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JP5912669B2 - Cationic dye-dyeable flame retardant polyester fiber and its fiber products - Google Patents

Cationic dye-dyeable flame retardant polyester fiber and its fiber products Download PDF

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JP5912669B2
JP5912669B2 JP2012045985A JP2012045985A JP5912669B2 JP 5912669 B2 JP5912669 B2 JP 5912669B2 JP 2012045985 A JP2012045985 A JP 2012045985A JP 2012045985 A JP2012045985 A JP 2012045985A JP 5912669 B2 JP5912669 B2 JP 5912669B2
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flame retardant
dyeable
cationic dye
phosphorus
fiber
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JP2013181259A (en
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純哉 今北
純哉 今北
弘美 西古
弘美 西古
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Mitsubishi Rayon Textile Co Ltd
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Description

本発明は、カチオン染料可染性及び難燃性を有するカチオン可染性難燃ポリエステル繊維に関する。   The present invention relates to a cationic dyeable flame retardant polyester fiber having cationic dye dyeability and flame retardancy.

ポリエチレンテレフタレート繊維で代表されるポリエステル繊維は、耐熱性、耐薬品性及び機械的性質に優れていることから、衣料用途や産業用途に広く利用されている。しかしながら、反面ポリエステル繊維は、繊維構造が強固であるため、通常、染色は高温高圧下で行わなければならず、エネルギーコストの面で問題がある。   Polyester fibers typified by polyethylene terephthalate fibers are widely used in clothing and industrial applications because of their excellent heat resistance, chemical resistance and mechanical properties. However, since polyester fibers have a strong fiber structure, dyeing usually has to be performed under high temperature and high pressure, which is problematic in terms of energy cost.

従来より、ポリエステル繊維の染色性を改良する目的で、ポリエステル重合体を改質して染色性を改良する方法が多数提案され、例えば、5−ナトリウムスルホイソフタル酸等の金属スルホネート基含有酸成分をポリエステルに共重合してカチオン染料による可染性を付与する方法が知られている(特許文献1)。また、5−ナトリウムスルホイソフタル酸等の金属スルホネート基含有酸成分に加えてアジピン酸等の酸成分をポリエステルに共重合して、分散染料、カチオン染料による常圧での染色可能な染色性を付与する方法も知られている(特許文献2)。   Conventionally, in order to improve the dyeability of polyester fibers, many methods for improving the dyeability by modifying the polyester polymer have been proposed. For example, a metal sulfonate group-containing acid component such as 5-sodiumsulfoisophthalic acid has been proposed. A method of imparting dyeability with a cationic dye by copolymerizing with polyester is known (Patent Document 1). Also, in addition to metal sulfonate group-containing acid components such as 5-sodium sulfoisophthalic acid, an acid component such as adipic acid is copolymerized with polyester to provide dyeability that can be dyed at normal pressure with disperse dyes and cationic dyes. The method of doing is also known (patent document 2).

一方、カーテン(シャワーカーテン及びレースカーテンを含む)、寝装具、ウォールクロス、インクジェットクロス及びカーペット等の繊維製品への難燃化が求められており、これらの繊維製品に使用されるポリエステル繊維にも当然ながら難燃化が求められている。そして、特にこれらの繊維製品の分野では、難燃性とともに、染め上がりの製品を鮮やかにするために分散染料及びカチオン染料に常圧で染色可能な染色性もポリエステル繊維
に求められているが、金属スルホネート基含有酸成分等を共重合させたポリエステル繊維は、炎症し易いという問題があり、用途に制限がある。
On the other hand, there is a demand for flame resistance to textile products such as curtains (including shower curtains and lace curtains), bedding, wall cloths, inkjet cloths and carpets, and polyester fibers used in these textile products are also required. Of course, flame retardancy is required. Particularly in the field of these textile products, in addition to flame retardancy, in order to make the dyed product vivid, dyeing properties that can be dyed at normal pressure with disperse dyes and cationic dyes are also required for polyester fibers. Polyester fibers obtained by copolymerizing a sulfonate group-containing acid component or the like have a problem that they are easily irritated and have limited applications.

また、金属スルホネート含有化合物を0.5〜5モル%及びリン系難燃剤をリン原子を基準として5000〜15000ppmとなる含有量を共重合させたポリエステル重合体を用いて難燃性でカチオン染料可染性のポリエステル繊維とすることが知られている(特許文献3)。しかしながら、この難燃性カチオン染料可染性ポリエステル繊維は、カチオン染料で染色可能なものの、常圧可染性という面では不十分であった。   In addition, flame retardant and cationic dyes can be used using a polyester polymer obtained by copolymerizing a metal sulfonate-containing compound in an amount of 0.5 to 5 mol% and a phosphorus flame retardant with a content of 5000 to 15000 ppm based on phosphorus atoms. It is known to use a dyeable polyester fiber (Patent Document 3). However, this flame retardant cationic dye dyeable polyester fiber can be dyed with a cationic dye, but is insufficient in terms of atmospheric pressure dyeability.

特公昭34−10497号公報Japanese Patent Publication No.34-10497 特開平8−269820号公報JP-A-8-269820 特開2005−273043号公報Japanese Patent Laid-Open No. 2005-273043

本発明は、従来のポリエステル重合体の改質状況に鑑み、さらに検討し改良してなさたものであり、本発明の目的は、常圧でのカチオン染料に対する優れた可染性及び優れた難燃性を有するカチオン染料可染性難燃ポリエステル繊維を提供し、また本発明の他の目的は、かかるカチオン染料可染性難燃ポリエステル繊維を用いた繊維製品を提供することにある。   The present invention has been made by further study and improvement in view of the state of modification of conventional polyester polymers. The object of the present invention is to achieve excellent dyeability and excellent difficulty for cationic dyes at normal pressure. A cationic dye-dyeable flame-retardant polyester fiber having flame retardancy is provided, and another object of the present invention is to provide a textile product using the cationic dye-dyeable flame-retardant polyester fiber.

本発明の第1の発明の要旨は、主たる繰り返し単位がエチレンテレフタレートであるポリエステルに、スルホイソフタル酸のアルカリ金属塩、炭素数4〜10の脂肪族ジカルボン酸及びリン系難燃剤が下記条件(a)、(b)、(c)を満足するよう共重合された共重合ポリエステル樹脂にて構成されたカチオン染料可染性難燃ポリエステル繊維にある。
(a)0.8≦S≦3.0
(b)3.0≦A≦10.0
(c)3000≦P≦10000
(但し、式中、Sはスルホイソフタル酸のアルカリ金属塩の共重合量(モル%)、Aは炭素数4〜10の脂肪族ジカルボン酸の共重合量(モル%)、Pはリン系難燃剤のリン原子を基準とした共重合量(ppm)を示す)
本発明の第2の発明の要旨は、前記カチオン染料可染性難燃ポリエステル繊維を用いてなる繊維製品にある。
The gist of the first invention of the present invention is that a polyester whose main repeating unit is ethylene terephthalate, an alkali metal salt of sulfoisophthalic acid, an aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and a phosphorus-based flame retardant are the following conditions (a ), (B), and (c), a cationic dye-dyeable flame retardant polyester fiber composed of a copolyester resin copolymerized.
(A) 0.8 ≦ S ≦ 3.0
(B) 3.0 ≦ A ≦ 10.0
(C) 3000 ≦ P ≦ 10000
(Wherein S is the copolymerization amount (mol%) of the alkali metal salt of sulfoisophthalic acid, A is the copolymerization amount (mol%) of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and P is the phosphorus-based difficulty. (Shows the amount of copolymerization (ppm) based on the phosphorus atom of the flame retardant)
The gist of the second invention of the present invention resides in a fiber product using the cationic dye-dyeable flame retardant polyester fiber.

本発明のカチオン染料可染性難燃ポリエステル繊維は、その構成の樹脂の重合体中にスルホイソフタル酸のアルカリ金属塩及び炭素数4〜10の脂肪族ジカルボン酸が共重合されていることによりカチオン染料に対して優れた可染性を示し、常圧での染色で良好な染色性を発揮する。また本発明のカチオン染料可染性難燃ポリエステル繊維は、重合体中にリン系難燃剤が含まれ延焼し難い優れた難燃性を発揮する。さらに本発明のカチオン染料可染性難燃ポリエステル繊維の製造に際しては、紡糸工程、製糸工程での融着等がなく繊維物性、作業上良好に得ることができ、カチオン染料可染性難燃ポリエステル繊維は繊維製品として幅広く用いられるものである。   The cationic dye-dyeable flame retardant polyester fiber of the present invention has a cation formed by copolymerization of an alkali metal salt of sulfoisophthalic acid and an aliphatic dicarboxylic acid having 4 to 10 carbon atoms in a polymer of the resin having the constitution. It exhibits excellent dyeability for dyes and exhibits good dyeability when dyed at normal pressure. Further, the cationic dye-dyeable flame retardant polyester fiber of the present invention exhibits excellent flame retardancy that contains a phosphorus flame retardant in the polymer and is difficult to spread. Furthermore, in the production of the cationic dye-dyeable flame retardant polyester fiber of the present invention, the fiber property and workability can be obtained without fusion in the spinning process and the yarn making process, and the cationic dye-dyeable flame retardant polyester can be obtained. Fiber is widely used as a textile product.

以下、本発明の実施の形態について、詳細に説明する。
〈共重合ポリエステル樹脂〉
本発明において、カチオン染料可染性難燃ポリエステル繊維を構成する共重合ポリエステル樹脂は、主たる繰り返し単位がエチレンテレフタレートであるポリエステルに、スルホイソフタル酸のアルカリ金属塩が0.8〜3.0モル%、炭素数4〜10の脂肪族ジカルボン酸が3.0〜10.0モル%及びリン系難燃剤がリン原子を基準とした含有量で3000〜10000ppm共重合された共重合ポリエステル樹脂である。
Hereinafter, embodiments of the present invention will be described in detail.
<Copolymerized polyester resin>
In the present invention, the copolyester resin constituting the cationic dye-dyeable flame retardant polyester fiber is a polyester whose main repeating unit is ethylene terephthalate, and an alkali metal salt of sulfoisophthalic acid is 0.8 to 3.0 mol%. The polyester resin is a copolymerized polyester resin having a content of 3.0 to 10.0 mol% of an aliphatic dicarboxylic acid having 4 to 10 carbon atoms and a phosphorus flame retardant content of 3000 to 10000 ppm based on a phosphorus atom.

〈スルホイソフタル酸のアルカリ金属塩〉
共重合ポリエステル樹脂におけるスルホイソフタル酸のアルカリ金属塩は、カチオン染料の染着座席を付与してカチオン染料による染着性を得るものであり、その共重合量は、0.8〜3.0モル%、好ましくは1.5〜2.5モル%であることが必要である。スルホイソフタル酸のアルカリ金属塩の共重合量が0.8モル%未満では、カチオン染料の染着座席が不足して染着量が少なくなるだけでなく、カチオン染料特有の鮮明性にも乏しくなる。またスルホイソフタル酸のアルカリ金属塩の共重合量が3.0モル%を超えると、重合時において重合体の溶融粘度が上昇し、低粘度の重合体しか得られず、その結果、紡糸された繊維は繊維強度の低下したものとなる。
<Alkali metal salt of sulfoisophthalic acid>
The alkali metal salt of sulfoisophthalic acid in the copolymerized polyester resin provides a dyeing seat for the cationic dye to obtain a dyeing property by the cationic dye, and the copolymerization amount is 0.8 to 3.0 mol. %, Preferably 1.5 to 2.5 mol%. If the copolymerization amount of the alkali metal salt of sulfoisophthalic acid is less than 0.8 mol%, not only the dyeing seat of the cationic dye is insufficient, but the dyeing amount is reduced, and the sharpness peculiar to the cationic dye is also poor. . When the copolymerization amount of the alkali metal salt of sulfoisophthalic acid exceeds 3.0 mol%, the melt viscosity of the polymer is increased during the polymerization, and only a low-viscosity polymer is obtained. As a result, spinning is performed. The fiber has a reduced fiber strength.

スルホイソフタル酸のアルカリ金属塩としては、例えば、5−ナトリウムスルホイソフタル酸、5−カリウムスルホイソフタル酸、5−リチウムスルホイソフタル酸、5−ルビジウムスルホイソフタル酸、5−セシウムスルホイソフタル酸等が挙げられ、特に好ましいものとして5−ナトリウムスルホイソフタル酸が挙げられる。また必要に応じて、スルホイソフタル酸のアルカリ金属塩にマグネシウム、カルシウム等のアルカリ土類金属塩を併用してもよい。   Examples of the alkali metal salt of sulfoisophthalic acid include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5-rubidium sulfoisophthalic acid, and 5-cesium sulfoisophthalic acid. Particularly preferred is 5-sodium sulfoisophthalic acid. Moreover, you may use together alkaline earth metal salts, such as magnesium and calcium, with the alkali metal salt of sulfo isophthalic acid as needed.

〈炭素数4〜10の脂肪族ジカルボン酸〉
共重合ポリエステル樹脂における炭素数4〜10の脂肪族ジカルボン酸は、繊維の非晶構造に適度な乱れを与え、染料の進入を容易にして染色性の向上に寄与するもので、その共重合量は、3.0〜10.0モル%、好ましくは4.0〜7.0モル%であることが必要である。炭素数4〜10の脂肪族ジカルボン酸の共重合量が3.0モル%未満では、常圧染色における染色性が低下する。また炭素数4〜10の脂肪族ジカルボン酸の共重合量が10.0モル%を超えると、重合体のガラス転移温度や融点が低下し、繊維或いは繊維製品として必要な力学特性、摩擦堅牢性、耐熱性等が不足する。
<C4-C10 aliphatic dicarboxylic acid>
The aliphatic dicarboxylic acid having 4 to 10 carbon atoms in the copolyester resin gives an appropriate disorder to the amorphous structure of the fiber, facilitates the ingress of the dye, and contributes to the improvement of the dyeability. Is required to be 3.0 to 10.0 mol%, preferably 4.0 to 7.0 mol%. When the copolymerization amount of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms is less than 3.0 mol%, the dyeability in atmospheric dyeing is lowered. Moreover, when the copolymerization amount of aliphatic dicarboxylic acid having 4 to 10 carbon atoms exceeds 10.0 mol%, the glass transition temperature and melting point of the polymer are lowered, and mechanical properties and friction fastness required for fibers or fiber products are reduced. Insufficient heat resistance.

炭素数4〜10の脂肪族ジカルボン酸としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸が挙げられ、これらは単独でまた組み合わせて用いてもよい。本発明において特に好ましい脂肪族ジカルボン酸としてアジピン酸が挙げられる。   Examples of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and these may be used alone or in combination. A particularly preferred aliphatic dicarboxylic acid in the present invention is adipic acid.

〈リン系難燃剤〉
また、共重合ポリエステル樹脂には、環境への負荷を少なくし、難燃性を付与しうる非ハロゲン系であるリン系難燃剤が、リン原子を基準として3000〜10000ppm含有されるよう共重合されることが必要である。重合体におけるリン系難燃剤のリン原子の含有量が、3000ppm未満では、有効な難燃性は得られず、10000ppmを超えると、難燃性には優れるものの、製造コストが高くなるだけでなく、重合体及び繊維を安定に製造することが困難になる。
<Phosphorus flame retardant>
In addition, the copolymerized polyester resin is copolymerized so that a non-halogen-based phosphorus flame retardant that reduces the burden on the environment and imparts flame retardancy is contained in an amount of 3000 to 10,000 ppm based on phosphorus atoms. It is necessary to If the phosphorus atom content of the phosphorus flame retardant in the polymer is less than 3000 ppm, effective flame retardancy cannot be obtained, and if it exceeds 10,000 ppm, the flame retardancy is excellent, but not only the production cost is increased. In addition, it becomes difficult to stably produce the polymer and the fiber.

本発明において、特に好ましいリン系難燃剤として下記の一般式(1)で表されるリン化合物が挙げられ、前記金属スルホネートイソフタル酸、脂肪族ジカルボン酸と組み合わせたときに、持続性のある難燃性を得ることができる。   In the present invention, as a particularly preferable phosphorus-based flame retardant, a phosphorus compound represented by the following general formula (1) can be mentioned, and when combined with the metal sulfonate isophthalic acid and the aliphatic dicarboxylic acid, a durable flame retardant Sex can be obtained.

(但し、式中、Rは水素原子またはC1〜C8のヒドロキシアルキル基である) (In the formula, R 1 is a hydrogen atom or a C1-C8 hydroxyalkyl group)

〈共重合ポリエステル樹脂の物性〉
本発明のカチオン染料可染性難燃ポリエステル繊維を構成する共重合ポリエステル樹脂は、ガラス転移温度が60〜70℃、融点が215〜240℃であることが好ましい。ガラス転移温度が60〜70℃、融点が215〜240℃であることにより、常圧染色における染色性が良好で、かつ繊維製品として必要な力学特性、堅牢性、耐熱性等が良好である。
<Physical properties of copolymer polyester resin>
The copolymer polyester resin constituting the cationic dye-dyeable flame retardant polyester fiber of the present invention preferably has a glass transition temperature of 60 to 70 ° C and a melting point of 215 to 240 ° C. When the glass transition temperature is 60 to 70 ° C. and the melting point is 215 to 240 ° C., the dyeability in atmospheric dyeing is good, and the mechanical properties, fastness, heat resistance, and the like necessary for a fiber product are good.

〈共重合ポリエステル樹脂の製造〉
本発明における共重合ポリエステル樹脂は、例えば次のようにして製造することができる。
すなわち、テレフタル酸とエチレングリコールとを直接エステル化させる、或いはテレフタル酸ジメチルエステルとエチレングリコールとをエステル交換させて、ビスヒドロキシルエチルテレフタレート及びその低重合物のオリゴマーを合成し、次いで、その反応系に共重合成分としてスルホイソフタル酸のアルカリ金属塩、炭素数4〜10の脂肪族ジカルボン酸、さらにリン系難燃剤をそれぞれ所定量添加した後、重縮合反応を開始する。
<Manufacture of copolyester resin>
The copolyester resin in the present invention can be produced, for example, as follows.
That is, terephthalic acid and ethylene glycol are directly esterified or terephthalic acid dimethyl ester and ethylene glycol are transesterified to synthesize oligomers of bishydroxylethyl terephthalate and its low polymer, and then into the reaction system. After adding a predetermined amount of an alkali metal salt of sulfoisophthalic acid, an aliphatic dicarboxylic acid having 4 to 10 carbon atoms and a phosphorus flame retardant as copolymerization components, a polycondensation reaction is started.

スルホイソフタル酸のアルカリ金属塩、炭素数4〜10の脂肪族ジカルボン酸、リン系難燃剤の添加は、エチレングリコールに分散させて添加してもよいし、エチレングリコールのエステルとしてエチレングリコール溶液として添加してもよい。   Addition of alkali metal salt of sulfoisophthalic acid, aliphatic dicarboxylic acid having 4 to 10 carbon atoms and phosphorus-based flame retardant may be performed by dispersing in ethylene glycol, or added as an ethylene glycol solution as an ethylene glycol ester. May be.

重縮合反応は、三酸化アンチモン、二酸化ゲルマニウム等の重縮合触媒を用い、減圧下で高温で生成する重合体の固有粘度が0.55〜0.65となるまで行う。また重合での任意の段階で、他の共重合成分を必要に応じ添加し共重合させてもよいし、抗酸化剤、蛍光剤、艶消剤、耐光性改良剤等の添加剤を添加してもよい。重縮合反応の終了後は取り出された共重合樹脂はペレットとされ乾燥される。   The polycondensation reaction is performed using a polycondensation catalyst such as antimony trioxide and germanium dioxide until the intrinsic viscosity of the polymer produced at a high temperature under reduced pressure becomes 0.55 to 0.65. In addition, at any stage of the polymerization, other copolymer components may be added and copolymerized as necessary, or additives such as antioxidants, fluorescent agents, matting agents, and light resistance improvers may be added. May be. After completion of the polycondensation reaction, the taken copolymer resin is pelleted and dried.

〈カチオン染料可染性難燃ポリエステル繊維の製造〉
共重合ポリエステル樹脂を用いて繊維にする際は、通常のポリエステル繊維を製造するのと同様の溶融紡糸法により、共重合ポリエステル樹脂の融点より高い温度で溶融紡糸し、延伸し、さらに必要に応じ仮撚加工等の糸加工を施し、繊維製品を得るに好適な形態の繊維とする。繊維にする際の繊維断面形状、繊度等については特に制限はない。
<Manufacture of cationic dye dyeable flame retardant polyester fiber>
When making a fiber using a copolyester resin, it is melt-spun at a temperature higher than the melting point of the copolyester resin and stretched by the same melt spinning method as that for producing a normal polyester fiber. Yarn processing such as false twisting is applied to obtain a fiber in a form suitable for obtaining a fiber product. There is no restriction | limiting in particular about the fiber cross-sectional shape at the time of making a fiber, a fineness, etc.

〈カチオン染料可染性難燃ポリエステル繊維を用いた繊維製品〉
本発明のカチオン染料可染性難燃ポリエステル繊維は、カーテン、寝装具、カーペット、ウオールクロス等の繊維製品に用いることができる。繊維製品にするに当たっては、本発明のカチオン染料可染性難燃ポリエステル繊維単独で用いてもよいし、カチオン染料による染色性及び難燃性を損なわない範囲で、他の繊維と複合して、光沢感、清涼感、シャリ感、ウェット感等を付与することができる。
<Fiber products using cationic dyeable flame retardant polyester fiber>
The cationic dye-dyeable flame retardant polyester fiber of the present invention can be used for textile products such as curtains, bedding, carpets and wall cloths. In making a textile product, the cationic dye dyeable flame retardant polyester fiber of the present invention may be used alone, or in combination with other fibers within a range that does not impair the dyeability and flame retardancy by the cationic dye, Glossy feeling, cool feeling, sharp feeling, wet feeling and the like can be imparted.

以下、本発明を実施例により具体的に説明する。なお、実施例中の測定項目は、次の方法に拠った。   Hereinafter, the present invention will be specifically described by way of examples. The measurement items in the examples were based on the following method.

〈リン原子(P)含有量〉
リガク社製、電光X線スペクトロメーター3270型にて、蛍光X線法により定量した。
<Phosphorus atom (P) content>
Quantification was carried out by fluorescent X-ray method using a lightning X-ray spectrometer model 3270 manufactured by Rigaku Corporation.

〈難燃性〉
JIS L1091 D法(45度コイル法)により測定した。
D法では、100mm、1gとなるようサンプルの試験体を準備し、試験体が10mmになるまでの接炎回数を測定する。測定回数は5回とし、各測定において、10mmになるまでの接炎回数が全て3回以上であれば合格(○)、5つの試験体の測定のうち1つの試験体でも接炎回数が2回以下であれば不合格(×)とする。
<Flame retardance>
It was measured by JIS L1091 D method (45 degree coil method).
In the method D, a sample specimen is prepared so as to be 100 mm and 1 g, and the number of times of flame contact until the specimen becomes 10 mm is measured. The number of times of measurement is 5 times, and in each measurement, if the number of flame contact until reaching 10 mm is all 3 times or more, it is acceptable (O), and the number of flame contact is 2 even in one of the five test specimens. If it is less than or equal to the number of times, it will be rejected (x).

〈固有粘度[η]〉
共重合ポリエステル樹脂0.25gを粉砕し、フェノール/テトラクロルエタン(50/50)の混合溶媒50mlに溶解し、25℃に温調した自動粘度計(サン電子工業社製、AVL−4型)で測定した。なお、計算式は以下の通りである。
[η]={(1+1.04ηsp)1/2 −1}/0.26
<Intrinsic viscosity [η]>
0.25 g of copolyester resin was pulverized, dissolved in 50 ml of a mixed solvent of phenol / tetrachloroethane (50/50), and temperature-controlled at 25 ° C. (manufactured by Sun Electronics Co., Ltd., AVL-4 type) Measured with The calculation formula is as follows.
[Η] = {(1 + 1.04ηsp) 1/2 −1} /0.26

〈ガラス転移温度(Tg)及び融点〉
セイコー電子工業社製、DSC220を用いて、昇温速度10℃/分で共重合ポリエステル樹脂のTg(℃)及び融点(℃)を測定した。
<Glass transition temperature (Tg) and melting point>
The Tg (° C.) and the melting point (° C.) of the copolyester resin were measured using a DSC220 manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature rising rate of 10 ° C./min.

〈カチオン染料可染性〉
カチオン染料(保土ケ谷化学社製、AIZEN CATHILON MARINE BLUE GPLH)の濃度1.5%owf(対繊維質量)の染浴で、温度98℃で60分間常圧染色し、染色性を鮮明性と均染性とで判断し、優れるものから劣るまでを、◎、○、△、×の4段階で評価した。
<Cationic dye dyeability>
Dye bath with cationic dye (AIZEN CATHILON MARINE BLUE GPLH manufactured by Hodogaya Chemical Co., Ltd.) at a concentration of 1.5% owf (for fiber mass) and dyeing under normal pressure at a temperature of 98 ° C. for 60 minutes. Judging by the property, it was evaluated in four stages of ◎, ○, Δ, and × from superior to inferior.

(実施例1)
(1)ポリエステルオリゴマーの存在するエステル化反応缶にテレフタル酸(以下、TPAと略記する)とエチレングリコール(以下、EGと略記する)とのモル比が1/1.6のスラリーを供給し、エステル化反応を行った。その結果、反応率95%のポリエステルオリゴマーを得た。引き続き、得られたポリエステルオリゴマーを重縮合反応缶に移送した。
(2)その重縮合反応缶に、アジピン酸(以下、ADと略記する)のEG分散液を、重合体中のAD濃度が5モル%となるように添加し、前記化学式(1)におけるRがヒドロキシエチル(CHCHOH)基であるリン系難燃剤を、濃度が60質量%に調整されたEG溶液として、生成重合体中のリン原子(P)の含有量が6000ppmとなるように添加した。
(3)重縮合反応缶に、色調調整剤としてトリエチルホスフェートを添加し、さらに、5−ナトリウムスルホイソフタル酸(以下、DMSと略記する)のEGエステルのEG溶液を、重合体中のDMS濃度が1.75モル%となるように添加した。
(4)さらに、重縮合反応缶に、重縮合触媒として三酸化アンチモンを添加し、減圧下に重縮合を行い、共重合ポリエステル樹脂を得た。得られた共重合ポリエステル樹脂はチップとし、常法にて乾燥した。表1にその樹脂の特性値を示した。
(5)次いで、得られた共重合ポリエステル樹脂のペレットを原料とし、孔径0.25mm、36ホールの円形紡糸孔の紡糸口金を設置した紡糸装置を用いて、紡糸温度260℃、紡糸速度2000m/分で溶融紡糸し、得られた未延伸糸を延伸速度600m/分、延伸温度78℃、熱セット温度145℃、最大延伸倍率の0.73倍で延伸し、84dtex/36フィラメントのポリエステル繊維を得た。
(6)得られたポリエステル繊維を20ゲージの筒編機にて編地を作成し、燃焼試験を実施して難燃性を測定し表1に示した。また得られた編地のカチオン染料可染性を評価し、その結果を表1に示した。
Example 1
(1) A slurry having a molar ratio of terephthalic acid (hereinafter abbreviated as TPA) and ethylene glycol (hereinafter abbreviated as EG) to 1/1. An esterification reaction was performed. As a result, a polyester oligomer having a reaction rate of 95% was obtained. Subsequently, the obtained polyester oligomer was transferred to a polycondensation reaction can.
(2) An EG dispersion of adipic acid (hereinafter abbreviated as AD) is added to the polycondensation reaction vessel so that the AD concentration in the polymer is 5 mol%, and R in the chemical formula (1) is added. When the phosphorus flame retardant 1 in which 1 is a hydroxyethyl (CH 2 CH 2 OH) group is used as an EG solution adjusted to a concentration of 60% by mass, the content of phosphorus atoms (P) in the resulting polymer is 6000 ppm. Was added as follows.
(3) Triethyl phosphate is added to the polycondensation reaction can as a color tone adjusting agent, and an EG solution of EG ester of 5-sodiumsulfoisophthalic acid (hereinafter abbreviated as DMS) is further added to the DMS concentration in the polymer. It added so that it might become 1.75 mol%.
(4) Further, antimony trioxide was added to the polycondensation reaction can as a polycondensation catalyst, and polycondensation was performed under reduced pressure to obtain a copolymer polyester resin. The obtained copolyester resin was used as a chip and dried by a conventional method. Table 1 shows the characteristic values of the resin.
(5) Next, using the obtained polyester polyester resin pellets as a raw material and using a spinning device in which a spinneret of a 36-hole circular spinning hole was installed, a spinning temperature of 260 ° C., a spinning speed of 2000 m / The resulting undrawn yarn was drawn at a drawing speed of 600 m / min, a drawing temperature of 78 ° C., a heat setting temperature of 145 ° C., and a maximum drawing ratio of 0.73 times to obtain a polyester fiber of 84 dtex / 36 filaments. Obtained.
(6) A knitted fabric was prepared from the obtained polyester fiber with a 20-gauge cylinder knitting machine, and a flame test was performed to measure flame retardancy. Further, the dyeability of the obtained knitted fabric was evaluated, and the results are shown in Table 1.

(実施例2〜5及び比較例1〜3)
実施例1において、DMS、AD及びリン系難燃剤(Pとして)のそれぞれの添加量を表1に示したように変更した以外は、実施例1と同様にして、共重合ポリエステル樹脂を得、得られた共重合ポリエステル樹脂を用いて溶融紡糸してポリエステル繊維を得た。得られた繊維で編地を作成し、難燃性を測定し、またカチオン染料可染性の評価をし、その結果を表1に示した。
(Examples 2-5 and Comparative Examples 1-3)
In Example 1, a copolymer polyester resin was obtained in the same manner as in Example 1 except that the addition amounts of DMS, AD and phosphorus flame retardant (as P) were changed as shown in Table 1. A polyester fiber was obtained by melt spinning using the obtained copolyester resin. A knitted fabric was prepared from the obtained fibers, the flame retardancy was measured, and the dyeability of the cationic dye was evaluated. The results are shown in Table 1.

本発明のカチオン染料可染性難燃ポリエステル繊維は、そのカチオン染料による鮮明性と均染性に優れた染色性、難燃性が発揮しうるカーテン、寝装具、カーペット、ウオールクロス等の繊維製品に好適なるものであり、また染色性、難燃性が要求される分野であれば、衣料用途にも有用なるものである。   The cationic dye-dyeable flame retardant polyester fiber of the present invention is a textile product such as a curtain, bedding, carpet, wall cloth, etc., which can exhibit the sharpness and leveling excellent dyeing property and flame retardancy with the cationic dye. If it is a field where dyeability and flame retardancy are required, it is also useful for clothing.

Claims (4)

主たる繰り返し単位がエチレンテレフタレートであるポリエステルに、スルホイソフタル酸のアルカリ金属塩、炭素数4〜10の脂肪族ジカルボン酸及びリン系難燃剤が下記条件(a)、(b)、(c)を満足するよう共重合され、融点215〜240℃の樹脂である共重合ポリエステル樹脂にて構成されたカチオン染料可染性難燃ポリエステル繊維。
(a)0.8≦S≦3.0
(b)3.0≦A≦10.0
(c)3000≦P≦10000
(但し、式中、Sはスルホイソフタル酸のアルカリ金属塩の共重合量(モル%)、Aは炭素数4〜10の脂肪族ジカルボン酸の共重合量(モル%)、Pはリン系難燃剤のリン原子を基準とした共重合量(ppm)を示す)
Polyester whose main repeating unit is ethylene terephthalate, alkali metal salt of sulfoisophthalic acid, aliphatic dicarboxylic acid having 4 to 10 carbon atoms and phosphorus flame retardant satisfy the following conditions (a), (b) and (c) A cationic dye-dyeable flame retardant polyester fiber composed of a copolyester resin which is a resin having a melting point of 215 to 240 ° C.
(A) 0.8 ≦ S ≦ 3.0
(B) 3.0 ≦ A ≦ 10.0
(C) 3000 ≦ P ≦ 10000
(Wherein S is the copolymerization amount (mol%) of the alkali metal salt of sulfoisophthalic acid, A is the copolymerization amount (mol%) of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and P is the phosphorus-based difficulty. (Shows the amount of copolymerization (ppm) based on the phosphorus atom of the flame retardant)
リン系難燃剤が、下記化学式(1)で表されるリン化合物である請求項1に記載のカチオン染料可染性難燃ポリエステル繊維。
(但し、式中、Rは水素原子またはC1〜C8のヒドロキシアルキル基である)
The cationic dye-dyeable flame retardant polyester fiber according to claim 1, wherein the phosphorus flame retardant is a phosphorus compound represented by the following chemical formula (1).
(In the formula, R 1 is a hydrogen atom or a C1-C8 hydroxyalkyl group)
共重合ポリエステル樹脂が、ガラス転移温度60〜70℃の樹脂である請求項1または2に記載のカチオン染料可染性難燃ポリエステル繊維。The cationic dyeable dyeable flame retardant polyester fiber according to claim 1 or 2, wherein the copolyester resin is a resin having a glass transition temperature of 60 to 70 ° C. 請求項1〜3のいずれか一項に記載されたカチオン染料可染性難燃ポリエステル繊維を用いてなる繊維製品。 A fiber product using the cationic dye-dyeable flame retardant polyester fiber according to any one of claims 1 to 3.
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