JPS63120111A - Production of modified polyester yarn - Google Patents
Production of modified polyester yarnInfo
- Publication number
- JPS63120111A JPS63120111A JP18523987A JP18523987A JPS63120111A JP S63120111 A JPS63120111 A JP S63120111A JP 18523987 A JP18523987 A JP 18523987A JP 18523987 A JP18523987 A JP 18523987A JP S63120111 A JPS63120111 A JP S63120111A
- Authority
- JP
- Japan
- Prior art keywords
- glycol
- yarn
- component
- modified polyester
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 101
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000009987 spinning Methods 0.000 claims abstract description 26
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims 2
- 239000003513 alkali Substances 0.000 abstract description 20
- 238000007334 copolymerization reaction Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 43
- 238000002474 experimental method Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 12
- 238000006864 oxidative decomposition reaction Methods 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000981 basic dye Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- -1 glycol ester Chemical class 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は塩基性染料可染型の改質ポリエステル域雑の製
造方法に関するものでおる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing modified polyesters dyeable with basic dyes.
更に詳しくは、染色性が良好で糸強度が高く、耐アルカ
リ性に優れ、かつ染色物の耐光堅牢性に優れた塩基性染
料可染型の改質ポリエステルＩＩｉ維の′ｊＡ造方法に
関するものである。More specifically, it relates to a method for producing modified polyester IIi fibers dyeable with basic dyes, which have good dyeability, high yarn strength, excellent alkali resistance, and excellent light fastness of dyed products. .
［従来の技術］
従来より、特公昭３４−１０４９７号公報において塩基
性染料可染型ポリエステルは知られているが、この方法
は染色性を満足させるために金属スルホネート基を含有
するイソフタル酸成分（以下Ｓ成分と略す）を多量に含
有させるため、通常の方法で紡糸すると、ポリマの溶融
粘度が高く紡糸が困難となる。従ってＳ成分を多量に含
有したポリマを通常の方法で紡糸するにはポリマの重合
度を低くし、溶融粘度を通常紡糸できる範囲まで下げる
必要がある。この結果、糸強度が低下し、また多量のＳ
成分の添加により耐アルカリ性が低下するので得られた
ポリエステル繊維の用途が制限される。ざらにまたＳ成
分を多量に添加すると、当然ながら原料コストが大幅に
アップする。[Prior Art] A basic dye dyeable polyester has been known in Japanese Patent Publication No. 34-10497, but this method uses an isophthalic acid component containing a metal sulfonate group ( Since the polymer contains a large amount of the S component (hereinafter abbreviated as component S), the melt viscosity of the polymer is high and spinning becomes difficult when spinning using a normal method. Therefore, in order to spin a polymer containing a large amount of the S component by a conventional method, it is necessary to lower the degree of polymerization of the polymer and lower the melt viscosity to a range that allows normal spinning. As a result, the yarn strength decreases and a large amount of S
The use of the resulting polyester fibers is limited because the alkali resistance decreases due to the addition of these components. Naturally, if a large amount of S component is added, the raw material cost will increase significantly.
上記問題点を改善するためにＳ成分を減少させ、それに
よる染色性低下を補うために、イソフタル酸、アジピン
酸などの酸成分等、グリコール成分を共重合する方法が
知られている。In order to improve the above-mentioned problems, a method is known in which the S component is reduced, and in order to compensate for the resulting decrease in dyeability, a method is known in which a glycol component, such as an acid component such as isophthalic acid or adipic acid, is copolymerized.
例えば特公昭５５−１７８０６号公報にはＳ成分を共重
合したコポリマーにポリアルキレングリコールを１〜１
０重量％共重合する例が記載されている。かかる例では
確かにグリコール成分の共重合により染色性が向上して
いるが、糸強度が不充分でありアルカリ処理に耐えられ
る糸質は得られていない。For example, in Japanese Patent Publication No. 55-17806, 1 to 1 polyalkylene glycol is added to a copolymer prepared by copolymerizing the S component.
An example of 0% by weight copolymerization is described. In such examples, the dyeability is certainly improved by the copolymerization of the glycol component, but the yarn strength is insufficient and a yarn quality that can withstand alkali treatment cannot be obtained.
［発明が解決しようとする問題点］
本発明者らはＳ成分共重合系でグリコール成分を共重合
させることにより以下のことが可能となることを見い出
している。[Problems to be Solved by the Invention] The present inventors have discovered that the following becomes possible by copolymerizing a glycol component in an S component copolymerization system.
その一つはグリコール成分の共重合により少ないＳ成分
の共重合量で満足できる染色性を得ることが出来ること
で、これはグリコール成分がポリマー中のＳ成分の塩基
性染料に対する有効利用率をめげる働き（染色性向上効
果）があるからである。One of them is that by copolymerizing glycol components, satisfactory dyeing properties can be obtained with a small amount of S component copolymerized, and this is because the glycol component reduces the effective utilization rate of the S component in the polymer for basic dyes. This is because it has a function (dying property improvement effect).
二つにはグリコール成分の共重合により、Ｓ成分共重合
系において同一溶融粘度で重合度の高いポリマーが得ら
れていることでこれはグリコール成分がＳ成分共重合系
において重合度を下げることなくポリマーの溶融粘度を
下げる鋤き（減粘効果）がおるからである。Secondly, by copolymerizing the glycol component, a polymer with the same melt viscosity and high degree of polymerization can be obtained in the S component copolymerization system, which means that the glycol component can be used in the S component copolymerization system without lowering the polymerization degree. This is because there is a plow (thinning effect) that lowers the melt viscosity of the polymer.
従って、Ｓ成分共重合系でグリコール成分を共重合する
ことにより加熱筒などの特殊な装置を用いなくても通常
の紡糸が可能な溶融粘度の範囲で満足できる染色性を有
し、かつ重合度８０〜１００の繊維を得るために必要な
重合度をもつポリマーが得られる。これはグリコール成
分の共重合によるＳ成分共重合量の減少による溶融粘度
の低下、グリコール成分共重合による溶融粘度の低下が
あってはじめて得られるものでおる。Therefore, by copolymerizing the glycol component with the S component copolymerization system, it is possible to achieve satisfactory dyeing properties within the melt viscosity range that allows normal spinning without using special equipment such as a heating tube, and the degree of polymerization is Polymers with the necessary degree of polymerization to obtain fibers of 80-100 are obtained. This can only be obtained by reducing the melt viscosity due to a decrease in the amount of copolymerized S component due to copolymerization of the glycol component, and by decreasing the melt viscosity due to the copolymerization of the glycol component.
しかしながら、通常紡糸可能な溶融粘度の範囲まで溶融
粘度を低下させるにはグリコール成分の共重合量を多く
する必要がおる。反面このグリコール成分の共重合ｍが
多くなると染色物の耐光堅牢性が低下する。したがって
染色物の耐光堅牢性を満足させるためにはグリコール成
分の共重合量はある一定量以下とする必要がおる。とこ
ろで前述したようにグリコール成分はＳ成分の塩基性染
料に対する有効利用率をあげる触きを（染色性向上効果
）もっているので、グリコール成分の共重合量をある一
定量以下とするならば、染色性を満足させるためにはＳ
成分の共重合量をおる一定量以上としなければならない
。However, in order to lower the melt viscosity to a range that allows normal spinning, it is necessary to increase the amount of copolymerized glycol component. On the other hand, when the copolymerization m of this glycol component increases, the light fastness of the dyed product decreases. Therefore, in order to satisfy the light fastness of the dyed product, the amount of copolymerized glycol component must be below a certain level. By the way, as mentioned above, the glycol component has the property of increasing the effective utilization rate of the S component for basic dyes (improving dyeability), so if the copolymerization amount of the glycol component is kept below a certain amount, the dyeing S for sexual satisfaction
The amount must be at least a certain amount below the amount of copolymerization of the components.
一方糸強度を満足させるためには重合度を低くし過ぎる
ことはできないので、染色性、染色物の耐光堅牢性を満
足させるようにＳ成分、グリコール成分の共重合量を定
める必要があり、その糸強度を満足する重合度のポリマ
ーの粘度は通常のポリエステルの粘度の１．８〜３．０
倍となる。On the other hand, in order to satisfy the yarn strength, the degree of polymerization cannot be made too low, so it is necessary to determine the amount of copolymerization of the S component and glycol component so as to satisfy the dyeability and light fastness of the dyed product. The viscosity of a polymer with a degree of polymerization that satisfies thread strength is 1.8 to 3.0, which is the viscosity of normal polyester.
It will be doubled.
しかしこの粘度の高いポリマーを加熱筒などの特殊な装
置を使用しないで、通常の方法で紡糸すると強伸度の低
い糸しか得られないという問題がある。However, if this highly viscous polymer is spun using a normal method without using special equipment such as a heating tube, there is a problem in that only yarn with low strength and elongation can be obtained.
そこで本発明者らはポリマ組成および紡出条件に関し、
鋭意検討を行った結果、本発明に到達したものでおる。Therefore, the present inventors investigated the polymer composition and spinning conditions.
As a result of extensive research, we have arrived at the present invention.
すなわち本発明の目的は、延伸糸強度が４（］／ｄ以上
といった高い糸強度を持ち、耐アルカリ性に優れかつ染
色物の耐光堅牢性に優れた塩基性可染型の改質ポリエス
テル繊維を製造することである。That is, the purpose of the present invention is to produce a basic dyeable modified polyester fiber that has high yarn strength such as a drawn yarn strength of 4(]/d or more, has excellent alkali resistance, and has excellent light fastness of dyed products. It is to be.
［問題点を解決するための手段］
前述した本発明の目的は１．０〜２．０モル％の金属ス
ルホネート基を含有するイソフタル酸成分と０．５〜１
．９重量％の分子量４００〜６０００のグリコール成分
を共重合しており、かつ重合度が８２〜１０５である改
質ポリエステルを、下記の各式を満足する条件下で紡糸
した後、延伸する°ことを特徴とする改質ポリエステル
繊維の製造方法
ズリ速度（１）≦１０ ’ ｓｅｃ −１ドラフト
≦２５０
口金背面圧ＣＤ）≧４０に９／ｃボ
ズリ応力（τ）≦（Ｑ十０．７） ｘ
ｌｏ ７ ｄｙｎｅ／ ｃｔＡ
（Ｑは単孔当り吐出＠ｇ／ｍｉｎ、 ｈｏｌｅ）によっ
て達成できる。[Means for Solving the Problems] The object of the present invention described above is to provide an isophthalic acid component containing 1.0 to 2.0 mol % of metal sulfonate groups and 0.5 to 1 mol % of an isophthalic acid component containing metal sulfonate groups.
．． A modified polyester copolymerized with 9% by weight of a glycol component having a molecular weight of 400 to 6000 and having a degree of polymerization of 82 to 105 is spun under conditions that satisfy the following formulas, and then stretched. Method for producing modified polyester fiber characterized by shear rate (1) ≦10' sec -1 draft
This can be achieved by ≦250 mouthpiece back pressure CD)≧40 and 9/c bozzle stress (τ)≦(Q10.7) x lo 7 dyne/ctA (Q is discharge per single hole @g/min, hole).
本発明においてＳ成分とは次式で示される化合物であり
、具体的にはジメチル（５−ナトリウムスルホ）イソフ
タレート、ビス−２−ヒドロキシエチル（５−ナトリウ
ムスルホ）イソフタレート、ビス−４−ヒドロキシブチ
ル（５−ナトリウムスルホ）イソフタレート等が挙げら
れる。In the present invention, the S component is a compound represented by the following formula, specifically dimethyl (5-sodium sulfo) isophthalate, bis-2-hydroxyethyl (5-sodium sulfo) isophthalate, bis-4-hydroxy Butyl (5-sodium sulfo) isophthalate and the like can be mentioned.
（但しＭはＮａ、Ｌｉ、になどのアルカリ金属を示し、
Ａ、Ａ”は−ＯＨ３または−（Ｃｔ１２）ｎＯＨを示す
。ｎは２以上の整数を示ず。）好ましいＳ成分としては
ジメチル（５−ナトリウムスルホ）イソフタレート、ビ
ス−２−ヒドキシエチル（５−ナトリウムスルホ）イソ
フタレートが挙げられる。Ｓ成分は得られるポリエステ
ルに対し１．０〜２．０モル％共重合させる必要があり
、ざらに１．３〜１．８モル％共重合させることが好ま
しい。Ｓ成分が１．０モル％より少ないとグリコール共
重合量を増大させ、あるいは染色温度を上げても満足で
きる染色性が得られない。これは塩基性染料と反応する
ポリマー中のＳ成分が不足するためである。一方Ｓ成分
が２．０モル％を越えた場合、重合度８０以上の繊維を
得るために必要な重合度をもつポリマを得ようとすると
、Ｓ成分を多量に共重合したために、ポリマーの溶融粘
度が著しく大きくなり、強伸度の高いポリエステル繊維
を得ることができない。(However, M represents an alkali metal such as Na, Li, etc.
A, A'' represents -OH3 or -(Ct12)nOH. n does not represent an integer greater than or equal to 2.) Preferred S components include dimethyl (5-sodium sulfo) isophthalate, bis-2-hydroxyethyl (5- Examples include sodium sulfo)isophthalate.The S component must be copolymerized in an amount of 1.0 to 2.0 mol%, preferably 1.3 to 1.8 mol%, based on the resulting polyester. If the S component is less than 1.0 mol%, satisfactory dyeing properties cannot be obtained even if the amount of glycol copolymerized is increased or the dyeing temperature is raised.This is because the S component in the polymer that reacts with basic dyes On the other hand, if the S component exceeds 2.0 mol%, in order to obtain a polymer with the degree of polymerization necessary to obtain fibers with a degree of polymerization of 80 or more, it is necessary to copolymerize a large amount of the S component. As a result, the melt viscosity of the polymer increases significantly, making it impossible to obtain polyester fibers with high strength and elongation.
Ｓ成分の添加時期はポリエステルの製造反応が完結する
迄であればいつでもよいが、添加されたＳ成分が充分に
ポリエステル鎖中に共重合されるために重縮合反応初期
以前の段階で添加するのが好ましい。なおＳ成分がグリ
コールエステルの場合には、エステル交換反応またはエ
ステル化反応終了時点から重縮合反応開始までの間で添
加するのが好ましい。The S component can be added at any time until the polyester manufacturing reaction is completed, but it is recommended to add it before the beginning of the polycondensation reaction in order for the added S component to be sufficiently copolymerized into the polyester chain. is preferred. When the S component is a glycol ester, it is preferably added between the end of the transesterification reaction or the esterification reaction and the start of the polycondensation reaction.
グリコール成分としては分子量が４００〜６０００のも
のでおることが必要で、分子量が４００未満のものは染
色性向上効果が小さく、かつグリコールの沸点が低いこ
とに起因して重縮合反応中に系外へのグリコール飛散が
生じ、一定量の共重合をさせることが困難となる。一方
、分子量が６０００を越えたグリコール成分は、共重合
したポリマーの耐酸化分解性が悪化するとともに、グリ
コール成分が均一に共重合し難いことに起因して、染色
性および得られる繊維から作成した布帛の抗フロスティ
ング性が低下する。なおグリコール成分の分子量は４０
０〜２０００がより好ましく、４００〜９００が特に好
ましい。It is necessary that the glycol component has a molecular weight of 400 to 6,000. If the molecular weight is less than 400, the effect of improving dyeing properties will be small, and due to the low boiling point of glycol, it will be removed from the system during the polycondensation reaction. glycol scattering occurs, making it difficult to copolymerize a certain amount. On the other hand, a glycol component with a molecular weight exceeding 6000 deteriorates the oxidative decomposition resistance of the copolymerized polymer, and also makes it difficult to uniformly copolymerize the glycol component. The anti-frosting properties of the fabric are reduced. The molecular weight of the glycol component is 40
0-2000 is more preferable, and 400-900 is particularly preferable.
前記分子ｍ ４００〜６０００のグリコール成分の代表
例としては、式ＨＯ−（ＣＨ２−ＣＨ２−０）ｍ −Ｒ
−０−（ＣＨ２−ＣＨ２−０） ｎ −Ｈ（Ｒは炭素原
子数３〜２０の二価の脂肪族炭化水素基、フェニル基、
ビスフェニル基、ナフタレン基等の二価の芳香族炭化水
素基、ｍ−ｎは同一または異なる整数で１≦ｍ＋ｎ≦１
００である。）で示されるグリコール、ビスフェノール
へ−エチレンオキサイド付加物および次式で示されるポ
リアルキレングリコール等があげられる。As a representative example of the glycol component of the molecule m 400 to 6000, the formula HO-(CH2-CH2-0)m -R
-0-(CH2-CH2-0) n -H (R is a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a phenyl group,
Divalent aromatic hydrocarbon group such as bisphenyl group or naphthalene group, m−n is the same or different integer, 1≦m+n≦1
It is 00. ), a bisphenol-ethylene oxide adduct, and a polyalkylene glycol represented by the following formula.
Ａ （Ｃｎ Ｈ２ｎｏ＞ｍ Ｈ
ざらに、グリコール成分としてはポリアルキレングリコ
ールがより好ましい。これはポリアルキレングリコール
の減粘効果が他のグリコールより大きいため、重合度８
０〜１００のＩ維を得るために必要な重合度をもつポリ
マを得るには他のグリコールより有利なことによる。そ
してポリアルキレングリコールとしては、両末端にＯＨ
基を有するポリエチレングリコールがより好ましい。こ
れはアルキレンオキサイド単位が短いほど、またグリコ
ールをランダムに共重合するほど染色性向上効果、減粘
効果が大きいためである。A (Cn H2no>m H Generally speaking, polyalkylene glycol is more preferable as the glycol component. This is because polyalkylene glycol has a greater viscosity-reducing effect than other glycols, so the degree of polymerization is 8.
This is due to its advantage over other glycols in obtaining polymers with the degree of polymerization necessary to obtain I fibers of 0 to 100. And as a polyalkylene glycol, OH is added to both ends.
Polyethylene glycol having groups is more preferred. This is because the shorter the alkylene oxide unit and the more randomly copolymerized the glycol, the greater the effect of improving dyeability and reducing viscosity.
グリコール成分の共重合量は得られるポリエステルに対
して０．５〜１６９重但％の範囲とする必要がおる。こ
の範囲より少ないと染色性向上効果が小さく、多くなる
と特性、特に染色物の耐光堅牢性の低下および耐酸化分
解性の低下が大になる。このためグリコール成分の共重
合は０．７〜１．５ｉ１％がより好ましい。The copolymerized amount of the glycol component needs to be in the range of 0.5 to 169% by weight based on the resulting polyester. If the amount is less than this range, the effect of improving dyeing properties will be small, and if it is more than this range, the properties, especially the light fastness of the dyed product and the oxidative decomposition resistance will be greatly reduced. For this reason, the copolymerization of the glycol component is more preferably 0.7 to 1.5i1%.
グリコール成分の添加時期はポリエステルの製造反応が
完結するまでの任意の段階でよいが、重縮合反応初期以
前の段階で添加するのが好ましい。また添加に際して前
記Ｓ成分と同時に添加しても、また別々に任意の順序で
添加してもよい。The glycol component may be added at any stage until the polyester production reaction is completed, but it is preferably added at a stage before the initial stage of the polycondensation reaction. Furthermore, upon addition, the S component may be added at the same time as the S component, or may be added separately in any order.
本発明で得られる改質ポリエステル繊維の重合度は８０
〜１００とすることが好ましく、更には、８５〜１００
であることがより好ましい。通常紡糸時にポリマを溶融
する際、重合度が低下するため、上記重合度の繊維を得
るためには、ポリマの重合度は８２〜１０５とする必要
がある。ポリマの重合度が８２未満でおると本発明で目
的とするポリエステル繊維の糸強度（４，０ｃ＋／ｄ以
上）を満足することができず、ポリマの重合度が１０５
を越えるとポリマの溶融粘度が著しく大きくなり、目的
とする強伸度の高い繊維を１ｑることかできない。The degree of polymerization of the modified polyester fiber obtained by the present invention is 80
It is preferable to set it to 100 to 100, more preferably 85 to 100.
It is more preferable that Normally, when a polymer is melted during spinning, the degree of polymerization decreases, so in order to obtain fibers with the above degree of polymerization, the degree of polymerization of the polymer needs to be 82 to 105. If the polymerization degree of the polymer is less than 82, it will not be possible to satisfy the yarn strength of the polyester fiber (4.0c+/d or more) aimed at in the present invention, and the polymerization degree of the polymer will be less than 105.
If it exceeds 1 q, the melt viscosity of the polymer increases significantly, making it impossible to produce 1 q of fibers with the desired high strength and elongation.
重合度８２〜１０５の改質ポリエステルを得る方法とし
ては重縮合反応のみで得ても良いし、固相重合反応を併
用しても良い。The modified polyester having a degree of polymerization of 82 to 105 may be obtained by polycondensation reaction alone, or by a combination of solid phase polymerization reaction.
本発明では、上記改質ポリエステルを特定な紡糸条件で
紡糸する必要がある。紡糸条件の中でも特に溶融状態で
の流動、変形の挙動を特定の範囲とすることが重要であ
り、具体的には以下に示す条件を採用する必要がある。In the present invention, it is necessary to spin the modified polyester under specific spinning conditions. Among the spinning conditions, it is particularly important to keep the flow and deformation behavior in the molten state within a specific range, and specifically, the conditions shown below need to be adopted.
スＩ、Ｉ速度（ｔ） ≦１０４ｓｅｃ −１ドラフト
≦２５０
口金背面圧（ｐ）≧４０ＫＩ／ｃｔｔｔズリ応力（τ）
≦（Ｑ＋ ０．７） ｘｌｏ ７ｄｙｎｅ／ ｃｉ
（Ｑは単孔当り吐出１ｇ／ｍｉｎ −ｈｏｌｅ）ここで
、ズリ速度、ズリ応力の値は紡糸口金部での流動特性を
必られすものであり、次式により計算する。S I, I speed (t) ≦104sec -1 draft
≦250 Back pressure of base (p)≧40KI/cttt Shear stress (τ)
≦(Q+ 0.7) xlo 7dyne/ci (Q is discharge per single hole 1 g/min -hole) Here, the values of shear speed and shear stress are those that require the flow characteristics at the spinneret part, Calculate using the following formula.
〒＝３２ｑ／πＤ３ρ（ＳｅＣ−１）
Ｄ二ロ金孔径（ｃｍ ）
ｑ ：単孔当り吐出ｍ （ｇ／ｓｅｃ −ｈｏｌｅ）ρ
：溶融ポリマ密度（ｇ／ｃｍり
τ＝ ９．８ｘ１０５ ＰＤ／ ４Ｌ （ｄｙｎ／ｃｍ
）Ｐ：口金背面圧（Ｋｇ／ｃｙｔ）
Ｌ：口金孔深度（ｃｍ ）
ｔ、τが前記上限値を越えると、本発明のポリマーは溶
融粘度が高いため、口金部での流動挙動が均一とならず
、糸の強伸度特性が低下する。〒=32q/πD3ρ (SeC-1) D2 gold hole diameter (cm) q: Discharge per single hole m (g/sec -hole) ρ
: Molten polymer density (g/cm τ = 9.8x105 PD/4L (dyn/cm
) P: Back pressure of the mouthpiece (Kg/cyt) L: Mouth hole depth (cm) If t and τ exceed the above upper limit values, the polymer of the present invention has a high melt viscosity, so the flow behavior at the mouthpiece becomes uniform. Therefore, the strength and elongation properties of the yarn deteriorate.
前記口金背面圧（Ｐ）は４０に’ｔ／ｃｍ以上としなけ
ればならない。Ｐがｌｌ０Ｋｇ／ｃｒｔｒ未満では、口
金での吐出孔間の流動が不均一となり、単糸間のムラお
よび単糸間ムラに起因する強伸度低下が起こる。なお口
金背面圧は５０Ｋｒｊ／ｃｒｉ以上が好ましく、６０Ｋ
ｇ／ｃｒ７を以上がより好ましい。The mouthpiece back pressure (P) must be greater than 40't/cm. If P is less than 10 Kg/crtr, the flow between the discharge holes in the die becomes uneven, and the strength and elongation decreases due to unevenness between single yarns and unevenness between single yarns. The back pressure of the mouthpiece is preferably 50Krj/cri or more, and 60K
g/cr7 or more is more preferable.
紡糸ドラフトは２５０以下とする必要があり、紡糸ドラ
フトが２５０を越えると糸の繊度斑が大きくなることに
起因して強伸度の低下が起る。The spinning draft needs to be 250 or less, and if the spinning draft exceeds 250, the strength and elongation will decrease due to increased fineness unevenness of the yarn.
また前記繊度斑はウースター斑の測定における大波とし
て表われるものでおり、繊度斑が大きくなると染斑が発
生する。Furthermore, the fineness unevenness appears as large waves in the measurement of Worcester's spots, and when the fineness unevenness becomes large, staining spots occur.
また本発明で言うポリエステルとは構成中位の少なくと
も８０モル％がエチレンテレフタレート又はブチレンテ
レフタレートでおり、前記Ｓ成分及びグリコール成分以
外に１０モル％以下、好ましくは５モル％以下の他の成
分を共重合していてもよい。また前記共重合成分の他に
通常のエステル交換触媒、重合触媒、リン化合物やアル
カリ金属塩などの副反応防止剤、二酸化チタンなどのつ
や瀾し剤、着色防止剤、および酸化分解防止剤などを含
んでいてもよい。特にアルカリ金属塩は副生ジエチレン
グリコール量の抑制効果があり、また酸化分解防止剤は
グリコール共重合によるポリマーの酸化分解性悪化の抑
制効果があり、使用するのが好ましい。In addition, the polyester referred to in the present invention is one in which at least 80 mol% of the composition is ethylene terephthalate or butylene terephthalate, and other components other than the S component and the glycol component are 10 mol% or less, preferably 5 mol% or less. It may be polymerized. In addition to the above-mentioned copolymerization components, ordinary transesterification catalysts, polymerization catalysts, side reaction inhibitors such as phosphorus compounds and alkali metal salts, glossing agents such as titanium dioxide, coloring inhibitors, and oxidative decomposition inhibitors are also used. May contain. In particular, alkali metal salts have the effect of suppressing the amount of by-product diethylene glycol, and oxidative decomposition inhibitors have the effect of suppressing deterioration of the oxidative decomposition properties of the polymer due to glycol copolymerization, so it is preferable to use them.
本発明の改質ポリエステル繊維は優れた塩基性染料可染
性を有し、その染色温度は域維を溝成するポリマ組成に
よって適宜変更できるが、ｉｉｏ〜１４０℃の範囲が好
ましく、１２０〜１３５°Ｃの範囲がより好ましい。The modified polyester fiber of the present invention has excellent dyeability with basic dyes, and the dyeing temperature can be changed as appropriate depending on the polymer composition forming the fibers, but is preferably in the range of Iio to 140°C, and 120 to 135°C. A range of °C is more preferred.
［実施例］
以下に実施例を挙げて本発明を具体的に説明する。なお
、実施例における特性値測定方法は次のとおりでおる。[Example] The present invention will be specifically explained with reference to Examples below. The method of measuring characteristic values in the examples is as follows.
（グリコール成分の共重合量）
ポリマをアミン分解したのちガスクロマトグラフィー、
またはカリボール滴定で定量する。(Amount of copolymerized glycol component) After decomposing the polymer with amines, gas chromatography,
Or quantify by Calibol titration.
（重合度）
重合度は単位１当りの末端基数を通常用いられる方法で
求め、次式により算出する。(Degree of Polymerization) The degree of polymerization is calculated by determining the number of terminal groups per unit by a commonly used method and using the following formula.
Ｘ１０６
重合度＝ □
末端基数（コ／１０６（］）ＸＭ
（Ｍとはポリマ（又は糸）中のくり返し単位の分子量の
平均値を意味する。）
（極限粘度）
ポリマをオルソクロロフェノール中に溶解し、２５℃で
の測定値で表示する。X106 Degree of polymerization = □ Number of terminal groups (co/106 (]) and display the measured value at 25°C.
（筒編の作成方法）
評価すべきフィラメント糸を２７ゲージの靴下編機（重
油機械製作所（！１製）により、筒編地を編成する。(Method for creating tubular knitted fabric) A tubular knitted fabric is knitted using the filament yarn to be evaluated using a 27-gauge sock knitting machine (manufactured by Juyu Kikai Seisakusho (!1)).
（精練方法）
評価すべき筒編地を常法により０．２％の非イオン活性
剤（サンデッドＧ−９００（三洋化成ｌ製）〕と０．２
％のソーダ灰を含む沸騰水で５分間煮沸精練し、次いで
水洗、乾燥する。(Scouring method) The cylindrical knitted fabric to be evaluated was treated with 0.2% nonionic activator (Sanded G-900 (manufactured by Sanyo Kasei)) and 0.2% by a conventional method.
% of soda ash for 5 minutes, then washed with water and dried.
（耐光堅牢性）
評ｆ［［ｆｉすべきフィラメントから得られた精練され
た筒編地をＥｓｔｒｏｌ ［３１ｕｅ Ｎ−３ＲＬ（商
標名住友化学製）１．５％ｏｗｆ 、酢酸０．５ｄ／
Ｑ 、酢酸ソーダ０．１５１；ｌ／Ωからなる浴比１：
１００の１２０’Ｃ水溶液中で６０分間染色を行なった
後、常法に従いハイドロザルファイト２ＣＩ／ Ｑ 、
Ｎａ ＯＨ２ｇ／ＱサンデッドＧ −９００２ｇ／Ω
からなる８０’Ｃの水溶液中で２０分間還元洗浄を行な
い水洗乾燥する。(Lightfastness) Evaluation: The refined tubular knitted fabric obtained from the filament to be treated was washed with Estrol [31ue N-3RL (trade name: manufactured by Sumitomo Chemical) 1.5% owf, acetic acid 0.5d/
Q, sodium acetate 0.151; bath ratio 1 consisting of l/Ω:
After staining for 60 minutes in a 120'C aqueous solution of 100%, hydrozulfite 2CI/Q,
Na OH2g/Q Sanded G -9002g/Ω
Reduction cleaning is carried out for 20 minutes in an aqueous solution at 80'C consisting of the following, followed by washing with water and drying.
この染色した筒餡地を、フェードメータ（スガ試験機（
（５）製）を用いてＪＩＳ−Ｌ１０４４に準じて光退色
させ、ブルースケール基準で測定する。This dyed cylindrical filling material is measured using a fade meter (Suga Test Machine).
(5)) according to JIS-L1044, and measured using a blue scale standard.
（染色性）
評価すべきフィラメントから得られた精練後の筒編地を
マラカイトグリーン（商標名関東化学製）５％ＯＷｆ、
酢１０．５ａｅ／ Ｑ 、酢酸ソーダ０．２ｑ／Ωから
なる浴比１：１００の１２０°Ｃの熱水溶液中で６０分
間染色を行なう。次いで、この筒編地を引き上げた後の
染色残液中の染料濃度を測定し、筒編地の染料吸尽率を
求める。(Dyeability) The tube knitted fabric after scouring obtained from the filament to be evaluated was dyed with malachite green (trade name: Kanto Kagaku) 5% OWf,
Dyeing is carried out for 60 minutes in a hot aqueous solution at 120° C. with a bath ratio of 1:100 consisting of 10.5 ae/Q of vinegar and 0.2 q/Ω of sodium acetate. Next, the dye concentration in the dyed residual liquid after pulling up this tubular knitted fabric is measured, and the dye exhaustion rate of the tubular knitted fabric is determined.
（耐アルカリ性）
Ｎａ ０＋−１５０ＣＩ／Ｑの濃度の水溶液中テ温度９
５℃、浴比１：１００の条件で糸を処理し、減量率２０
％のときの糸強力特性により求める。(Alkali resistance) Temperature 9 in an aqueous solution with a concentration of Na 0+-150CI/Q
The yarn was treated at 5℃ and a bath ratio of 1:100, and the weight loss rate was 20.
Determined from the yarn strength characteristics when %.
（耐酸化分解性）
Ｄｉｆｆｅｒｅｎｔｉａｌ ｔｈｅｒｍａｌ ａｎａｌ
ｙｓｉｓを用いて、酸化分解開始温度を測定しその値か
ら求める。(Oxidative decomposition resistance) Differential thermal anal
The oxidative decomposition start temperature is measured using ysis and determined from that value.
実施例１
ジメチルテレフタレート１５０Ｋｇ、エチレングリコー
ル９４Ｋｇ、酢酸リチウム２水塩２１０（］、酢酸マン
ガン４水塩３０ｇ、三酸化アンチモン６０（ｌの混合物
にジメチル（５−ナトリウムスルホ）イソフタレート４
Ｋｇ＜１．７モル％共重合）を添加し、大気圧下１４０
°Ｃから２３５°Ｃまで殴拌しながら４時間かけて昇温
しエステル交換反応を終了した。Example 1 Dimethyl (5-sodium sulfo)isophthalate 4 was added to a mixture of 150 Kg dimethyl terephthalate, 94 Kg ethylene glycol, 210 Kg lithium acetate dihydrate, 30 g manganese acetate tetrahydrate, and 60 L antimony trioxide.
Kg<1.7 mol% copolymerization) was added, and 140 mol% was added under atmospheric pressure.
The temperature was raised from °C to 235 °C over 4 hours with stirring to complete the transesterification reaction.
次いでトリメチルフォスフエイト６４．５（１、二酸化
チタンを１６重屯％含有したエチレングリコールスラリ
ーをａｉｏｇおよび酸化分解防止剤であるイルガノック
ス１０１０（チバガイギー社製） ｉｓｏｇを添加した
後、缶内を５００ｍＨｇに減圧し２５Ｋｇのエチレング
リコールを留去した。その後第１表に記載するグリコー
ル成分を添加し、２時間で２４０℃から２８０℃に昇温
しかつ１時間かけて７６０ｍＨｇからｌＭＨＤまで減圧
し、ｌｍＨｇ以下の減圧を維持して２８０’Ｃでざらに
１．５時間、合計３時間３０分重縮合反応させた。Next, an ethylene glycol slurry containing trimethyl phosphate 64.5 (1, 16 tons by weight) and titanium dioxide was added to AIOG and Irganox 1010 (manufactured by Ciba Geigy) isog, which is an oxidative decomposition inhibitor, and the inside of the can was heated to 500 mHg. 25 kg of ethylene glycol was distilled off.Then, the glycol components listed in Table 1 were added, and the temperature was raised from 240°C to 280°C over 2 hours, and the pressure was reduced from 760 mHg to 1MHD over 1 hour. The polycondensation reaction was carried out at 280'C for roughly 1.5 hours, for a total of 3 hours and 30 minutes, while maintaining the following reduced pressure.
得られたポリマーの特性を第１表に示す。The properties of the obtained polymer are shown in Table 1.
（以下余白）
次いで前記各ポリマーを真空乾燥し、下記第２表に示す
条件で溶融紡糸した。この場合、紡糸特性であるドラフ
トは９４、ズリ速度は５８００ｓｅｃ−１、口金背面圧
は６０〜８０匈／ｃｒＡ、ズリ応力は０．８９〜１．２
Ｘ １０７ ｄｙｎｅ／ ｃｔＡであり、本発明で規定
している紡糸条件を満足するものであった。(The following is a blank space.) Next, each of the above polymers was vacuum dried and melt-spun under the conditions shown in Table 2 below. In this case, the draft, which is the spinning characteristic, is 94, the shear rate is 5800 sec-1, the spinneret back pressure is 60 to 80 匈/crA, and the shear stress is 0.89 to 1.2.
X 107 dyne/ctA, which satisfied the spinning conditions specified in the present invention.
第２表
ざらに得られ？前記各未延伸糸を下記第３表の延伸条件
でホットロール延伸を行ない、７５デニール・３６フイ
ラメントの延伸糸を得た。得られた延伸糸の糸物性およ
び染色性、耐光堅牢性、耐アルカリ性を第４表に表示し
た。Did you get the second table? Each of the undrawn yarns was subjected to hot roll drawing under the drawing conditions shown in Table 3 below to obtain drawn yarns of 75 denier and 36 filaments. Table 4 shows the yarn physical properties, dyeability, light fastness, and alkali resistance of the obtained drawn yarn.
第 ４ 表
第１表、第４表から明らかなように本発明の要件を満足
する実験番＠１〜７では糸禄度、染色性、耐光堅牢性、
耐アルカリ性（アルカリ処理後の強力）、安定共重合性
、（添加量に対する共重合量の比率）酸化分解性が良好
であった。Table 4 As is clear from Tables 1 and 4, the experimental numbers @1 to 7 that satisfied the requirements of the present invention had a high degree of stringiness, dyeability, light fastness,
It had good alkali resistance (strong after alkali treatment), stable copolymerizability, and oxidative decomposition (ratio of copolymerization amount to added amount).
これに対し比較例１，２．３はグリコールの分子量が本
発明の範囲より低いため安定共重合性が悪く、かつ染色
性が低いために本発明の効果が発揮できない。On the other hand, in Comparative Examples 1, 2, and 3, the molecular weight of the glycol was lower than the range of the present invention, resulting in poor stable copolymerization and poor dyeability, so that the effects of the present invention could not be exhibited.
また比較例４はグリコールの分子量が本発明の範囲で規
定した上限を越えるため染色性および酸化分解性が悪く
本発明が目的とする糸は得られなかった。Furthermore, in Comparative Example 4, the molecular weight of the glycol exceeded the upper limit specified in the scope of the present invention, so the dyeability and oxidative decomposition properties were poor, and the yarn targeted by the present invention could not be obtained.
また比較例５，６はグリコールの共重合量が本発明で規
定した上限を越えるため、酸化分解性および耐光堅牢性
が悪く満足な糸とならなかった。In addition, in Comparative Examples 5 and 6, the amount of copolymerized glycol exceeded the upper limit specified in the present invention, so the oxidative decomposition properties and light fastness were poor, resulting in unsatisfactory yarns.
比較例７はグリコール共重合量が本発明で規定した下限
以下であるため、染色性が悪く満足な糸は得られなかっ
た。In Comparative Example 7, the amount of glycol copolymerized was less than the lower limit specified in the present invention, so the dyeability was poor and a satisfactory yarn could not be obtained.
実施例２
添加共重合するジメチル（５−ナトリウムスルホ）イソ
フタレートを第５表の如く添加し、添加共重合するグリ
コールをポリエチレングリコール（分子１６００）とし
、かつグリコール添加量を１．０重量％とする以外はす
べて実施例１と同様な方法で重合、製糸を行なった。Example 2 Dimethyl (5-sodium sulfo)isophthalate to be added and copolymerized was added as shown in Table 5, the glycol to be added and copolymerized was polyethylene glycol (molecular 1600), and the amount of glycol added was 1.0% by weight. Polymerization and yarn spinning were carried out in the same manner as in Example 1 except for the following.
ポリマーの特性、紡糸特性、得られた延伸糸の糸物性、
染色性、耐光堅牢性、耐アルカリ性を第５表に示した。Polymer properties, spinning properties, yarn physical properties of the obtained drawn yarn,
Dyeability, light fastness, and alkali resistance are shown in Table 5.
（以下余白）
（価考）
（１）紡糸特性のうち、ズリ速度およびドラフトは実験
番号８〜１３のいずれも一定値とし、ズリ速度は５８０
０ｓｅｃ ’ 、ドラフトは９４とした。(Margins below) (Remarks) (1) Of the spinning characteristics, the shear speed and draft were all constant values for experiment numbers 8 to 13, and the shear speed was 580.
0sec', the draft was set to 94.
（２） 実験番＠１３のポリマーは、実験番号１２で
冑たポリマーを１９０℃で２時間、真空下で固相重合し
たポリマーでおる。(2) The polymer of Experiment No. 13 is a polymer obtained by solid-phase polymerizing the polymer obtained in Experiment No. 12 at 190° C. for 2 hours under vacuum.
前記第５表から明らかなように、実験番号９〜１１はジ
メチル（５−ナトリウム）スルホイソフタレート共重合
量が本発明で規定した範囲を満足するものでおり、糸物
性、糸の染色性、耐アルカリ性、耐光堅牢性等はいずれ
も満足できるものでめった。これに対し、実験番号８は
ジメチル（５−す１ヘリウム）スルホイソフタレート共
重合量が本発明で規定した下限以下であるため染色性が
不満足であり、実験番号１２はポリマの重合度が本発明
の下限以下であるため糸物性（強度、伸度）、耐アルカ
リ性が不満足である。As is clear from Table 5 above, in Experiment Nos. 9 to 11, the amount of dimethyl (5-sodium) sulfoisophthalate copolymerized satisfied the range specified in the present invention, and the yarn physical properties, yarn dyeability, Alkali resistance, light fastness, etc. were all satisfactory. On the other hand, in Experiment No. 8, the dyeability was unsatisfactory because the amount of dimethyl (5-1 helium) sulfoisophthalate copolymerized was below the lower limit specified in the present invention, and in Experiment No. 12, the degree of polymerization of the polymer was Since it is below the lower limit of the invention, the yarn physical properties (strength, elongation) and alkali resistance are unsatisfactory.
また実験番号１３はジメチル（５−ナトリウム）スルホ
イソフタレート共重合量が本発明の上限を越えるため、
ポリマー重合度を８２以上とするとポリマー溶融粘度が
高くなり、そのため紡糸特性が本発明で規定した範囲外
となる。このため実験Ｎα１３で得られた糸の糸物性、
耐アルカリ性は不満足なものとなる。In addition, in experiment number 13, the amount of dimethyl (5-sodium) sulfoisophthalate copolymerized exceeded the upper limit of the present invention.
When the degree of polymerization is 82 or more, the polymer melt viscosity becomes high, and therefore the spinning characteristics fall outside the range specified in the present invention. Therefore, the physical properties of the yarn obtained in experiment Nα13,
Alkali resistance becomes unsatisfactory.
実施例３
ジメチル（５−ナトリウムスルホ）インフタレートを１
．７モル％、グリコールをポリエチレングリコール（平
均分子１６００）とし、グリコール共重合量を１．０重
優％とする以外はすべて実施例１と同様な方法で行ない
重縮合時間を変化させて重合度７０．８２．９１．１０
０のポリマーを製造し、このうちの重合度１００のポリ
マーを固相重合して重合度１１３のポリマーを得た。次
いでこれらの各ポリマーを実施例１と同様な方法で製糸
を行なった。Example 3 Dimethyl (5-sodium sulfo) inphthalate at 1
．． The polymerization degree was 70% by changing the polycondensation time except that the glycol was polyethylene glycol (average molecular weight 1600) and the glycol copolymerization amount was 1.0% by weight. .82.91.10
A polymer with a polymerization degree of 113 was obtained by solid phase polymerization of a polymer with a polymerization degree of 100. Next, each of these polymers was subjected to yarn spinning in the same manner as in Example 1.
得られたポリマーのポリマー特性、紡糸特性、得られた
糸の糸物性、染色性、耐光堅牢性、耐アルカリ性を第６
表に示した。The polymer properties, spinning properties, yarn physical properties, dyeability, light fastness, and alkali resistance of the obtained polymer were evaluated in the 6th test.
Shown in the table.
（備考）
紡糸特性のうち、ズリ速度およびドラフトは実験番号１
４〜１８のいずれも一定値とし、ズリ速度は５８００ｓ
ｅｃ ’ 、ドラフトは９４とした。第６表からも明ら
かな通り、実験番号１５〜１７は重合度が本発明で規定
した範囲であったので染色性、耐光堅牢性、糸物性、耐
アルカリ性は良好であった。これに対し実験番号１４は
重合度が本発明で規定した範囲外であったので、糸物性
耐アルカリ性が不満足なレベルであり、また実験番号１
８は糸の重合度が本発明の上限を越えるためズリ応力が
本発明の範囲外であったので糸物性、耐アルカリ性が不
満足なレベルでおった。(Note) Among the spinning characteristics, shear speed and draft are based on experiment number 1.
All of 4 to 18 are constant values, and the shear speed is 5800 s.
ec', the draft was set to 94. As is clear from Table 6, in Experiment Nos. 15 to 17, the degree of polymerization was within the range specified by the present invention, so the dyeability, light fastness, thread properties, and alkali resistance were good. On the other hand, in Experiment No. 14, the degree of polymerization was outside the range specified in the present invention, so the alkali resistance of the thread properties was at an unsatisfactory level.
In No. 8, the degree of polymerization of the thread exceeded the upper limit of the present invention, and the shear stress was outside the range of the present invention, so the thread physical properties and alkali resistance were at an unsatisfactory level.
比較例
ジメチル（５−ナトリウム）スルホイソフタリートを２
．０モル％としたこと、及びグリコールを添加しないこ
との外は実施例１と同様な方法で溶融重縮合反応を行な
った。（ｑられたポリマ特性は極限粘度が０．５６ 、
融点は２５４℃でめった。このポリマを実施例１と同様
な方法で製糸を行なって（ｑた糸の糸物性は重合度８５
、強度が４．１ａ／ｄ 、伸度３３％でおり、この糸の
染色性は４５％、耐光堅牢性は４．仮、耐アルカリ性は
２１５（Ｉｌ’ｉつだ。糸物性、耐光堅牢性、耐アルカ
リ性は満足できるレベルでめったが、染色性が不満足で
あった。Comparative Example Dimethyl (5-sodium) sulfoisophthalate 2
．． A melt polycondensation reaction was carried out in the same manner as in Example 1 except that the concentration was 0 mol % and no glycol was added. (The q polymer properties are that the intrinsic viscosity is 0.56,
The melting point was reached at 254°C. This polymer was spun into yarn in the same manner as in Example 1 (the physical properties of the yarn were as follows: degree of polymerization: 85
The strength is 4.1 a/d, the elongation is 33%, the dyeability of this yarn is 45%, and the light fastness is 4. Temporarily, the alkali resistance was 215.Thread properties, light fastness, and alkali resistance were rarely at a satisfactory level, but the dyeability was unsatisfactory.
実施例４
実施例１、実験ＮＯ１２のポリマーを用いて、紡糸条件
を変更して製糸を行なった。なお延伸条件は第３表と同
じとした。製糸性および得られた延伸糸特性の結果を第
７表に表示した。Example 4 Using the polymer of Example 1, Experiment No. 12, yarn spinning was carried out by changing the spinning conditions. Note that the stretching conditions were the same as in Table 3. The results of the spinning properties and the properties of the drawn yarn obtained are shown in Table 7.
なお、第７表にあける延伸優等率は１Ｋｇ巻の未延伸糸
を１０本延伸した時の、延伸時の糸切れ、単糸切れ、毛
羽などの欠点が発生しなかった延伸糸の本数の割合で表
わした。In addition, the drawing excellence ratio shown in Table 7 is the percentage of the number of drawn yarns in which no defects such as yarn breakage, single yarn breakage, or fuzz occurred during drawing when 10 undrawn yarns of 1 kg were drawn. It was expressed as
（以下余白）
第７表からも明らかな通り実験番号１９．２２はズリ速
度、ズリ応力、口金背面圧、ドラフトの各特性が本発明
の範囲であったので糸特性は良好であった。これに対し
実験番号２０はズリ応力が、実験番号２１はズリ速度、
ズリ応力が、実験番号２３はドラフトが、実験番号２４
は口金背面圧が、それぞれ本発明の範囲外でおったので
糸特性が不満足なレベルであった。(The following is a blank space) As is clear from Table 7, the yarn properties of Experiment No. 19.22 were good because the properties of shear speed, shear stress, mouth back pressure, and draft were within the range of the present invention. On the other hand, experiment number 20 was based on shear stress, and experiment number 21 was based on shear velocity.
Shear stress, experiment number 23, draft, experiment number 24
In each case, the back pressure of the spindle was outside the range of the present invention, so the yarn properties were at an unsatisfactory level.
本発明はポリマ組成、重合度及び紡糸条件を厳密にコン
１〜ロール、組み必わせることであり、本発明により初
めて糸強度が４（］／ｄ以上と高強度でかつ耐アルカリ
性、染色性、染色物の耐光堅牢性に侵れた塩基性染利可
染型の改質ポリエステル繊維が工業的に安定して′ｌ！
造できる。The present invention is to strictly combine the polymer composition, degree of polymerization, and spinning conditions from control 1 to roll.With this invention, for the first time, the yarn strength is as high as 4(]/d or more, and it has alkali resistance and dyeing properties. The modified polyester fibers, which can be dyed with basic dyes, are industrially stable and the light fastness of dyed products has deteriorated.
Can be built.
Claims (2)
有するイソフタル酸成分と０．５〜１．９重量％の分子
量４００〜６０００のグリコール成分を共重合しており
、かつ重合度が８２〜１０５である改質ポリエステルを
、下記の各式を満足する条件下で紡糸した後、延伸する
ことを特徴とする改質ポリエステル繊維の製造方法。 ズリ速度（■）≦１０＾４ｓｅｃ＾−＾１ ドラフト≦２５０ 口金背面圧（ｐ）≧４０Ｋｇ／ｃｍ＾２ ズリ応力（τ）≦（Ｑ＋０．７）×１０＾７ｄｙｎｅ／
ｃｍ＾２ （Ｑは単孔当り吐出量ｇ／ｍｉｎ．ｈｏｌｅ）(1) 1.0 to 2.0 mol% of an isophthalic acid component containing a metal sulfonate group and 0.5 to 1.9% by weight of a glycol component with a molecular weight of 400 to 6000 are copolymerized, and the degree of polymerization is A method for producing a modified polyester fiber, which comprises spinning a modified polyester having a polyester of 82 to 105 under conditions that satisfy the following formulas, and then drawing the modified polyester. Shearing speed (■)≦10^4sec^-^1 Draft≦250 Mouth back pressure (p)≧40Kg/cm^2 Shearing stress (τ)≦(Q+0.7)×10^7dyne/
cm^2 (Q is discharge amount per single hole g/min.hole)
が下式で示されるポリアルキレングリコールであること
を特徴とする特許請求の範囲第（１）項記載の改質ポリ
エステル繊維の製造方法。 Ａ（ＣｎＨ＿２ｎＯ）ｍＨ （ＡはＣｌＨ＿２ｌ＋＿１Ｏ又はＯＨ、ｌは１〜１０、
ｎは２〜５、ｍは３〜１００）(2) The method for producing a modified polyester fiber according to claim (1), wherein the glycol component having a molecular weight of 400 to 6,000 is a polyalkylene glycol represented by the following formula. A(CnH_2nO) mH (A is ClH_2l+_1O or OH, l is 1 to 10,
n is 2-5, m is 3-100)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18523987A JPS63120111A (en) | 1987-07-23 | 1987-07-23 | Production of modified polyester yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18523987A JPS63120111A (en) | 1987-07-23 | 1987-07-23 | Production of modified polyester yarn |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57118440A Division JPS5926521A (en) | 1982-07-09 | 1982-07-09 | Modified polyester fiber and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63120111A true JPS63120111A (en) | 1988-05-24 |
| JPH0120248B2 JPH0120248B2 (en) | 1989-04-14 |
Family
ID=16167323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18523987A Granted JPS63120111A (en) | 1987-07-23 | 1987-07-23 | Production of modified polyester yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120111A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008114313A (en) * | 2006-11-01 | 2008-05-22 | Mitsutoyo Corp | Manipulator |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5184926A (en) * | 1975-01-23 | 1976-07-24 | Toyo Boseki | HORIESUTER USENINOSEIZOHO |
| JPS51136922A (en) * | 1975-05-20 | 1976-11-26 | Kuraray Co Ltd | Polyester fibers with improved properties |
| JPS5291916A (en) * | 1976-01-29 | 1977-08-02 | Toray Ind Inc | Melt spinning of polyester |
| JPS5926521A (en) * | 1982-07-09 | 1984-02-10 | Toray Ind Inc | Modified polyester fiber and preparation thereof |
-
1987
- 1987-07-23 JP JP18523987A patent/JPS63120111A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5184926A (en) * | 1975-01-23 | 1976-07-24 | Toyo Boseki | HORIESUTER USENINOSEIZOHO |
| JPS51136922A (en) * | 1975-05-20 | 1976-11-26 | Kuraray Co Ltd | Polyester fibers with improved properties |
| JPS5291916A (en) * | 1976-01-29 | 1977-08-02 | Toray Ind Inc | Melt spinning of polyester |
| JPS5926521A (en) * | 1982-07-09 | 1984-02-10 | Toray Ind Inc | Modified polyester fiber and preparation thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008114313A (en) * | 2006-11-01 | 2008-05-22 | Mitsutoyo Corp | Manipulator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0120248B2 (en) | 1989-04-14 |
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