TW491865B - Novel copolyester material having non-round cross-section - Google Patents

Abstract

New synthesis copolyester material for new copolyester staple fiber have non-round cross-section that are retained. These non-round cross-section fibers provide fabrics having outstanding comfort qualities of moisture-management, dryness and comfort, along with minimal pilling.

Description

491865 V. Description of the invention (1) The present invention is a synthetic polyester material that can be spun into irregularly shaped fibers, especially a cloth woven with irregular grooved oval shell-shaped cross-sections and irregularly shaped fibers. Making clothes will have good ball characteristics, good feel (touch) and dry characteristics. Twenty years ago, 'there are some patent documents mentioning how to make cut fibers', such as US Patent No. 3, 9 1 4, 488, US Patent No. 4, 634, 625, and US Patent No. 4, 707. No. 407 and other patent specifications tell people the continuous manufacturing of irregular cross-section fibers and cotton. In addition, U.S. Patent Application No. 08/662, 804 (1996) 08 / 778,462 (1997), 08 / 778,458 No. (1997 Patent Specification 'U.S. Patent Nos. 5,591,523 and 5,626,96 Certificate 1 and World Patent Nos. WO 97/02374 (1997), WO 08 / 497,495 (1995) ^ ff〇97 / 02372 ( (1997) > WO 08 / 642,650 (1996), ff〇97 / 02373 (1997) and other special books; the book tells people how to spin spinning methods with irregular cross-sections and how to design nozzles. But the above patents can be spun out Cotton with an irregular cross section does not improve the problem of voluminous balls made of irregular silk or cotton. US Patent No. 3,3 3,5,2 11 tells Poly _ Add tetraethy silicate to adjust the relative viscosity (reiative viscosit to 17 'and at 275 ° C, at a melt viscosity of ι, 6,000 to 6,000 poise), can improve the fluff phenomenon. US Patent Nos. 3,018,272 and 3,104,450 said! The cross section therefore, Anti-pilling surface irregularities J. Book, on the method. 9) and other patents say that M description parts and spinning and easy-piling rabbits are) at 10 (poise book tells 491865 V. Description of the invention (2) 5〜 During the process of diethyl phthalate, the addition of 3,5 one bis (m-transylethoxycarbonyl) sodium benzoate can improve the fluff phenomenon, and the relative viscosity of the synthetic copolyester is 14. 5 ~ 17.5.

In US Patent Nos. 5,559,205 and 5,607,765, it is mentioned that after adding 0.5 to 5 moles of sodium 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate It can improve the fluffing phenomenon, but it is not easy to spin. Therefore, changing the monomer to 3,5-bis (m-hydroxyethoxycarbonyl) lithium benzoate can improve the spinning situation. And in the patent specification of World Patent No. 92/1 31 20, it is mentioned that after adding 3, 5-bis (m-hydroxyethoxycarbonyl) benzenesulfonic acid sodium or potassium salt, titanium dioxide can be added to make As a matting agent. U.S. Patent No. 3,3 3 5,2 11 mentions that polyethylene glycol can be used to improve the spinning of copolyesters synthesized by the addition of sodium 3,5-bis (m-hydroxyethoxyquinyl) benzenesulfonate. Silkiness and fluffing. But after adding polyethylene glycol (Polyethylene glycol), its spinning properties and stiffness are not enough, so it is not easy to spin into special-shaped fibers. Therefore, ethyl silicate or trimethylel propane and trioxide are added. Titanium is used to adjust the relative viscosity of the synthesis, improve the spinnability and fluffing phenomenon.

The present invention uses 6 to 12 carbon tricarboxylic or tricarboxylic anhydride compounds (which can be aliphatic or aromatic), 3,5-bis (methoxycarbonyl) benzenesulfonate or 3,5-bis ( M-hydroxyethoxycarbonyl) benzenesulfonate or isophthalate sulfonate, polyethylene glycol and diethylhydroxyterephthalate [BHET; bis (hydroxy ethoxy) terephalate] as reactants, and then Co-polyesters are synthesized by chemical or transesterification and polycondensation reactions, and the synthetic copolyesters have an acid relative viscosity of 8 to 12, non-

Page 5 491865 V. Description of the invention (3) Non-acid relative viscosity (Non-Acid relative viscosity) minus acid The relative viscosity value is between 1 and 3. The synthetic copolyester mentioned in the present invention has an acid relative viscosity value in a preferred range of 9 to 11. The tricarboxylic acid or tricarboxylic anhydride compound of 6 to 12 carbons mentioned in the present invention, wherein the tricarboxylic acid compound of 6 to 12 carbons may be 1,2,3-tricarboxylic acid propane (Propane-1, 2,3-tricarboxylic acid), Benzene-1,2,3-tricarboxylic acid, Benzene-1,2,4-tricarboxylic acid tricarboxylic acid), 6 to 12 carbon tricarboxylic anhydride compounds may be 1,2,4-tricarboxylic anhydride (Tricarboxylic anhydride) and the like. Isophthalic xanthate can be Sod i um salt of sulfoisophthalic acid, potassium isophthalate sulfonate, lithium isophthalate sulfonate, magnesium isophthalate sulfonate , 2,6-dicarboxylic acid-naphthalene-4-sulfonic acid, sodium 3,5-cyclohexanedicarboxylic acid -4-su1fonic acid), and the 3, 5-bis (methoxycarbonyl) benzenesulfonate can be 3,5-bis (methoxycarbonyl) benzenesulfonic acid sodium, 3,5-bis (methoxycarbonyl) benzene Potassium dibasic acid, lithium 3,5-bis (methoxycarbonyl) benzenesulfonate, magnesium 3,5-bis (methoxycarbonyl) benzenesulfonate, 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate The acid salt may be sodium 3,5-bis (m-xylethoxycarbonyl) benzene phthalate, potassium 3,5-bis (m-xylethoxycarbonyl) benzenesulfonate, 3,5-bis ( M-Hydroxyethoxycarbonyl) benzenesulfonic acid, 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonic acid

Page 6 491865 V. Description of Invention (4) Town. Polyethylene glycol used in the present invention has a molecular weight of 200 to 5,000, with a molecular weight of 300 to 2,000 being the preferred molecular weight. The diethyl hydroxy terephthalate used in the present invention is synthesized from terephthalic acid and ethylene glycol through an esterification reaction at 2 20 to 260 t: reaction temperature, or via dimethyl terephthalate. Ester and ethylene glycol are synthesized by reaction at 2000 ~ 250 ° C and transesterification catalyst. The transesterification catalyst can be magnesium acetate, calcium acetate, manganese acetate, cobalt acetate, zinc acetate, and lead acetate. The catalysts used in the present invention are recording compounds (such as antimony trioxide, acid recording, etc.) 'tin compounds [such as two Butyl stannous oxide (dibudyltin oxide, dibutyl dilauryl tin, etc.), titanium compounds [such as tetrabutyl titanate, tetraisopropyltitanate], etc. are poly Condensed coal, using acetic acid # 5, acetic acid, manganese acetate, lead acetate, acetic acid, and lead acetate as transesterification reaction catalysts. It can also be used in combination with sodium acetate, potassium acetate, and lithium acetate. . The process of the present invention can use stabilizers, such as trimethyl phosphate, triphenyl phosphate, phosphoric acid, Irganox 100, and the like. The amount of the tri-acid or tri-zoic anhydride compound of 6 to 12 carbons used in the present invention is 20 to 100 ppm (based on diethylhydroxyterephthalate). Among them, 40 ~ 50 0 ppm is the best use range, 3, 5-2

491865 V. Description of the invention (5) The amount of (methoxycarbonyl) benzenesulfonate or 3,5-bis (m-hydroxyethoxycarbonyl) benzoate or isophthalate sulfonate is 0.5 ~ 5 mol%-(Diethylhydroxyparaben dicarboxylate is 〇00%), of which the preferred amount is 0.5 ~ 3 mol% is the preferred amount, and the polyethylene glycol is used as 0.5 to 10 weight percent (100% based on diethylhydroxyterephthalate), with 0.5 to 5 weight percent being the preferred range of use. A few examples are described below. The examples described are merely general illustrations of the method of the present invention, and are not intended to limit the scope of the invention.

Example 1 Sodium A, 3, 5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate can be purchased directly from the market (40% ethylene glycol solution) or synthesized as follows: (1) isophthalic acid Sodium sulfonate and ethylene glycol are directly esterified to synthesize 40% of 3,5-bis (m-hydroxyethoxycarbonyl) benzene sulfonate in ethylene glycol solution. The synthesis process requires the addition of sodium acetate and potassium acetate. Or lithium acetate can inhibit the formation of diethylene glycol. The synthesis conditions are the same as the general esterification reaction conditions. The reaction temperature is about 2 3 0 to 2 50. (:.

(2) Transesterification reaction between sodium 3,5-bis (methoxycarbonyl) benzylsulfonate and ethylene glycol in the presence of transesterification catalysts such as manganese acetate, etc., needs to be carried out between 14 ° C and 220 ° C. Lithium acetate, potassium acetate or sodium acetate are used to inhibit the formation of diethylene glycol. B. Copolyester synthesis Put the reactants terephthalic acid and ethylene glycol (Mole ratio 1 to 4)

$ 8 pages 491865 V. Description of the invention (6)

In the reaction tank, after the esterification reaction to synthesize diethyl terephthalate (reaction temperature 240 ~ 2 60 ° C), add 3, 5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate and three The amount of carboxylic anhydride compound and polyethylene glycol is shown in Table 1 ', and added with trioxide / zinc acetate / manganese / manganese acetate / sodium acetate (300ppm / 20ppm / 20ppm / 20ppm), and trimethylamine Phosphate is a stabilizer. After the internal temperature rises to 24 0 ° C, vacuum is started. The vacuum rate is adjusted down by 10 cmHg every 10 minutes at a vacuum degree until the vacuum reaches 76 cmHg (76 cmHg is high vacuum) (0cmHg is 1 atmosphere), then use a high-powered motor to draw a high vacuum. At this time, the temperature in the reaction tank is maintained at about 270 ° C. This condition is maintained until the stirring torque rises to that of the synthetic polyparaphenylene. At the reaction temperature of diethyl diformate (280 ~ 290 ° c), after the stirring torque rises to a certain value (in this synthesis reaction, the torque rise number is 4 divisions), the synthetic copolyester is stirred at this stress. The melt viscosity is the same, the gas is broken under vacuum, and the material is discharged under pressure. The obtained sample is analyzed for an acid phase. The viscosity and non-acid relative viscosity, as shown in Table 1. * With acid relative viscosity (AR V) test method. Using hexafluoroisopropanol as a solvent, adding 98 ppm of 98% reduced-grade concentrated sulfuric acid as a solvent, and dissolving the synthesized copolymerized polymer g in hexafluoroisopropanol (containing PPM) agricultural sulfuric acid). The solution is dissolved at 25 ° C and its concentration is 4.75 wt%. At 25 t, the time for the sample solution to flow through the viscosity tube is measured using a canned viscosity tube. The time for pure hexafluoroisopropanol to flow through the viscosity tube is Relative acid viscosity is t /%, refers to the part of copolyester

491865 V. Description of the invention (7) After the crosslink is decomposed by concentrated sulfuric acid, the relative dryness is measured. * Non-acid relative viscosity (NR V) test method The above synthetic copolyester is dissolved in hexafluoroisopropanol and (dissolved at 25 ° C) 'its concentration is 4.75 wt%' at 25 ° C: The time for the sample solution to flow through the viscosity tube was measured using a Cannon-! Type dehumidity tube, and the time for pure hexafluoroisopropanol to flow through the dehumidity tube was tG '. The purpose is to measure the relative viscosity only after dissolving in hexamethylene isopropanol (in the presence of some cross-linking). △ RV = NRV-ARV = non-acid relative viscosity ~ with acid relative viscosity, which quite describes the partial crosslinking of copolyester. Table 1 · Composition of synthetic copolyester, the relationship between acid relative viscosity (AR V), non-acid relative viscosity (NRV) and ARV (= NRV-ARV)

Number composition (composition ratio *) NRV ARV ARV 〇1 TPA / SIPE / PEG / TMAC100 / 2/1/300) 11.5 9.6 1 · 9 〇 TPA / SIPE / PEG / BTCA (100/2/1/400) 12.4 9. 5 2.9 〇3 TPA / SIPE / PEG / TMA 12.2 10 · 1 2 · 1 (100 / 2.5 / 1.5 / 300) 〇4 TPA / SI PE / PEG / PTCA (1 0 0/2/1 / 360) 13 1 0.8 2.2 〇5 TPA (IOO) 11.5--

^ 1865, Description of the invention (8) Note: (1) TPA is terephthalic acid. ^ (2) The amount of SiPE used is 3,5-bis (m-hydroxyethoxycarbon) sodium sulfonate mainly in mole%, and the amount of terephthalic acid is 100 mole%). (3) PEG is polyether with a molecular weight of 60 () (100% by weight of terephthalic acid; weight% by weight). (4) TMA is 1,2,4-trimellitic anhydride, and its unit is ppm, which is mainly relative to the weight of terephthalic acid. (5) BTCA is 1,2,4-tricarboxylic acid benzene, the amount of which is used as a unit of ppm, and it is mainly relative to the weight of terephthalic acid. (6) PTCA is 1,2,3-tricarboxylic acid propane, and its amount is expressed in ppm, which is mainly relative to the weight of p-dicarboxylic acid. Example 2 Example Nos. 〇1, 〇3, and 05 after spinning were spun at 285 ~ 2900 ° C. The spinning nozzle had 72 spinning orifices, each spinning orifice was 0.3mm in diameter, and was wound up. The speed is 1,370 m / min (the winding speed of No. 05 is 2,400 m / min), and the roller (Roi 1 er) at 85 ° C is extended 3 times (PET 2 · 4 times); 150 Crimp is applied to the heating plate at ° C. The single bundle of filament is 150 denier / 72, and the cooling air is 19 ° C. After the spun silk and cotton silk were combined (50/50), the amount of fluff balls was measured:

491865 V. Description of the invention (9) The single strand strength and elongation are measured by J IS-L-1 017 method. The amount of fluff is measured according to ASTM D 3512. Table 2.Physical properties measured after spinning No. 1 Breaking point strength Breaking point elongation 01 3.8 g / Denny 25%

03 3.5 grams / denier 23% 05 4.0 grams / denier 30% * is the number of the copolyester synthesized in Example 1 Table 3. After blending with cotton yarn, the amount of wool balls was measured

No. 氺 Measurement time Pilling volume 01 60 minutes 1. 4 03 60 minutes 1. 5 05 30 minutes 1. 3

Page 12 1 is the copolyester number spinning and cotton blending synthesized in Example 1.

Claims (1)

491865 6. Scope of patent application 1. A synthetic copolymeric material, which comprises (1) diethylhydroxy p-dibenzoate, and (2) 3, 5-bis (methoxycarbonyl) benzene sulfonate, or 3, The amount of 5-bis (m-hydroxyethoxycarbonyl) benzyl sulfonate or m-benzyl di-acid sulfonate is 0.5 to 5 mole% (1.00% to diethylhydroxybenzyl dicarboxylate) ), And (3) the amount of tricarboxylic acid or tricarboxylic acid gf compound of 6 to 12 carbons is 20 ~ 100 0 ppm (based on (4) poly (p-phenylenedicarboxylic acid) Ethylene glycol, molecular weight of 200 to 5000, so that the amount of rejection is 0.5 to 10% by weight (100% of diethylhydroxy dibenzyl dicarboxylate). After heating the reaction in the reaction tank, open the Evacuation reaction, the degree of vacuum is gradually reduced to less than 4 torr, and the reaction temperature is 200 to 30 0 ° C. 2. A synthetic copolyester material, such as terephthalic acid Diethyl hydroxy ester is synthesized by hydrazine di-f-acid and ethylene glycol through 180 ~ 25 0 ° C reaction. 3. A synthetic copolyester material as described in item 1 of the patent application scope, where Diethylhydroxyl dibenylate, whether dimethyl dibenzate and ethylene glycol, in the presence of a transesterification catalyst, 80 ~ 25 (TC reaction temperature, synthesis of p-dibenzoate Diethyl hydroxy ester.-4. A synthetic copolyester material according to item 1. of the patent application scope, wherein 3, 5-bis (methoxycarbonyl) benzenesulfonate or 3, 5-bis (m- 5〜 The amount of hydroxyethoxycarbonyl) benzene sulfonate or isophthalate sulfonate is 0. 5 ~ Page 13 491865 VI. Patent application scope-3 mole% (1 G (]% with diethylhydroxyterephthalate) 〇 5. As a synthetic copolyester material in the first patent application scope, Among them, 3,5-bis (methoxycarbonyl) benzylsulfonic acid salt is 3,5-bis (methoxycarbonyl) benzenesulfonic acid alkali metal salt or alkaline earth metal salt. A synthetic copolyester lining, wherein the 3, 5-bis (methoxycarboxy) benzenesulfonic acid alkali metal salt or alkaline earth metal salt is 3, 5-bis (methoxycarbonyl) sodium sulfonate, 3, 5- Di (methoxycarbonyl) potassium benzenesulfonate, 3,5-bis (methoxycarbonyl) lithium sulfonate, 3,5-bis (methoxycarbonyl). Magnesium sulfonate. Item 1 is a synthetic copolyester material in which 3, 5 · -bis (m-hydroxyethoxycarbonyl) benzenesulfonate is an alkali metal salt of 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate Or alkaline earth metal salts. 8. A synthetic copolyester compound according to item 7 of the patent application, wherein 3, · 5-bis (m-hydroxyethylfluorenylcarbonyl) benzenesulfonic acid alkali metal salt or alkaline earth metal salt For 3, 5-two ( -Sodium hydroxyethoxycarbonyl) benzyl sulfonate, Potassium 3,5-bis (m-hydroxyethoxycarbonyl) benzenesulfonate, 'lithium 3,5-bis (m-hydroxyethoxy) benzyl acid 3,5-Di (m-Ethoxyethoxyweilyl) benzene sulfonate. 9. For example, a synthetic copolyester material in the scope of patent application No. 1 in which m-benzenedicarboxylic acid sulfonate is m-benzene An alkali metal salt or an alkaline earth metal salt of dicarboxylic acid sulfonate. 10, A synthetic copolyester material as described in item 9 of the scope of the patent application, wherein the alkali metal salt or alkaline earth metal salt of m-phenylene dicarboxylic acid is m-phenylene Sodium formate sulfonate, potassium isophthalate sulfonate, lithium isophthalate f acid sulfonate, m Page 14 491865 VI. Patent application scope Benzoic acid sulphonic acid ^ XX, ^ ^ 11 If one of the first patent application patent garden materials, the amount of tricarboxylic acid or tricarboxylic acid anhydride of ^ to 12 carbons It is 40 ～ 500 ppm (based on di-6-hydroxyl terephthalate). 12. A synthetic copolyester material according to item 1 of the scope of the patent application, in which 6 to 12 dishes of tri-acid or diacid-acid compounds are 1, 3 " " Tribenzyl acid benzene, 1,2, tartaric acid, 1,2,4-trimellitic anhydride. 13 A synthetic copolyester material according to item 1 of the patent application, wherein the polyglycol has a molecular weight of 300 to 2000 and an amount of 0.5 to 10 weight percent (in terms of diethylhydroxyterephthalate). 100%) ° Page 15