant, which improved the dyeability of the island weave. The invention uses terephthalic acid (or dimethyl terephthalate), adipic acid, pentaerythritol and polyethanol as raw materials to synthesize a copolyester as an island material, which is used to improve the dyeability of the island weave. The fiber will not be partially dissolved by sodium argonate during weight reduction. 0 _ The sea or core material of the present invention can be used to synthesize 1,4-bis (hydroxyl) with terephthalic acid (or dimethyl terephthalate) and ethylene glycol. Ethoxycarbonyl) benzene, or diethyl p-benzylate, ethylene glycol, or comonomers (such as bisacids, bis, dianhydrides, bisols, polyetherols, bisacids, bis Copolyester synthesized from raw materials such as esters and acid salts. The (1) diacid mentioned above may be isophthali (acid), phthanc acid, 1,4-cyclohexyl diψ acid ζ Λ Λ _ ^, 1 '4 ~ cyc 1 ohexane di carboxy 1 ic acid), adipic acid 444 030 _ cable number 88106612 amended on the day of the month _ V. Description of the invention (3) (adipic acid), 2,6-diphthalic acid (2,6-naphthalene dicarboxylic acid), etc. (2) The diester can be Dimethyl isophthalate, dimethyl phthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl adipate, dimethyl 2,6-dicarboxylate, etc. (3) Diester anhydride may be phthalic anhydride, etc., (4) Diol may be diethylene glycol, triethylene glycol, 1,4-cyclohexanediol ( 1,4-cyclohexane dimethanol), propylene glycol, 2-methyl-1,5-pentanediol, neoglutarase, xylene glycol, etc. (5) Polyol can be Polyacetic acid, polypropylene glycol, polytetramethylene glycol, or a copolymer thereof, etc. (6) The diacid sulfonate may be sodium salt of sulfoisophthalic acid ), Isophthalic acid, lithium isophthalate sulfonate, magnesium isophthalate sulfonate, sodium 2, 6-dicarboxylic acid-4-sulfonate (2,6-dicarboxylic acid) acid naphthalene-4-sulfonic acid), 3,5-cyclohexane di carboxy1i c acid-4-sulfonic acid, (7) diester acid salt can be 3, Sodium 5-bis (methylcarbonyl) benzenesulfonate, Potassium 3,5-bis (methylcarbonyl) benzenesulfonate, Lithium 3,5-bis (methylcarbonyl) benzenesulfonate, 3, 5-Di (fluorene) Carbonyl) magnesium benzenesulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) sodium benzenesulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 3, 5- Lithium bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 3,5-bis (m-hydroxyethoxycarbonyl) benzene wall Tetrabutyl vinegar 4 A4 Ο 3 Ο _ case number 88106612 $ month? Amendment _ V. Description of the invention (4) phosphonium-3,5-di (beta-hydroxyethoxycarbony 1) benzene sulfonate], 3,5-bis (methoxythionyl) phenylphosphonic acid tetra-butyl vinegar [tetrabutyl phosphonium -3,5-di (carbomethoxy) benzene sulfonate], 3,5-di (methoxybothyl) cyclohexyl sodium sulfonate (sodium salt of 3,5-dicarbomethoxy cyclohexane sulfonic acid), 3, 5-di ( Sodium salt of 3,5-di (beta-hydroxyethoxycarbony 1) cyclohexane sulfonic acid, 3,5-di (methoxycarbonyl) cyclohexanesulfonic acid Tetra butyl phosphonium-3,5-di (carbomethoxy) cyclohexane sulfonate, 3, 5-bis (m-hydroxyethoxycarbonyl) cyclohexanesulfonic acid Ester [VII 61; ^ 1) 11171 卩} 108-port 11011111111- (beta-hydroxyethoxycarbonyl) cyclohexane sulfonate] and the like. The invention uses terephthalic acid (or dimethyl terephthalate), ethylene glycol, tri or tetraol (or acid) functional groups and polyethylene glycol as raw materials to synthesize a copolyester as an island or sheath material. In order to improve the dyeing property of the composite spinning weight-loss fabric. The molecular weight of polyethylene glycol mentioned in the present invention is 200 to 20,000, and a molecular weight of 200 to 4,000 is a better molecular weight of polyethanol. In addition, the tri- or tetra-ol (or acid) functional group of the present invention may be glycerol, trimethyl ethene (e.e. 1 e thane), tetramethanol or pentaerythritol (pentaerythritol), heptamate ( 1: rime 1 1 iticanhydride) and so on. A few examples are described below. The examples are only for the present invention. Said __ _ cable number 88106612 V. Description of the invention (5) General illustration of the method 'is not intended to limit the scope of the invention, so it is stated here that the embodiment of the invention is divided into (1) island synthesis, (2) sea Synthetic, (3) Composite spinning 'woven into socks tube and reduced dyeing parts. The descriptions are as follows: (1) Example 1 of the island synthesis part Put reactants such as terephthalic acid and ethylene glycol (terephthalic acid / ethylene glycol molar ratio 1 / 1.3) into a 2000 liter reaction tank. After the reaction degree of stearic acid and ethylene glycol reaches 96¾ or more, polyethylene glycol (molecular Dong 400) 2 5 weight percent (based on the weight of the synthetic copolymer) and pentaerythritol are added. pentaerythritol) weight 520 ppm (based on the weight of paraben), adding antimony trioxide / manganese acetate / acetic acid / sodium acetate / triphenyl phosphoric acid (the dosage is 300ppm / 20 0ppm / 200ppm / 20 0ppm / 30 0ppm 'Based on the weight of terephthalic acid), etc., the temperature rises to 265 C' After a suitable time ', the vacuum is lowered, and the vacuum degree is adjusted down by 10 cmHg every 6 minutes until the vacuum degree reaches 6 torn In the following case, the high vacuum motor is started and the temperature in the reaction tank is increased to 285 ° C. Maintain this temperature until the stirring torque rises to the normal torsional value of synthetic polyethylene terephthalate, then use nitrogen to break the vacuum and pressurize the material. The pelletized copolyester particles are tested after dehydration, cooling and drying. The V. value is 066 dl / g. * The method for measuring IV is based on the weight ratio of tetragas ethane / phenol 40/60 as the solvent, in which the concentration of the prepared sample is 0.5g / dl, 0.33 g / dl, 0.213 g / dl and 0_125 g / dl. Test the sample solution at ° C using Cannon-1 50 viscosity tube Page 9 • 'Xin 4403005. Explanation of the invention (6) and the time for the solvent to flow through the viscosity tube, the IV value is calculated and calculated (及. V. The test is measured at 30 ° C) ^ (2) Example 2 of the synthesis section of marine materials A terephthalic acid, ethylene glycol (terephthalic acid / ethylene glycol molar ratio of 1 / 1.3), and methylene dicarboxylic acid, ethylene glycol ( Terephthalic acid / isophthalic acid molar ratio is 100/15, isophthalic acid / glycollic acid molar ratio is 1 / κ5) and other reactants are put into a 200 liter reaction tank to wait for the degree of esterification reaction. More than 9 63 (; when adding 3'5-bis (m-hydroxyethoxycarbonyl) benzene sulfonate (40% ethylene glycol solution) 'of which 3, 5-bis (m-hydroxyethyl Carbonyl) sodium benzenesulfonate / molar ratio of terephthalic acid 1/1. Add antimony trioxide / manganese acetate / zinc acetate / sodium cool acid / triphenyl phosphate (the amount is 300 ppm / 2) 〇〇ppm / 200ppm / 200ppin / 300ppm, based on the weight of terephthalic acid) etc. When the temperature rises to 265 ° C, after a suitable time, the vacuum is lowered, and the degree of vacuum is adjusted down every 10 minutes. cmHg until vacuum When the pressure is less than 6 t or r, the high-vacuum motor is started, and the high-vacuum is started. The temperature in the reaction tank rises to around 280 ° C. Maintain this temperature until the stirring torque reaches the normal synthetic polyethylene terephthalate. After the torque value, nitrogen was used to break the vacuum, cut off the material under pressure, pelletize the obtained copolyester, dehydrate, cool dry, dry and recrystallize, and then solidify. Its solidification conditions are 60 eC (after 6 hours) ' 6 hours after heating to 7 5 ° C, and then to 90 ° C. After 6 hours, the temperature is increased to 100 ° C. After 6 hours, the temperature is increased to 1 35 ° C, and after 8 hours, the temperature is increased to After 1 60 ° C (the above-mentioned solidification temperature refers to the external temperature), ester particles were obtained after solidification for tens of hours. After analyzing the I, V · values, the value was 0.62 dl / g. Page 10 ί; / 14 〇3 Ο __ Case No. 88106612 g *) Car j month? Day correction _ V. Description of the invention (7) Example 2 B Polyethylene terephthalate monoethyl vinegar is made into isophthalic acid and ethylene glycol (the isophthalic acid / ethylene glycol molar ratio is 1 / 1_5 ), And 3,5-bis (m-hydroxyethoxycarbonyl) benzoic acid sodium (40% ethanedase solution), in which polyethylene terephthalate / isophthalic acid / 3, 5- Reactants such as sodium bis (m-hydroxyethoxycarbonyl) benzene sulfonate with a molar ratio of 100/15/10) were placed in a 200 liter reaction tank and reacted until the degree of isophthalate was greater than 96¾, then added Antimony dioxide / manganese acetate / acetic acid / sodium acetate / triphenyl phosphate (the dosage is 300 ppm / 200 ppra / 200 ppm / 200 ppm / 300 ppm, based on polyethylene terephthalate), etc., the temperature rises To 265 ℃, after a certain period of time, the vacuum is lowered, and the vacuum degree is adjusted down by 10 cmHg every 10 minutes. 'When the vacuum reaches 6 torr or less, the high vacuum motor is started.' The temperature in the reaction tank rose to around 28 ° C. 'When this temperature is maintained until the torque of the blending reaches the stirring torque of synthetic polyethylene terephthalate' Breaking the vacuum with nitrogen, pressurized cutting, pelletizing the resulting copolyester 'dehydrated and air dried, after recrystallization and drying, subjected to solid polymerization. The solidification conditions are 60 ° C (after 6 hours), and the temperature is raised to 75 eC. After 6 hours, the temperature is increased to 90 ° C. After 6 hours, the temperature is increased to 1000c. After 6 hours, the temperature is increased again. To 1 3 5 ° C 'After 8 hours, then increase the temperature to 160 ° C (the above-mentioned solidification temperature refers to the external temperature)' After solidification for tens of hours, ester particles were obtained. After IV analysis, the IV was measured. The value was 0.6 4 d 1 / g. (3) Composite spinning, weaving into a sock tube, dyeing analysis Example 3 A sea-island type ultra-fine fiber composite spinning, using PET (I. V. is 0.64 444 03 Ο ___Case No. 88106612 ”Car ^ a Today __ V. Description of the invention (8)) or the copolyester synthesized in Example 1 is an island, and the synthetic copolyester in Example 2 is used as a marine material for composite spinning The composite spinning conditions are as follows: there are 60 spinning holes (spindles) on the spinet, and there are 20 island monofilaments (fi 1 ament) in each single bundle of composite spinning. The ratio is 80/20. In addition, its spinning temperature is 287 ° C, and its spinning speed is 9 00 m / min. The spun composite yarn is stretched 4 times at 2 ° C. The analysis results are shown in Table 1 * The method of measuring the single-strength and elongation of composite spinning is tested according to JIS-l-1 0 1 7 Method "* The reduction of composite spinning is performed after boiling for 60 minutes in a 2% aqueous solution of argon sodium. Dissolve the sea, get the island weaving, and measure its fineness. In addition, the sea argon oxide solubilization is measured as the fiber weight after the reduction divided by the weight before the reduction multiplied by 100 percent. Example 3 B will be implemented Example 3A: The microfibers after weaving the sea were woven into socks, and the results of dyeing were shown in Table 2. The dyeing and finishing conditions are as follows: (1) Dyeing: Dispersibility The dye is Palanil Red 3BE 150% (manufactured by BASF). Swelling agent 20% o-phenyiphenol. Bath ratio is 1/20. Dyeing temperature and time are 130 ° C and 60 minutes. (2) Drying _f110 ° C Dry heat treatment after drying, temperature is 190 ° C, treatment 60 Page 12 ΛΑΛ 03 Ο (3) Soaking treatment: solution concentration sodium hydroxide aqueous solution of sulfuric acid (hydrosulfite) non-ionic surfactant bath ratio: 1/20 soaking temperature is 80 ° C, soaking time is 25 minutes (4) after soaking in 1 1 Dry at 0 ° c. After the above treatment, the socks are dried and the secret value is measured. The dyeing fastness test is the first m; its color development is π T now lacking Ίιΐ Θ females are called, and the test is washed and filled (according to JIS-L0844 test method) Test) ^ t,, Japan > Shitutomu I 丨 4, helmet and light resistance test (tested according to JIS-L0841 test method) mainly, the results of β Α see Table 2 » Ο 3 Ο _ Cable No. 88106612 Sept. I. 5. Description of the invention () 0) Table 1. Physical properties and reduction analysis results of composite spinning No. Island composition Sea composition Island / Hyper single bundle island filament number Single bundle island strength (Denny / gram) Single bundle elongation (%) Island monofilament fineness UM) Decrease percentage (%) 31 PET example 2A 80/20 20 3.4 40 0.1 80 32 PET example 2B 80/20 20 3.5 38 0.1 80 33 Example 1 Example 2A 80/20 20 3.7 42 0.08 80 34 Example 1 Example 2B 80/20 20 3.8 43 0.07 80 Table 2. Offshore ultrafine fiber woven into socks for implementation 3 A The results of post-tube staining analysis are as follows: Chromogenicity L value Dyeing fastness Judging by the naked eye 31 22.1 5 5 〇32 22.4 5 5 〇33 25.1 7 8 ◎ 34 26.0 8 7 ◎ Recently, the dyeing depth of one round is lighter than that of two rounds. 1H · page 14 I A44 03 0-case number 88106612_d March? B __ 4. Abstract of Lingwen's invention (the name of the invention: an island or sheath material for improving the dyeing of composite fibers) In composite spinning, polyethylene terephthalate (pET; polyethylene terephthalate) is used as an island or le When the hot-water soluble polyester is a sea or core material, after composite spinning and weight reduction, it is not well dyed after weaving into cloth (color is not deep enough and bright). The present invention uses terephthalic acid (or Terephthalate), ethylene glycol, tri- or tetra-ol (or acid) functional groups and polyethylene glycol as raw materials. Synthetic copolymer vinegar is island or Le. Dyeing after cloth, its dyeing depth and bright color are better than using polyethylene terephthalate as an island or sheath material. English Abstract of Invention (Name of the invention: Novel Materials for Improved the Dyeabilitv of Conjugated Fibers) The core / sheath type and islands in sea type conjugated fibers have been used PET as core's or island's materials, and hot base water soluble copolyesters as sheath's or sea's materials. The dyeab i1i ty of conjugated fibers used PET as island ’s or core ’s material was not so good. ffe have used copolyester (prepared from terephthalate glycol, polyethylene glycol and pentaerythri tol as raw material) as island ’s or core ’s materials have been improved island ’s and core ’s dyeability in page 2 Bulletin An island or sheath material for improving composite spinning and dyeing, which is composed of terephthalic acid or dimethyl terephthalate, ethylene glycol, and (1) 3 alcohols or 3 g-energy-based compounds, or 3 The amount of acid or three or more acid functional groups is ⑽ by weight (using synthetic copolymerization and (2) polyacetic acid as raw materials, and the amount is from 1 to η by weight (using t as the weight of the copolyester as Benchmark) Synthetic copolyester, as an island or sheath material of sea-island type or sheath 'resistant microfiber. 2. An improved composite spinning two-color island or sheath material as described in the first item of the scope of patent application, Among them, three yeasts or more than three enzyme functional groups are combined, or three acids or three or more acid functional compounds are compounded, and the preferred amount is from 5% to 5% (based on the weight of the synthetic copolyester). An island or sheath material for improving composite spinning as described in the first item of the patent application scope, wherein three alcohols or three enzyme functional groups are combined, or three acids or three acid functional compounds are glycerol Triolethane, pentaerythritol, trimellitic anhydride. 6 As described in the first item of the scope of patent application An island or le material that improves the composite spinning β 'wherein the amount of polyethylene glycol is preferably from 1 to 5 weight percent (based on the weight of 10% of copolymerization), as described in the first item of the scope of patent application An improved composite spinning ', island or Lai material, wherein the molecular weight of the polyethanol is 2000 to 20,000. Page 15