JP4357312B2 - Hydrolysis resistant polyester fiber - Google Patents
Hydrolysis resistant polyester fiber Download PDFInfo
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- JP4357312B2 JP4357312B2 JP2004030870A JP2004030870A JP4357312B2 JP 4357312 B2 JP4357312 B2 JP 4357312B2 JP 2004030870 A JP2004030870 A JP 2004030870A JP 2004030870 A JP2004030870 A JP 2004030870A JP 4357312 B2 JP4357312 B2 JP 4357312B2
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- polycarbonate
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- 239000000835 fiber Substances 0.000 title claims description 48
- 229920000728 polyester Polymers 0.000 title claims description 39
- 230000007062 hydrolysis Effects 0.000 title claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 31
- 239000004417 polycarbonate Substances 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 229920001225 polyester resin Polymers 0.000 claims description 8
- 239000004645 polyester resin Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 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 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 238000009987 spinning Methods 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- -1 carbodiimide compound Chemical class 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Description
本発明は、染色加工、アルカリ減量加工、スチーム処理等の各種の処理が高温で繰り返し行われても、強力劣化の少ない耐加水分解性に優れたポリエステル繊維に関するものである。 The present invention relates to a polyester fiber excellent in hydrolysis resistance with little deterioration of strength even when various treatments such as dyeing, alkali weight reduction, and steam treatment are repeated at high temperatures.
ポリエステル繊維は、その優れた特性と低コストで得られることから、衣料用のみならず工業用にも幅広く利用されている。 Polyester fibers are widely used not only for clothing but also for industrial use because of their excellent properties and low cost.
しかしながら、ポリエステル繊維は、加水分解されやすいことが知られており、熱水の存在下、高温、高湿度条件下での分解が著しいという欠点がある。そこで、ポリエステル繊維の耐加水分解性を向上させ、このような条件下でのポリエステル繊維の使用を可能にするため、様々な提案がされている。例えば、特許文献１〜３には、ポリエステルにカルボジイミド化合物を添加する方法が記載されている。 However, polyester fibers are known to be easily hydrolyzed, and have a drawback that they are significantly decomposed under high temperature and high humidity conditions in the presence of hot water. Accordingly, various proposals have been made to improve the hydrolysis resistance of polyester fibers and to enable the use of polyester fibers under such conditions. For example, Patent Documents 1 to 3 describe a method of adding a carbodiimide compound to polyester.
しかしながら、このようにカルボジイミド化合物を用いた場合、この化合物は、ポリエステル繊維の着色の原因となるため、品位がよく白度の高いポリエステル繊維を得ることは困難であった。また、これらの化合物は高価であるため、製造コスト上昇の原因となっていた。 However, when such a carbodiimide compound is used, this compound causes coloring of the polyester fiber, and it is difficult to obtain a polyester fiber of good quality and high whiteness. Moreover, since these compounds are expensive, they have caused an increase in production costs.
また、特許文献４には、ポリカーボネートを添加することでカルボキシル末端基をキャップしたポリエステル及びこのポリエステルからなる繊維が記載されている。しかしながら、この発明はカルボキシル末端基含有量が極めて低いポリエステルを得ることを目的とするものではなく、タイヤコード等に使用するため、ゴム接着力を有するようにある程度の遊離カルボキシル末端基が必要なものである。このため、末端カルボキシル基濃度が十分に低い繊維ではなく、ポリカーボネートの添加量も少ないものであった。
本発明は、上記のような問題点を解決し、品位に優れ、かつ低コストで得ることができ、末端カルボキシル基濃度が低く、耐加水分解性に優れたポリエステル繊維を提供することを技術的な課題とするものである。 The present invention provides a polyester fiber that solves the above-mentioned problems, is excellent in quality, can be obtained at low cost, has a low terminal carboxyl group concentration, and is excellent in hydrolysis resistance. This is a major issue.
本発明者等は、上記課題を解決するために鋭意検討した結果、本発明に到達した。
すなわち、本発明は、主たる繰り返し単位がエチレンテレフタレートからなる重合終了後のポリエステル７０〜９７質量％とポリカーボネート３〜３０質量％のポリエステル樹脂組成物からなり、末端カルボキシル基濃度が２５ｅｑ／ｔ以下、湿熱処理後の強度保持率が８０％以上であることを特徴とする耐加水分解性ポリエステル繊維を要旨とするものである。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention comprises a polyester resin composition comprising 70 to 97% by weight of polyester and 3 to 30% by weight of polycarbonate after polymerization , the main repeating unit being ethylene terephthalate, and having a terminal carboxyl group concentration of 25 eq / t or less , wet A gist of the hydrolysis-resistant polyester fiber is characterized in that the strength retention after heat treatment is 80% or more .
本発明のポリエステル繊維は、ポリカーボネートを適量含有しているので、低コストで末端カルボキシル基濃度を低く、耐加水分解性に優れたものとすることができ、また染色性にも優れたものとすることができる。したがって、本発明のポリエステル繊維を用いた布帛等の製品は、染色加工、アルカリ減量加工、スチーム処理等の各種の処理を高温で繰り返し行っても強力劣化が少なく、耐加水分解性が要求される用途に好適に使用することが可能となる。 Since the polyester fiber of the present invention contains an appropriate amount of polycarbonate, the terminal carboxyl group concentration can be reduced at low cost, the hydrolysis resistance can be improved, and the dyeability can also be improved. be able to. Accordingly, products such as fabrics using the polyester fiber of the present invention are required to have high resistance to hydrolysis and little degradation even when various treatments such as dyeing, alkali weight loss, and steam are repeated at high temperatures. It becomes possible to use suitably for a use.
以下、本発明について詳細に説明する。
本発明の繊維を構成するポリエステル樹脂組成物は、ポリエチレンテレフタレート（ＰＥＴ）70〜97質量％とポリカーボネート3〜30質量％からなるものである。ポリカーボネートの含有量が３質量％未満であると、末端カルボキシル基濃度を下げる効果が少なく、十分な耐湿熱性能が得られない。一方、ポリカーボネートの含有量が30質量％を超えると、ポリエステル樹脂組成物の溶融粘度が高くなり、紡糸が困難となり、また得られたとしても染色品位が劣ったものとなる。
Hereinafter, the present invention will be described in detail.
The polyester resin composition constituting the fiber of the present invention comprises 70 to 97% by mass of polyethylene terephthalate (PET) and 3 to 30% by mass of polycarbonate. When the content of the polycarbonate is less than 3% by mass, the effect of lowering the terminal carboxyl group concentration is small, and sufficient wet heat resistance performance cannot be obtained. On the other hand, if the polycarbonate content exceeds 30% by mass, the melt viscosity of the polyester resin composition becomes high, spinning becomes difficult, and even if it is obtained, the dyeing quality is inferior.
本発明において用いられるポリカーボネートは、芳香族シ゛ヒドロキシ化合物、例えば、2，2-ビス(4-ヒドロキシフェニル)プロパン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)エタン等が挙げられる。 The polycarbonate used in the present invention is an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy). Phenyl) ethane and the like.
なお、上記のような本発明で使用するポリカーボネートを得るには、通常、塩化メチレン等の溶媒中において公知の酸受容体や分子量調整剤の存在下、対応するビスフェノールとホスゲンのようなカーボネート前駆体との反応により(界面重合法)、あるいは、対応するビスフェノールとジフェニルカーボネートのようなカーボネート前駆体とのエステル交換反応(溶融重合法)などによって製造することができる。 In order to obtain the polycarbonate used in the present invention as described above, a carbonate precursor such as bisphenol and phosgene corresponding to a conventional acid acceptor or molecular weight regulator in a solvent such as methylene chloride is usually used. (Interfacial polymerization method) or a transesterification reaction (melt polymerization method) between the corresponding bisphenol and a carbonate precursor such as diphenyl carbonate.
また、本発明の繊維を構成するＰＥＴは、特に限定するものではないが、エステル交換法、直接重合法等の従来公知の方法によって製造することができる。ＰＥＴ中には、本発明の効果を損なわない範囲内ならば共重合エステルを含有してもよい。共重合エステルの代表例には、3,3'-ジフェニルジカルボン酸などの芳香族ジカルボン酸、コハク酸などの脂肪族ジカルボン酸、ジエチレングリコール、1,4-ブタンジオール、1,4- シクロヘキサンジオールなどの脂肪族、脂環式ジオール、P-ヒドロキシ安息香酸等が挙げられる。 Moreover, although PET which comprises the fiber of this invention is not specifically limited, It can manufacture by conventionally well-known methods, such as a transesterification method and a direct polymerization method. The PET may contain a copolymerized ester as long as the effects of the present invention are not impaired. Representative examples of copolymerized esters include aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, diethylene glycol, 1,4-butanediol, and 1,4-cyclohexanediol. Aliphatic, alicyclic diol, P-hydroxybenzoic acid and the like.
そして、本発明の繊維を構成するポリエステル樹脂組成物中にポリカーボネートを含有させるには、ＰＥＴとポリカーボネートを溶融状態で混合することが好ましい。混合方法としては、1.ＰＥＴの重合終了時にポリカーボネートを混合する方法、2.紡糸時にチップの段階でＰＥＴとポリカーボネートを混合する方法、3.紡糸時に各々別々に溶融押し出しされたＰＥＴとポリカーボネートをノズルパック内で混練する方法が挙げられるが、溶融混合の際、ＰＥＴとポリカーボネートが反応し、発泡することがあるため、1.の方法においてポリカーボネートを減圧しながら脱泡し、混練する方法が好ましい。 And in order to contain a polycarbonate in the polyester resin composition which comprises the fiber of this invention, it is preferable to mix PET and a polycarbonate in a molten state. The mixing method is as follows: 1. Method of mixing polycarbonate at the end of polymerization of PET, 2. Method of mixing PET and polycarbonate at the tip stage during spinning, 3. Nozzle of PET and polycarbonate melted and extruded separately during spinning. Examples of the method include kneading in a pack. Since PET and polycarbonate may react and foam during melt mixing, the method of defoaming and kneading the polycarbonate while reducing the pressure in the method 1 is preferable.
また、本発明の効果を損なわない範囲内で、ポリエステル樹脂組成物中には、ヒンダードフェノール系化合物等の酸化防止剤、その他顔料、添加剤等が配合されていてもよい。 Moreover, within the range which does not impair the effect of this invention, antioxidants, such as a hindered phenol type compound, other pigments, an additive, etc. may be mix | blended in the polyester resin composition.
さらに、本発明のポリエステル繊維は、末端カルボキシル基濃度が25eq/t以下であることが必要である。末端カルボキシル基濃度が25eq/tを超えると、ポリエステル繊維の耐加水分解性は大幅に悪化する。このため、本発明のポリエステル繊維の末端カルボキシル基濃度としては、好ましくは、10eq/t以下であり、より好ましくは、5eq/t以下である。 Furthermore, the polyester fiber of the present invention needs to have a terminal carboxyl group concentration of 25 eq / t or less. When the terminal carboxyl group concentration exceeds 25 eq / t, the hydrolysis resistance of the polyester fiber is greatly deteriorated. For this reason, the terminal carboxyl group concentration of the polyester fiber of the present invention is preferably 10 eq / t or less, and more preferably 5 eq / t or less.
また、本発明のポリエステル繊維は、ポリカーボネートをポリエステル樹脂組成物中に3〜30質量％含有していても糸質性能の低下はほとんどないので、強度、伸度は用途に応じて適宜選択することができる。各種の処理が繰り返し、高温で行なわれる用途に用いる際には、強度3.0ｃN/dtex以上、中でも3.5ｃN/dtex以上とすることが好ましい。 Moreover, since the polyester fiber of the present invention hardly contains a decrease in yarn quality even when 3 to 30% by mass of polycarbonate is contained in the polyester resin composition, the strength and elongation should be appropriately selected according to the application. Can do. When various treatments are repeated and used at high temperatures, the strength is preferably 3.0 cN / dtex or more, and more preferably 3.5 cN / dtex or more.
なお、強度、伸度は、ＪＩＳ Ｌ−１０１３に従い、島津製作所製の引張試験機AG-100Gを使用し、つかみ間隔500mmとし、引張速度500mm/minとして、糸が切断した時の値を測定する。 The strength and elongation are measured in accordance with JIS L-1013, using a tensile tester AG-100G manufactured by Shimadzu Corporation, with a grip interval of 500 mm, a tensile speed of 500 mm / min, and a value when the yarn is cut. .
さらに、本発明のポリエステル繊維は、耐湿熱性に優れる特性値として、湿熱処理後の強度保持率が80％以上、中でも85％以上であることが好ましい。なお、強度保持率とは、ポリエステル繊維（繊維Ａ）を筒編して、135℃で16時間加圧処理を行い、処理後の筒編地より取り出した繊維（繊維Ｂ）と繊維Ａの強度を上記記載のＪＩＳの方法で測定し、その値から以下に示す式において、強度保持率を算出する。 Furthermore, the polyester fiber of the present invention preferably has a strength retention after wet heat treatment of 80% or more, and more preferably 85% or more, as a characteristic value excellent in wet heat resistance. The strength retention is the strength of the fiber A and the fiber (fiber B) taken out from the tube knitted fabric after the polyester fiber (fiber A) is subjected to pressure treatment at 135 ° C. for 16 hours. Is measured by the JIS method described above, and the strength retention is calculated from the value in the following equation.
強度保持率（％）＝（繊維Ｂの強度/繊維Ａの強度）×100
また、本発明のポリエステル繊維はマルチフィラメントでもモノフィラメントでもよく、長繊維としても短繊維として用いてもよい。また、断面形状も限定されるものではなく、丸断面のみならず、四角や三角形等の多角形状や中空部を有するものであってもよい。
Strength retention (%) = (strength of fiber B / strength of fiber A) × 100
The polyester fiber of the present invention may be a multifilament or a monofilament, and may be used as a long fiber or a short fiber. Further, the cross-sectional shape is not limited, and the cross-sectional shape may be not only a round cross-section but also a polygonal shape such as a square or a triangle or a hollow portion.
次に、本発明のポリエステル繊維の製造方法について説明する。前記のようにしてＰＥＴの重合終了時にポリカーボネートを減圧しながら脱泡し、混練してポリエステル樹脂組成物としたポリマーを常用の紡糸装置に供給して溶融紡糸を行うことが好ましい。このとき、2000m/min以上の高速紡糸により、半未延伸糸として巻き取るPOY法、あるいは一旦2000m/min以上の高速紡糸又は、2000m/min未満の低速紡糸で溶融紡糸し、巻き取った糸条を延伸熱処理する方法、一旦、巻き取ることなく、続けて延伸する紡糸延伸法のいずれを採用してもよい。 Next, the manufacturing method of the polyester fiber of this invention is demonstrated. As described above, it is preferable to carry out melt spinning by supplying the polymer obtained by defoaming the polycarbonate while reducing the pressure at the end of the polymerization of PET and kneading the mixture into a polyester resin composition to a conventional spinning device. At this time, the POY method of winding up as a semi-undrawn yarn by high-speed spinning of 2000 m / min or more, or melt spinning by high-speed spinning of 2000 m / min or more, or low-speed spinning of less than 2000 m / min, and the wound yarn Any of a method of drawing and heat-treating and a spinning drawing method of drawing continuously without winding may be adopted.
次に、実施例により本発明をさらに具体的に説明する。なお、実施例における各種の値の測定及び評価は次の通りに行った。
（１）極限粘度
フェノールと四塩化エタンの質量比1/1の混合物を溶媒とし、20℃で測定した。
（２）末端カルボキシル基濃度
得られたポリエステル繊維150mgを細かく切断してベンジルアルコール１０ｍｌに溶解 後、クロロホルム１０ｍｌを加えた後、１／10規定の水酸化カリウムベンジルアルコー ル溶液で滴定し、ブランクとの滴定量の差より算出した。
(３) 強度、伸度
前記の方法で測定した。
（４）強度保持率
前記の方法で測定した。
（５）染色斑
（４）の測定の際に得た筒編地を染色し、染色斑を目視で判定し、3段階で評価した。
○：良好
△：やや斑がある
×：斑の発生大
染色条件は、Terasil Nevy Blue SGL (ハ゛イエル社製原糸用染料)の2.0%omf 浴比
1:50の染液を用いて99℃で60分間、常法により染色した。
Next, the present invention will be described more specifically with reference to examples. In addition, measurement and evaluation of various values in the examples were performed as follows.
(1) Intrinsic viscosity A mixture of phenol and ethane tetrachloride in a mass ratio of 1/1 was used as a solvent and measured at 20 ° C.
(2) Terminal carboxyl group concentration 150 mg of the obtained polyester fiber was finely cut and dissolved in 10 ml of benzyl alcohol, 10 ml of chloroform was added, and titrated with a 1/10 normal potassium hydroxide benzyl alcohol solution. It was calculated from the difference in the titration amount.
(3) Strength and elongation Measured by the above method.
(4) Strength retention rate Measured by the above method.
(5) Dyeing spots The cylindrical knitted fabric obtained in the measurement of (4) was dyed, the dyeing spots were judged visually, and evaluated in three stages.
○: Good △: Slightly uneven ×: Large occurrence of spots Dyeing condition is 2.0% omf bath ratio of Terasil Nevy Blue SGL (Bayer dye yarn)
It dye | stained by the conventional method for 60 minutes at 99 degreeC using the dyeing liquid of 1:50.
実施例１
エチレンテレフタレートを常法により重縮合反応し、極限粘度0.64 のＰＥＴを得た後、ポリカーボネート（住友ダウ社製『カリバー301-30』）を全体量の５質量％となるように添加し、再減圧し、脱泡しながら溶融混練した。このポリエステルの極限粘度は0.66であり、これを常法によりカッティングして、チップ化した。次にこのチップを常法により乾燥し、295℃の押出機に供給し、紡糸装置より溶融紡糸を行った。紡糸口金には孔径0.25mmの紡糸孔48個が穿設されており、溶融紡糸された糸条を空気流により冷却し、オイリング装置を通過させて0.5質量％の付着量となるように油剤を付与した。引き続いて、集束ガイドで集束して交絡を付与した後、紡糸速度3500m/minのローラで引き取り、捲取機で巻き取った。
得られた繊維は255dtex/48fであり、毛羽、単糸切れによる欠点はなかった。次にこの繊維を通常の延伸装置を用い、700m/minの速度で延伸し、167dtex/48fの繊維を得た。
Example 1
Ethylene terephthalate is polycondensed by a conventional method to obtain PET with an intrinsic viscosity of 0.64, and then polycarbonate ("Caliber 301-30" manufactured by Sumitomo Dow) is added to 5 mass% of the total amount, and the pressure is reduced again. The mixture was melt kneaded while defoaming. This polyester had an intrinsic viscosity of 0.66 and was cut into chips by a conventional method. Next, this chip was dried by a conventional method, supplied to an extruder at 295 ° C., and melt spinning was performed from a spinning device. The spinneret has 48 spinning holes with a hole diameter of 0.25 mm. The melted and spun yarn is cooled by an air flow and passed through an oiling device, and an oil agent is applied so that the amount of adhesion is 0.5 mass%. Granted. Subsequently, after converging by converging with a converging guide, it was taken up with a roller having a spinning speed of 3500 m / min and wound up with a winder.
The obtained fiber was 255 dtex / 48f, and there was no defect due to fluff and single yarn breakage. Next, this fiber was drawn at a speed of 700 m / min using a normal drawing device to obtain a fiber of 167 dtex / 48f.
実施例２〜３、比較例１〜２
ポリカーボネートの添加量を表１記載の値に変更した以外は実施例１と同様に行い、ポリエステル繊維を得た。
Examples 2-3 and Comparative Examples 1-2
Except having changed the addition amount of polycarbonate into the value of Table 1, it carried out similarly to Example 1 and obtained the polyester fiber.
実施例４
極限粘度0.64 のＰＥＴとポリカーボネートを、チップの段階で質量比（ＰＥＴ／ポリカーボネート）95/5となるように混合して溶融混練し、単一孔の紡糸口金より紡糸を行った以外は実施例１と同様に行い、ポリエステル繊維を得た。
Example 4
Example 1 except that PET and polycarbonate having an intrinsic viscosity of 0.64 were mixed and melt-kneaded so as to have a mass ratio (PET / polycarbonate) of 95/5 at the tip stage, and spinning was performed from a single-hole spinneret. In the same manner as above, a polyester fiber was obtained.
実施例５
極限粘度0.64 のＰＥＴを押出機Ａに供給し、ポリカーボネートを押出機Ｂに供給し、質量比（ＰＥＴ／ポリカーボネート）95/5となるようにして、両者をノズルパック内で混練して単一孔の紡糸口金より紡糸を行った以外は実施例１と同様に行い、ポリエステル繊維を得た。
Example 5
PET with an intrinsic viscosity of 0.64 is supplied to Extruder A, Polycarbonate is supplied to Extruder B, and the mass ratio (PET / Polycarbonate) is 95/5. A polyester fiber was obtained in the same manner as in Example 1 except that spinning was performed from the above spinneret.
比較例３
チップの段階での質量比（ＰＥＴ／ポリカーボネート）を50/50とした以外は、実施例４と同様に行い、ポリエステル繊維を得た。
Comparative Example 3
A polyester fiber was obtained in the same manner as in Example 4 except that the mass ratio (PET / polycarbonate) at the tip stage was 50/50.
比較例４
質量比（ＰＥＴ／ポリカーボネート）を50/50とした以外は、実施例５と同様に行い、ポリエステル繊維を得た。
Comparative Example 4
A polyester fiber was obtained in the same manner as in Example 5 except that the mass ratio (PET / polycarbonate) was 50/50.
実施例１〜５、比較例１〜４で得られたポリエステル繊維の強度、伸度、末端カルボキシル基濃度、耐湿熱性及び染色斑の評価結果を表１に示す。 Table 1 shows the evaluation results of the strength, elongation, terminal carboxyl group concentration, wet heat resistance and dyeing spots of the polyester fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 4.
一方、比較例１のポリエステル繊維は、ポリカーボネートの含有量が少なかったため、末端カルボキシル基濃度が高く、強度保持率が低く、耐湿熱性に劣るものであった。比較例２のポリエステル繊維は、ポリカーボネートの添加量が多かったため、紡糸性が悪く、染色斑も発生した。比較例３〜４のポリエステル繊維は、ポリカーボネートの含有量が多すぎたため、紡糸の際に発泡が生じ、紡糸できなかった。 On the other hand, since the polyester fiber of Comparative Example 1 had a low polycarbonate content, the terminal carboxyl group concentration was high, the strength retention was low, and the heat and moisture resistance was poor. Since the polyester fiber of Comparative Example 2 had a large amount of polycarbonate added, the spinnability was poor and dyeing spots were also generated. Since the polyester fibers of Comparative Examples 3 to 4 contained too much polycarbonate, foaming occurred during spinning and spinning could not be performed.
Claims (1)
It consists of a polyester resin composition of 70 to 97% by weight of polyester and 3 to 30% by weight of polycarbonate after polymerization, the main repeating unit being ethylene terephthalate, and having a terminal carboxyl group concentration of 25 eq / t or less , strength retention after wet heat treatment Is a hydrolysis-resistant polyester fiber, characterized in that it is 80% or more .
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| US7849955B2 (en) | 2008-02-05 | 2010-12-14 | Crown Equipment Corporation | Materials handling vehicle having a steer system including a tactile feedback device |
| US7980352B2 (en) | 2008-02-05 | 2011-07-19 | Crown Equipment Corporation | Materials handling vehicle having a steer system including a tactile feedback device |
| US8172033B2 (en) | 2008-02-05 | 2012-05-08 | Crown Equipment Corporation | Materials handling vehicle with a module capable of changing a steerable wheel to control handle position ratio |
| US8412431B2 (en) | 2008-02-05 | 2013-04-02 | Crown Equipment Corporation | Materials handling vehicle having a control apparatus for determining an acceleration value |
| US8718890B2 (en) | 2008-02-05 | 2014-05-06 | Crown Equipment Corporation | Materials handling vehicle having a control apparatus for determining an acceleration value |
| US9421963B2 (en) | 2008-02-05 | 2016-08-23 | Crown Equipment Corporation | Materials handling vehicle having a control apparatus for determining an acceleration value |
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