JP5700332B2

JP5700332B2 - Method for producing modified yarn

Info

Publication number: JP5700332B2
Application number: JP2010257614A
Authority: JP
Inventors: 善英三村; 修一源中; 米澤　修一; 修一米澤; 和也西原; 堀　照夫; 照夫堀; 里子奥林
Original assignee: Kyoto Institute of Technology NUC; Suminoe Textile Co Ltd; University of Fukui
Current assignee: Kyoto Institute of Technology NUC; Suminoe Textile Co Ltd; University of Fukui
Priority date: 2010-11-18
Filing date: 2010-11-18
Publication date: 2015-04-15
Anticipated expiration: 2030-11-18
Also published as: JP2012107362A

Description

本発明は、グラフト重合反応により改質（難燃性付与、抗菌性付与、吸湿性付与、吸水性付与、制電性付与、防汚性付与等）がなされた、ポリエステル素材、ポリアミド素材又はウール素材の改質糸を安定して高速生産することのできる改質糸の製造方法に関する。 The present invention is a polyester material, polyamide material, or wool that has been modified by graft polymerization reaction (improving flame retardancy, imparting antibacterial properties, imparting moisture absorption, imparting water absorption, imparting antistatic properties, imparting antifouling properties, etc.) The present invention relates to a method for producing a modified yarn capable of stably and rapidly producing a modified yarn of a material.

糸の改質を行う技術は、古くから数多く提案されており、その中の一方法としてグラフト重合反応により糸の改質を行う方法が公知である。 Many techniques for modifying yarn have been proposed for a long time, and a method for modifying yarn by a graft polymerization reaction is known as one of them.

特許文献１には、糸状又は綿塊状繊維物質に、放射線グラフト重合を用いて、機能性官能基を有する重合性ビニルモノマーをグラフト重合させることにより改質糸を製造することが記載されている。また、糸に放射線を照射してラジカルを形成させ、これに重合性ビニルモノマーを反応させてグラフト重合させる前照射法と、糸を重合性ビニルモノマーの共存下で放射線を照射することによってラジカル形成とモノマーとの反応を行わせる同時照射法とがあることが記載されている。そして、前照射法の一例として、チーズボビンの周囲に糸を巻き付けたチーズに放射線を照射した後、この放射線照射糸を重合性ビニルモノマーに浸漬し、加熱することによって、グラフト重合改質糸を得ることが記載されている。 Patent Document 1 describes that a modified yarn is produced by graft polymerization of a polymerizable vinyl monomer having a functional functional group to a filamentous or cotton lump-like fiber material using radiation graft polymerization. Radiation is formed by irradiating the yarn with radiation before forming a radical, reacting this with a polymerizable vinyl monomer and graft polymerization, and irradiating the yarn with radiation in the presence of the polymerizable vinyl monomer. And a simultaneous irradiation method in which a reaction between a monomer and a monomer is performed. And as an example of the pre-irradiation method, after irradiating the cheese wrapped around the cheese bobbin with radiation, the radiation-irradiated yarn is immersed in a polymerizable vinyl monomer, and heated to thereby change the graft polymerization modified yarn. It is described to obtain.

特開２００２−３３９１８７号公報JP 2002-339187 A

しかしながら、上記特許文献１に記載の技術では、糸をチーズボビンの周囲に巻き付けたチーズを一旦製作して、この製作されたチーズを次の工程の放射線照射装置内にセットする、さらにチーズを次の浸漬、加熱工程で反応容器内にセットする、というような作業を要するものとなっており、従ってチーズ製作工程から放射線照射工程を経て浸漬、加熱工程に至るまでを一連の連続工程で実施することができないという問題があった。即ち、改質糸を連続工程で高速生産することができないという問題があった。 However, in the technique described in the above-mentioned Patent Document 1, a cheese obtained by winding a thread around a cheese bobbin is once manufactured, and the manufactured cheese is set in a radiation irradiation apparatus in the next step. Therefore, it is necessary to perform a series of continuous processes from the cheese manufacturing process through the radiation irradiation process to the immersion and heating process. There was a problem that I could not. That is, there is a problem that the modified yarn cannot be produced at high speed in a continuous process.

また、ポリエステル糸、ポリアミド糸、ウール糸は、ラジカルが生成し難くグラフト重合させ難いものであり、改質を行うには電子線の照射時間を大きく増大させなければならず、このためにポリエステル素材、ポリアミド素材又はウール素材を用いて高速生産で改質糸を製造することはできなかった。 Polyester yarns, polyamide yarns, and wool yarns are hard to generate radicals and are difficult to graft polymerize. For modification, it is necessary to greatly increase the electron beam irradiation time. The modified yarn could not be produced at high speed production using a polyamide material or a wool material.

本発明は、かかる技術的背景に鑑みてなされたものであって、グラフト重合反応により改質（例えば難燃化等）がなされた、ポリエステル素材、ポリアミド素材又はウール素材の改質糸を安定して高速生産できる改質糸の製造方法を提供することを目的とする。 The present invention has been made in view of such a technical background, and stabilizes a modified yarn of a polyester material, a polyamide material, or a wool material that has been modified (for example, flame retardant) by a graft polymerization reaction. An object of the present invention is to provide a method for producing a modified yarn that can be produced at high speed.

前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.

［１］ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸であって搬送されている糸に電子線を照射する電子線照射工程と、
前記電子線照射後の搬送糸にラジカル重合性モノマーを接触させる接触工程と、
前記接触工程後の糸を８０℃以上の温度で加熱することによって前記ラジカル重合性モノマーを糸にグラフト重合させるグラフト重合工程と、を含み、
前記電子線照射工程、前記接触工程および前記グラフト重合工程を不活性雰囲気で連続で実施することを特徴とする改質糸の製造方法。 [1] An electron beam irradiation step of irradiating an electron beam to a yarn that is selected from the group consisting of a polyester yarn, a polyamide yarn, and a wool yarn and is being conveyed;
A contact step of bringing a radical polymerizable monomer into contact with the carrier yarn after irradiation with the electron beam;
A graft polymerization step of graft-polymerizing the radical polymerizable monomer onto the yarn by heating the yarn after the contacting step at a temperature of 80 ° C. or more,
A method for producing a modified yarn, wherein the electron beam irradiation step, the contact step, and the graft polymerization step are continuously performed in an inert atmosphere.

［２］前記電子線照射工程の前に、巻き取り状態の糸の巻き出しと、該巻き出された糸の電子線照射工程への移送を不活性雰囲気で行う給糸工程を有する前項１に記載の改質糸の製造方法。 [2] In the preceding item 1 having a yarn feeding step of unwinding the wound yarn and transferring the unwound yarn to the electron beam irradiation step in an inert atmosphere before the electron beam irradiation step A method for producing the modified yarn as described.

［３］ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸であって搬送されている糸にラジカル重合性モノマーを接触させる接触工程と、
前記接触工程後の搬送糸に電子線を照射する電子線照射工程と、
前記電子線照射後の糸を８０℃以上の温度で加熱することによって前記ラジカル重合性モノマーを糸にグラフト重合させるグラフト重合工程と、を含み、
前記接触工程、前記電子線照射工程および前記グラフト重合工程を不活性雰囲気で連続で実施することを特徴とする改質糸の製造方法。 [3] A contact step of bringing a radical polymerizable monomer into contact with a yarn that is selected from the group consisting of a polyester yarn, a polyamide yarn, and a wool yarn and is being conveyed;
An electron beam irradiation step of irradiating an electron beam to the carrier yarn after the contact step;
A graft polymerization step of graft-polymerizing the radical polymerizable monomer onto the yarn by heating the yarn after the electron beam irradiation at a temperature of 80 ° C. or higher,
A method for producing a modified yarn, wherein the contacting step, the electron beam irradiation step, and the graft polymerization step are continuously performed in an inert atmosphere.

［４］前記接触工程の前に、巻き取り状態の糸の巻き出しと、該巻き出された糸の接触工程への移送を不活性雰囲気で行う給糸工程を有する前項３に記載の改質糸の製造方法。 [4] The modification according to item 3 above, further comprising a yarn feeding step of unwinding the wound yarn and transferring the unwound yarn to the contacting step in an inert atmosphere before the contacting step. Yarn manufacturing method.

［５］前記給糸工程から前記グラフト重合工程までの処理を、内部空間が給糸工程からグラフト重合工程まで連通されると共に該内部空間が不活性雰囲気である密閉可能な容器内で行う前項２または４に記載の改質糸の製造方法。 [5] The item 2 described above, wherein the processing from the yarn supplying step to the graft polymerization step is performed in a sealable container in which the internal space is communicated from the yarn supplying step to the graft polymerization step and the internal space is an inert atmosphere. Or the manufacturing method of the modified yarn of 4.

［６］前記グラフト重合工程において、糸を１００℃を超えて１５０℃以下の温度で加熱する前項１〜５のいずれか１項に記載の改質糸の製造方法。 [6] The method for producing a modified yarn as described in any one of 1 to 5 above, wherein in the graft polymerization step, the yarn is heated to a temperature exceeding 100 ° C and not more than 150 ° C.

［７］前記グラフト重合工程において、加熱槽内で前記糸の巻き取りを行いつつ糸を加熱することによって前記ラジカル重合性モノマーを糸にグラフト重合させる前項１〜６のいずれか１項に記載の改質糸の製造方法。 [7] The graft polymerization step according to any one of items 1 to 6, wherein the radical polymerizable monomer is graft polymerized onto the yarn by heating the yarn while winding the yarn in a heating tank. A method for producing a modified yarn.

［８］前記加熱槽内で糸の巻密度が０．３ｇ／ｃｍ³〜０．７ｇ／ｃｍ³になるように前記糸の巻き取りを行う前項７に記載の改質糸の製造方法。 [8] The method for producing a modified yarn according to item 7 for the yarn winding as the winding density of the yarn is 0.3g / cm ^³ ~0.7g / cm ³ in the heating chamber.

［９］前記電子線照射工程において、糸が電子線照射領域内を移動する合計距離（ｍｍ）を「Ｌ」とし、電子線照射装置の照射能力（ｋＧｙ・ｍ／ｍｉｎ）を「Ｐ」とし、糸搬送速度（ｍ／ｍｉｎ）を「Ｓ」とし、糸搬送方向の照射幅（ｍｍ）を「ｄ」としたとき、
｛Ｐ×（Ｌ／ｄ）｝／Ｓ ≧ ５０（ｋＧｙ）
の関係式が成立することを特徴とする前項１〜８のいずれか１項に記載の改質糸の製造方法。 [9] In the electron beam irradiation step, the total distance (mm) in which the yarn moves in the electron beam irradiation region is “L”, and the irradiation capability (kGy · m / min) of the electron beam irradiation device is “P”. When the yarn conveyance speed (m / min) is “S” and the irradiation width (mm) in the yarn conveyance direction is “d”,
{P × (L / d)} / S ≧ 50 (kGy)
9. The method for producing a modified yarn according to any one of 1 to 8 above, wherein the relational expression:

［１０］前記糸の搬送速度を１００ｍ／分〜１０００ｍ／分に設定することを特徴とする前項１〜９のいずれか１項に記載の改質糸の製造方法。 [10] The method for producing a modified yarn according to any one of items 1 to 9, wherein the yarn conveyance speed is set to 100 m / min to 1000 m / min.

［１１］前記接触工程において、ディップ法、スプレー法又はコーティング法を用いて糸にラジカル重合性モノマーを接触させる前項１〜１０のいずれか１項に記載の改質糸の製造方法。 [11] The method for producing a modified yarn according to any one of items 1 to 10, wherein in the contacting step, the radical polymerizable monomer is brought into contact with the yarn using a dipping method, a spray method, or a coating method.

［１２］前記不活性雰囲気は、酸素濃度が５００ｐｐｍ以下の不活性雰囲気である前項１〜１１のいずれか１項に記載の改質糸の製造方法。 [12] The method for producing a modified yarn according to any one of items 1 to 11, wherein the inert atmosphere is an inert atmosphere having an oxygen concentration of 500 ppm or less.

［１３］前記ラジカル重合性モノマーとして、カルボキシル基、スルホン酸基、アミノ基、パーフルオロアルキル基、シラノール基、リン酸エステル基、グリシジル基、Ｎ−アルキルアミド基からなる群より選ばれる１種または２種以上の官能基を有するラジカル重合性モノマーを少なくとも用いる前項１〜１２のいずれか１項に記載の改質糸の製造方法。 [13] As the radical polymerizable monomer, one selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a perfluoroalkyl group, a silanol group, a phosphate ester group, a glycidyl group, and an N-alkylamide group or 13. The method for producing a modified yarn according to any one of items 1 to 12, wherein at least a radical polymerizable monomer having two or more types of functional groups is used.

［１４］前項１〜１３のいずれか１項に記載の製造方法により得られた改質糸。 [14] A modified yarn obtained by the production method according to any one of items 1 to 13.

［１］の発明では、搬送されている糸に電子線を照射することでラジカルを形成せしめ、該電子線照射後の糸にラジカル重合性モノマーを接触させて加熱することでラジカル重合性モノマーを糸にグラフト重合させることができて、改質糸を製造できる。また、電子線照射工程、接触工程及びグラフト重合工程を不活性雰囲気で実施することで、電子線照射によって生成した活性種（ラジカル）の失活が起こり難くなるので、高いグラフト率の改質糸を製造できる。更に、グラフト重合工程において糸を８０℃以上の温度で加熱するから、従来はラジカルが生成し難くグラフト重合させ難かった糸（ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸）であるにもかかわらず、ラジカルを十分に反応させることができて糸にラジカル重合性モノマーを十分にグラフト重合させることができる。しかして、電子線照射工程、接触工程及びグラフト重合工程を一連の連続工程で実施することで、ポリエステル素材、ポリアミド素材又はウール素材の改質糸を高速で生産することが可能になる。 In the invention of [1], radicals are formed by irradiating the conveyed yarn with an electron beam, and the radically polymerizable monomer is brought into contact with the yarn after being irradiated with the radically polymerizable monomer and heated. The yarn can be graft polymerized to produce a modified yarn. In addition, by performing the electron beam irradiation step, the contact step and the graft polymerization step in an inert atmosphere, the active species (radicals) generated by the electron beam irradiation are less likely to be deactivated. Can be manufactured. Furthermore, since the yarn is heated at a temperature of 80 ° C. or higher in the graft polymerization step, conventionally, it is a yarn (a yarn selected from the group consisting of a polyester yarn, a polyamide yarn and a wool yarn) which is difficult to generate radicals and difficult to graft polymerize. Nevertheless, radicals can be sufficiently reacted and radically polymerizable monomers can be sufficiently grafted onto the yarn. Thus, by performing the electron beam irradiation process, the contact process, and the graft polymerization process in a series of continuous processes, it becomes possible to produce a modified yarn of a polyester material, a polyamide material, or a wool material at high speed.

［２］の発明では、電子線照射工程の前に、巻き取り状態の糸の巻き出しと、該巻き出された糸の電子線照射工程への移送を不活性雰囲気で行う給糸工程を設けているから、電子線照射により生成する活性種（ラジカル）の失活を十分に抑制することができ、より高いグラフト率の改質糸を製造できる。 In the invention of [2], before the electron beam irradiation step, a yarn feeding step for unwinding the wound yarn and transferring the unwound yarn to the electron beam irradiation step is provided in an inert atmosphere. Therefore, deactivation of active species (radicals) generated by electron beam irradiation can be sufficiently suppressed, and a modified yarn having a higher graft rate can be produced.

［３］の発明では、搬送されている糸にラジカル重合性モノマーを接触させ、次いで糸に電子線を照射した後に糸を加熱するので、糸におけるラジカル形成とラジカル重合性モノマーのグラフト重合を同時的に行わせることができて、改質糸を製造できる。また、接触工程、電子線照射工程及びグラフト重合工程を不活性雰囲気で実施することで、電子線照射によって生成した活性種（ラジカル）の失活が起こり難くなるので、高いグラフト率の改質糸を製造できる。更に、グラフト重合工程において糸を８０℃以上の温度で加熱するから、従来はラジカルが生成し難くグラフト重合させ難かった糸（ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸）であるにもかかわらず、ラジカルを十分に反応させることができて糸にラジカル重合性モノマーを十分にグラフト重合させることができる。しかして、電子線照射工程、接触工程及びグラフト重合工程を一連の連続工程で実施することで、ポリエステル素材、ポリアミド素材又はウール素材の改質糸を高速で生産することが可能になる。 In the invention of [3], since the radically polymerizable monomer is brought into contact with the yarn being conveyed, and then the yarn is heated after being irradiated with an electron beam, radical formation in the yarn and graft polymerization of the radically polymerizable monomer are simultaneously performed. The modified yarn can be manufactured. In addition, since the contact process, the electron beam irradiation process and the graft polymerization process are performed in an inert atmosphere, the active species (radicals) generated by the electron beam irradiation are less likely to be deactivated. Can be manufactured. Furthermore, since the yarn is heated at a temperature of 80 ° C. or higher in the graft polymerization step, conventionally, it is a yarn (a yarn selected from the group consisting of a polyester yarn, a polyamide yarn and a wool yarn) which is difficult to generate radicals and difficult to graft polymerize. Nevertheless, radicals can be sufficiently reacted and radically polymerizable monomers can be sufficiently grafted onto the yarn. Thus, by performing the electron beam irradiation process, the contact process, and the graft polymerization process in a series of continuous processes, it becomes possible to produce a modified yarn of a polyester material, a polyamide material, or a wool material at high speed.

［４］の発明では、接触工程の前に、巻き取り状態の糸の巻き出しと、該巻き出された糸の接触工程への移送を不活性雰囲気で行う給糸工程を設けているから、電子線照射により生成する活性種（ラジカル）の失活を十分に抑制することができ、より高いグラフト率の改質糸を製造できる。 In the invention of [4], before the contacting step, there is provided a yarn feeding step for unwinding the wound yarn and transferring the unwound yarn to the contacting step in an inert atmosphere. Deactivation of active species (radicals) generated by electron beam irradiation can be sufficiently suppressed, and a modified yarn having a higher graft rate can be produced.

［５］の発明では、給糸工程からグラフト重合工程までの処理を、内部空間が給糸工程からグラフト重合工程まで連通されると共に該内部空間が不活性雰囲気である密閉可能な容器内で行うから、電子線照射により生成する活性種（ラジカル）の失活をより十分に抑制することができる。 In the invention of [5], the processing from the yarn feeding process to the graft polymerization process is performed in a sealable container in which the internal space is communicated from the yarn feeding process to the graft polymerization process and the internal space is an inert atmosphere. Therefore, deactivation of active species (radicals) generated by electron beam irradiation can be more sufficiently suppressed.

［６］の発明では、グラフト重合工程において、糸を１００℃を超えて１５０℃以下の温度で加熱するから、従来はラジカルが生成し難くグラフト重合させ難かった糸（ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸）であるにもかかわらず、ラジカルをより十分に反応させることができて十分に改質がなされた改質糸を製造することができる。 In the invention of [6], in the graft polymerization step, the yarn is heated at a temperature exceeding 100 ° C. and not more than 150 ° C., and thus, conventionally, a yarn that hardly generates radicals and is difficult to graft polymerize (polyester yarn, polyamide yarn and wool). Despite being a yarn selected from the group consisting of yarns, it is possible to produce a modified yarn that can be sufficiently reacted with radicals and is sufficiently modified.

［７］の発明では、グラフト重合工程において、加熱槽内で糸の巻き取りを行いつつ糸を加熱するので、糸の搬送速度を高速に設定しても（例えば１００ｍ／分以上に設定しても）糸に対して十分な加熱を行うことができてグラフト重合反応を十分に行わせることができる。従って、改質糸をより高速で生産することが可能になる。 In the invention of [7], in the graft polymerization step, the yarn is heated while winding the yarn in a heating tank. Therefore, even if the yarn conveyance speed is set to a high speed (for example, set to 100 m / min or more). Also, the yarn can be sufficiently heated and the graft polymerization reaction can be sufficiently performed. Accordingly, the modified yarn can be produced at a higher speed.

［８］の発明では、加熱槽内で糸の巻密度が０．３ｇ／ｃｍ³〜０．７ｇ／ｃｍ³になるように糸の巻き取りを行うから、加熱された気体が糸の内部まで浸透して内部まで熱が伝わり、ムラなくグラフト重合反応させることができる利点がある。 In the invention [8], since is capable of winding the yarn as the winding density of the yarn is 0.3g / cm ^³ ~0.7g / cm ³ in a heated vessel, heated gas to the inside of the yarn There is an advantage that the heat can be transmitted to the inside through infiltration, and the graft polymerization reaction can be performed without unevenness.

［９］の発明では、電子線照射工程において、｛Ｐ×（Ｌ／ｄ）｝／Ｓ≧５０（ｋＧｙ）の関係式が成立するから、ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸に対し、十分なグラフト重合させるに足る十分な電子線を糸に照射することができ、ポリエステル素材、ポリアミド素材又はウール素材からなる十分に改質がなされた改質糸を製造することができる。 In the invention of [9], since the relational expression {P × (L / d)} / S ≧ 50 (kGy) is satisfied in the electron beam irradiation step, it is selected from the group consisting of polyester yarn, polyamide yarn and wool yarn. The yarn can be irradiated with a sufficient electron beam sufficient for sufficient graft polymerization, and a sufficiently modified yarn made of a polyester material, a polyamide material or a wool material can be produced. it can.

［１０］の発明では、糸の搬送速度を１００ｍ／分〜１０００ｍ／分に設定するから、高速で生産でき、低コストで大量の改質糸を製造することができる。 In the invention [10], since the yarn conveyance speed is set to 100 m / min to 1000 m / min, the yarn can be produced at high speed, and a large amount of modified yarn can be produced at low cost.

［１１］の発明では、ディップ法、スプレー法又はコーティング法を用いて糸にラジカル重合性モノマーを接触させるから、糸に対してモノマーを均一に塗布できる利点がある。 In the invention of [11], since the radically polymerizable monomer is brought into contact with the yarn using a dip method, a spray method or a coating method, there is an advantage that the monomer can be uniformly applied to the yarn.

［１２］の発明では、前記不活性雰囲気は、酸素濃度が５００ｐｐｍ以下の不活性雰囲気であるから、電子線照射によって生成した活性種（ラジカル）の失活がより起こり難くなり、さらに高いグラフト率の改質糸を製造できる。 In the invention of [12], since the inert atmosphere is an inert atmosphere having an oxygen concentration of 500 ppm or less, deactivation of active species (radicals) generated by electron beam irradiation is less likely to occur, and a higher graft ratio Can be produced.

［１３］の発明では、ラジカル重合性モノマーとして、カルボキシル基、スルホン酸基、アミノ基、パーフルオロアルキル基、シラノール基、リン酸エステル基、グリシジル基、Ｎ−アルキルアミド基からなる群より選ばれる１種または２種以上の官能基を有するラジカル重合性モノマーを少なくとも用いるから、吸湿性、撥水性、難燃性、反応性等に富む改質糸を製造できる。 In the invention of [13], the radical polymerizable monomer is selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a perfluoroalkyl group, a silanol group, a phosphate ester group, a glycidyl group, and an N-alkylamide group. Since at least a radically polymerizable monomer having one or more functional groups is used, a modified yarn rich in hygroscopicity, water repellency, flame retardancy, reactivity and the like can be produced.

［１４］の発明では、ポリエステル素材、ポリアミド素材又はウール素材からなる十分に改質がなされた改質糸が提供される。 In the invention of [14], a sufficiently modified yarn made of a polyester material, a polyamide material or a wool material is provided.

本発明の製造方法の一例を示す概略側面図である。It is a schematic side view which shows an example of the manufacturing method of this invention. 電子線照射装置（電子線照射領域）を通過する糸の通過態様を示す上面図である。It is a top view which shows the passage aspect of the thread | yarn which passes an electron beam irradiation apparatus (electron beam irradiation area | region). 電子線照射装置（電子線照射領域）を通過する糸の通過態様の他の例を示す上面図である。It is a top view which shows the other example of the passage aspect of the thread | yarn which passes an electron beam irradiation apparatus (electron beam irradiation area | region). 電子線照射装置（電子線照射領域）を通過する糸の通過態様のさらに他の例を示す上面図である。It is a top view which shows the further another example of the passage aspect of the thread | yarn which passes an electron beam irradiation apparatus (electron beam irradiation area | region). 糸が電子線照射領域内を移動する合計距離Ｌの算出法の説明図（上面図）である。It is explanatory drawing (top view) of the calculation method of the total distance L which a thread | yarn moves within an electron beam irradiation area | region.

第１発明に係る改質糸の製造方法は、ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸であって搬送されている糸に電子線を照射する電子線照射工程と、前記電子線照射後の糸にラジカル重合性モノマーを接触させる接触工程と、前記接触工程後の糸を８０℃以上の温度で加熱することによって前記ラジカル重合性モノマーを糸にグラフト重合させるグラフト重合工程と、を含み、前記電子線照射工程、前記接触工程および前記グラフト重合工程を不活性雰囲気で連続で実施することを特徴とする。 According to a first aspect of the present invention, there is provided a modified yarn manufacturing method comprising: an electron beam irradiation step of irradiating an electron beam to a yarn that is selected from the group consisting of polyester yarn, polyamide yarn, and wool yarn; A contact step in which a radical polymerizable monomer is brought into contact with the yarn after irradiation, and a graft polymerization step in which the radical polymerizable monomer is graft-polymerized on the yarn by heating the yarn after the contact step at a temperature of 80 ° C. or higher; The electron beam irradiation step, the contact step and the graft polymerization step are carried out continuously in an inert atmosphere.

第２発明に係る改質糸の製造方法は、ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸であって搬送されている糸にラジカル重合性モノマーを接触させる接触工程と、前記接触工程後の糸に電子線を照射する電子線照射工程と、前記電子線照射後の糸を８０℃以上の温度で加熱することによって前記ラジカル重合性モノマーを糸にグラフト重合させるグラフト重合工程と、を含み、前記接触工程、前記電子線照射工程および前記グラフト重合工程を不活性雰囲気で連続で実施することを特徴とする。 The method for producing a modified yarn according to the second invention includes a contact step of bringing a radical polymerizable monomer into contact with a yarn that is selected from the group consisting of a polyester yarn, a polyamide yarn, and a wool yarn and is being conveyed; An electron beam irradiation step of irradiating the yarn after the step with an electron beam, and a graft polymerization step of graft-polymerizing the radical polymerizable monomer onto the yarn by heating the yarn after the electron beam irradiation at a temperature of 80 ° C. or higher; And the contact step, the electron beam irradiation step and the graft polymerization step are carried out continuously in an inert atmosphere.

なお、上記第１、第２いずれの発明においても、前工程として、巻き取り状態の糸の巻き出しと、該巻き出された糸１の次工程（第１発明では電子線照射工程、第２発明では接触工程）への移送を不活性雰囲気で行う給糸工程を設けるのが好ましい。 In both the first and second inventions, as a previous step, unwinding of the wound yarn and subsequent steps of the unwound yarn 1 (in the first invention, the electron beam irradiation step, the second step) In the invention, it is preferable to provide a yarn feeding step in which the transfer to the contact step) is performed in an inert atmosphere.

上記第１、第２発明によれば、ラジカル重合性モノマーを搬送されている糸にグラフト重合させることができて、改質糸を製造できる。また、電子線照射工程、接触工程及びグラフト重合工程を不活性雰囲気で実施することで、電子線照射によって生成した活性種（ラジカル）の失活が起こり難くなるので、高いグラフト率の改質糸を製造できる。更に、グラフト重合工程において糸を８０℃以上の温度で加熱するから、従来はラジカルが生成し難くグラフト重合させ難かった糸（ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸）であるにもかかわらず、ラジカルを十分に反応させることができて糸にラジカル重合性モノマーを十分にグラフト重合させることができる。しかして、電子線照射工程、接触工程及びグラフト重合工程を一連の連続工程で実施することで、ポリエステル素材、ポリアミド素材又はウール素材の改質糸を高速で生産することが可能になる。 According to the first and second inventions described above, the radically polymerizable monomer can be graft polymerized to the yarn being conveyed, and a modified yarn can be produced. In addition, by performing the electron beam irradiation step, the contact step and the graft polymerization step in an inert atmosphere, the active species (radicals) generated by the electron beam irradiation are less likely to be deactivated. Can be manufactured. Furthermore, since the yarn is heated at a temperature of 80 ° C. or higher in the graft polymerization step, conventionally, it is a yarn (a yarn selected from the group consisting of a polyester yarn, a polyamide yarn and a wool yarn) which is difficult to generate radicals and difficult to graft polymerize. Nevertheless, radicals can be sufficiently reacted and radically polymerizable monomers can be sufficiently grafted onto the yarn. Thus, by performing the electron beam irradiation process, the contact process, and the graft polymerization process in a series of continuous processes, it becomes possible to produce a modified yarn of a polyester material, a polyamide material, or a wool material at high speed.

なお、表１に、糸素材として使用し得る各ポリマーのラジカルのＧ値を示す。「ラジカルのＧ値」とは、電子線のエネルギー吸収線量１００ｅＶ当たりの生成ラジカル数を意味するものであり、この数値が大きい程、電子線照射でより多くのラジカルを発生することができる。表１から明らかなように、ポリエステル素材、ポリアミド素材及びウール素材は、ラジカルのＧ値が他の素材よりも格段に小さく、電子線が照射されてもラジカルを非常に生成し難いことがわかる。 Table 1 shows the radical G value of each polymer that can be used as a yarn material. The “radical G value” means the number of radicals generated per 100 eV of the energy absorption dose of an electron beam, and the larger this value, the more radicals can be generated by electron beam irradiation. As is apparent from Table 1, the polyester material, the polyamide material, and the wool material have a radical G value that is much smaller than other materials, and it is very difficult to generate radicals even when irradiated with an electron beam.

第１発明の製造方法の一実施形態を図１に示す。本実施形態では、前記給糸工程から前記グラフト重合工程までの処理を、内部空間が給糸工程からグラフト重合工程まで連通されると共に該内部空間が窒素雰囲気である密閉可能な容器４０内で行う。 One embodiment of the manufacturing method of the first invention is shown in FIG. In the present embodiment, the processing from the yarn feeding step to the graft polymerization step is performed in a sealable container 40 in which the internal space is communicated from the yarn feeding step to the graft polymerization step and the internal space is a nitrogen atmosphere. .

前記容器４０は、給糸部４０Ａと、電子線照射部４０Ｂと、接触・重合部４０Ｃと、給糸部４０Ａと電子線照射部４０Ｂを連通する第１連通部４０Ｘと、電子線照射部４０Ｂと接触・重合部４０Ｃを連通する第２連通部４０Ｙと、を備えている（図１参照）。 The container 40 includes a yarn feeding unit 40A, an electron beam irradiation unit 40B, a contact / polymerization unit 40C, a first communication unit 40X that communicates the yarn feeding unit 40A and the electron beam irradiation unit 40B, and an electron beam irradiation unit 40B. And a second communicating portion 40Y that communicates with the contact / overlap portion 40C (see FIG. 1).

前記給糸部４０Ａ内に糸が巻き取られてなる糸ロールが配置され、該給糸部４０Ａ内で糸１の巻き出しと、該巻き出された糸１の電子線照射工程への移送が行われ、前記第１連通部４０Ｘを介して糸１が電子線照射部４０Ｂ内へ搬送される。この電子線照射部４０Ｂ内で、搬送されている（搬送移動中の）糸１に対して電子線照射装置２から電子線が照射される。電子線照射後の糸１Ａは、前記第２連通部４０Ｙを介して接触・重合部４０Ｃ内へ搬送される。接触・重合部４０Ｃ内には、ラジカル重合性モノマー液４を収容した接触処理槽３が上流側に配置されると共に下流側に加熱槽５が配置されている。しかして、電子線照射後の糸１Ａは、接触処理槽３内のラジカル重合性モノマー液４に浸漬され、浸漬後の糸（接触工程後の糸）１Ｂは、加熱槽５内に搬送され、該加熱槽５内で糸は巻き取られつつ８０℃以上の温度で加熱され、このような加熱によりラジカル重合性モノマーを糸にグラフト重合させて改質糸を得る。 A yarn roll formed by winding a yarn is disposed in the yarn supplying unit 40A, and unwinding of the yarn 1 in the yarn supplying unit 40A and transfer of the unwound yarn 1 to the electron beam irradiation step are performed. The yarn 1 is conveyed into the electron beam irradiation unit 40B through the first communication unit 40X. In the electron beam irradiation unit 40B, the electron beam irradiation device 2 irradiates the yarn 1 being conveyed (moving and moving) with the electron beam. The yarn 1A after the electron beam irradiation is conveyed into the contact / polymerization unit 40C through the second communication unit 40Y. In the contact / polymerization section 40C, the contact treatment tank 3 containing the radical polymerizable monomer liquid 4 is disposed on the upstream side, and the heating tank 5 is disposed on the downstream side. Thus, the yarn 1A after the electron beam irradiation is immersed in the radical polymerizable monomer solution 4 in the contact treatment tank 3, and the yarn (B after the contact process) 1B after the immersion is conveyed into the heating tank 5, The yarn is heated in the heating tank 5 at a temperature of 80 ° C. or higher while being wound, and the radical polymerizable monomer is graft-polymerized on the yarn by such heating to obtain a modified yarn.

本発明において、改質対象の糸としては、ポリエステル糸、ポリアミド糸またはウール糸を使用する。 In the present invention, polyester yarn, polyamide yarn or wool yarn is used as the yarn to be modified.

前記糸の種類としては、特に限定されるものではないが、例えば、モノフィラメント糸、マルチフィラメント糸、紡績糸、前記素材の混紡糸、前記素材の混合素材糸等が挙げられる。 The type of the yarn is not particularly limited, and examples thereof include monofilament yarn, multifilament yarn, spun yarn, blended yarn of the material, and mixed material yarn of the material.

（電子線照射工程）
電子線の照射量は、照射対象の糸の性能や照射による糸物性の低下を考慮して適宜決めればよいが、１０ｋＧｙ〜３００ｋＧｙの範囲に設定するのが好ましい。照射量が１０ｋＧｙ以上であることでグラフト重合に必要な量の活性種が得られると共に、３００ｋＧｙ以下であることで糸を構成する繊維の主鎖の切断を防止できて糸物性の低下を防止できる。電子線照射は不活性雰囲気で行う。前記不活性雰囲気とは、電子線照射によって生成した活性種が失活したり、揮散しないような状況下をいう。前記不活性雰囲気の具体例としては、フィルムで密閉したり容器に入れ可能な限り空気を抜いて酸素濃度を低くした状態の他、窒素雰囲気などが挙げられる。 (Electron beam irradiation process)
The irradiation amount of the electron beam may be appropriately determined in consideration of the performance of the yarn to be irradiated and the deterioration of the yarn physical property due to the irradiation, but is preferably set in the range of 10 kGy to 300 kGy. When the irradiation amount is 10 kGy or more, an amount of active species necessary for graft polymerization can be obtained, and when the irradiation amount is 300 kGy or less, the main chain of the fibers constituting the yarn can be prevented from being broken and the deterioration of the yarn physical properties can be prevented. . Electron beam irradiation is performed in an inert atmosphere. The inert atmosphere refers to a situation where active species generated by electron beam irradiation are not deactivated or volatilized. Specific examples of the inert atmosphere include a nitrogen atmosphere in addition to a state in which the oxygen concentration is lowered by removing air as much as possible by sealing with a film or putting in a container.

この電子線照射工程では、例えば、改質対象の糸を電子線照射領域２０で複数回以上往復移動させて該糸に電子線を照射する。図１、２に示すように、電子線照射装置２による電子線照射領域２０に配置された複数個の糸反転用ローラ１９に糸１を誘導しつつ各糸反転用ローラ１９で糸の移送方向を順次反転させることによって改質対象の糸１を電子線照射領域２０で複数回以上往復移動させ、こうして電子線が照射された糸１Ａを得る。なお、改質対象の糸を電子線照射領域２０で複数回以上往復移動させる形態は、図２に例示したものに特に限定されるものではない。 In this electron beam irradiation step, for example, the yarn to be modified is reciprocated a plurality of times in the electron beam irradiation region 20 to irradiate the yarn with the electron beam. As shown in FIGS. 1 and 2, the yarn transfer direction of each yarn reversing roller 19 while guiding the yarn 1 to a plurality of yarn reversing rollers 19 arranged in the electron beam irradiation region 20 by the electron beam irradiation device 2. Are sequentially reversed so that the yarn 1 to be modified is reciprocated a plurality of times in the electron beam irradiation region 20, thereby obtaining the yarn 1A irradiated with the electron beam. The form in which the yarn to be modified is reciprocated a plurality of times in the electron beam irradiation region 20 is not particularly limited to that illustrated in FIG.

電子線照射領域２０における糸の搬送態様としては、図３、４に示す搬送態様を採用してもよい。図３では、電子線照射領域２０において、糸をロールの外周面に複数回巻き付けつつ搬送しており、これにより糸に対し照射する電子線量を顕著に増大させることができ、こうして十分に電子線が照射された糸１Ａを得ることができる。また、図４では、電子線照射領域２０において、複数個の糸反転用ローラ２１を介して糸を複数回略反転させて搬送しており、これにより糸に対し照射する電子線量を顕著に増大させることができ、こうして十分に電子線が照射された糸１Ａを得ることができる。 As the conveyance mode of the yarn in the electron beam irradiation region 20, the conveyance mode shown in FIGS. In FIG. 3, in the electron beam irradiation region 20, the yarn is conveyed while being wound around the outer peripheral surface of the roll a plurality of times, whereby the electron dose irradiated to the yarn can be remarkably increased, and thus the electron beam is sufficiently produced. Can be obtained. Also, in FIG. 4, in the electron beam irradiation region 20, the yarn is conveyed by being substantially reversed a plurality of times via a plurality of yarn reversing rollers 21, thereby significantly increasing the electron dose irradiated to the yarn. Thus, the yarn 1A sufficiently irradiated with the electron beam can be obtained.

電子線照射工程において、糸１が電子線照射領域内を移動する合計距離（ｍｍ）を「Ｌ」とし、電子線照射装置の照射能力（ｋＧｙ・ｍ／ｍｉｎ）を「Ｐ」とし、糸搬送速度（ｍ／ｍｉｎ）を「Ｓ」とし、糸搬送方向の照射幅（ｍｍ）を「ｄ」としたとき（図５参照）、
｛Ｐ×（Ｌ／ｄ）｝／Ｓ ≧ ５０（ｋＧｙ）
の関係式が成立するのが好ましく、この場合には糸（ポリエステル糸、ポリアミド糸及びウール糸からなる群より選ばれる糸）に対し、十分なグラフト重合させるに足る十分な電子線を糸に照射することができ、十分に改質がなされた改質糸を製造できる。 In the electron beam irradiation process, the total distance (mm) that the yarn 1 moves in the electron beam irradiation region is set to “L”, the irradiation capacity (kGy · m / min) of the electron beam irradiation device is set to “P”, and the yarn is conveyed. When the speed (m / min) is “S” and the irradiation width (mm) in the yarn conveyance direction is “d” (see FIG. 5),
{P × (L / d)} / S ≧ 50 (kGy)
In this case, the yarn is irradiated with a sufficient electron beam to sufficiently graft polymerize the yarn (yarn selected from the group consisting of polyester yarn, polyamide yarn and wool yarn). It is possible to produce a modified yarn that has been sufficiently modified.

なお、糸１が電子線照射領域内を移動する合計距離Ｌは、図５において太線で示す糸の照射部分（電子線が照射される部分）の長さの総和である。 Note that the total distance L in which the yarn 1 moves within the electron beam irradiation region is the sum of the lengths of the yarn irradiation portions (portions irradiated with the electron beams) indicated by thick lines in FIG.

（接触工程）
接触工程では、糸にラジカル重合性モノマーを接触させる。糸にラジカル重合性モノマーを接触させる方法としては、ラジカル重合性モノマーを水、低級アルコール等の溶媒に希釈した溶液に糸を浸漬するディップ法、前記希釈溶液をローラー等で糸に塗布するコーティング法、前記希釈溶液を糸にスプレー塗布するスプレー法などが挙げられる。前記希釈溶液におけるラジカル重合性モノマーの濃度は、設定するグラフト率により適宜設定すればよいが、通常、１〜７０容量％とするのがよい。前記ラジカル重合性モノマーの糸への付与量（付着量）は、糸１００質量部に対し０．５〜５０質量部に設定するのが好ましい。 (Contact process)
In the contacting step, a radical polymerizable monomer is brought into contact with the yarn. As a method of bringing the radical polymerizable monomer into contact with the yarn, a dipping method in which the yarn is immersed in a solution obtained by diluting the radical polymerizable monomer in a solvent such as water or lower alcohol, and a coating method in which the diluted solution is applied to the yarn with a roller or the like And a spray method in which the diluted solution is spray-coated on the yarn. The concentration of the radically polymerizable monomer in the diluted solution may be appropriately set depending on the graft ratio to be set, but it is usually preferably 1 to 70% by volume. The amount (attachment amount) of the radical polymerizable monomer to the yarn is preferably set to 0.5 to 50 parts by mass with respect to 100 parts by mass of the yarn.

前記ラジカル重合性モノマーとしては、ラジカル重合可能なモノマーであれば特に限定されない。前記ラジカル重合性モノマーとしては、カルボキシル基、スルホン酸基、アミノ基、パーフルオロアルキル基、シラノール基、リン酸エステル基、グリシジル基、Ｎ−アルキルアミド基からなる群より選ばれる１種または２種以上の官能基を有するラジカル重合性モノマーを少なくとも用いるのが好ましい。前記ラジカル重合性モノマーは、１種を単独で用いてもよいし、２種以上を混合して用いてもよい。前記ラジカル重合性モノマーを選択することにより、吸水性、制電性、防汚性、抗菌性、難燃性、吸湿性等の様々な性能を糸に付与して改質することができる。 The radical polymerizable monomer is not particularly limited as long as it is a monomer capable of radical polymerization. The radical polymerizable monomer is one or two selected from the group consisting of carboxyl group, sulfonic acid group, amino group, perfluoroalkyl group, silanol group, phosphate ester group, glycidyl group and N-alkylamide group. It is preferable to use at least a radical polymerizable monomer having the above functional group. The radical polymerizable monomer may be used alone or in combination of two or more. By selecting the radically polymerizable monomer, various properties such as water absorption, antistatic property, antifouling property, antibacterial property, flame retardancy, and hygroscopic property can be imparted to the yarn for modification.

糸に難燃性を付与する場合には、リン酸系ラジカル重合性モノマー（リン酸基及びラジカル重合性基を含有するモノマー）を少なくとも用いるのが好ましい。中でも、下記一般式（１）で表されるビニルホスフェート化合物を用いるのが特に好ましい。 When imparting flame retardancy to the yarn, it is preferable to use at least a phosphoric acid radical polymerizable monomer (a monomer containing a phosphate group and a radical polymerizable group). Among these, it is particularly preferable to use a vinyl phosphate compound represented by the following general formula (1).

（式中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立して水素原子またはメチル基を表し、ｎは１〜３の整数を表し、ｍは１〜６の整数を表す）。 (Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 3, and m represents an integer of 1 to 6).

中でも、一般式（１）におけるＲ¹がメチル基であり、Ｒ²が水素原子であるビニルホスフェート化合物を用いるのが好ましい。また、Ｒ³は水素原子であるのが好ましい。また、水溶液として難燃加工を行う場合には、ｎは１または２であるのが好ましい。 Among them, it is preferable to use a vinyl phosphate compound in which R ¹ in the general formula (1) is a methyl group and R ² is a hydrogen atom. R ³ is preferably a hydrogen atom. Moreover, when performing a flame-retardant process as aqueous solution, it is preferable that n is 1 or 2.

一般式（１）で表されるビニルホスフェート化合物としては、例えば、モノ（２−アクリロイルオキシエチル）ホスフェート、モノ（２−メタクリロイルオキシエチル）ホスフェート、ビス（２−アクリロイルオキシエチル）ホスフェート、ビス（２−メタクリロイルオキシエチル）ホスフェート、ジエチル−（２−アクリロイルオキシエチル）ホスフェート、ジエチル−（２−メタクリロイルオキシエチル）ホスフェート、ジフェニル−（２−アクリロイルオキシエチル）ホスフェート、ジフェニル−（２−メタクリロイルオキシエチル）ホスフェート、ポリアルキレングリコール−（２−アクリロイルオキシエチル）ホスフェート、ポリアルキレングリコール−（２−メタクリロイルオキシエチル）ホスフェート等が挙げられる。 Examples of the vinyl phosphate compound represented by the general formula (1) include mono (2-acryloyloxyethyl) phosphate, mono (2-methacryloyloxyethyl) phosphate, bis (2-acryloyloxyethyl) phosphate, and bis (2 -Methacryloyloxyethyl) phosphate, diethyl- (2-acryloyloxyethyl) phosphate, diethyl- (2-methacryloyloxyethyl) phosphate, diphenyl- (2-acryloyloxyethyl) phosphate, diphenyl- (2-methacryloyloxyethyl) phosphate , Polyalkylene glycol- (2-acryloyloxyethyl) phosphate, polyalkylene glycol- (2-methacryloyloxyethyl) phosphate, and the like.

（グラフト重合工程）
グラフト重合工程では、糸を加熱することによってラジカル重合性モノマーを糸にグラフト重合させる。前記加熱温度は８０℃〜１５０℃に設定するのが好ましい。８０℃以上とすることで重合速度が大きくなり十分なグラフト率を得ることができると共に、１５０℃以下とすることでグラフト鎖同士の結合により重合の停止反応が起こることを抑制することができる。中でも、グラフト重合工程では糸を１００℃を超えて１５０℃以下の温度で加熱するのが特に好ましい。 (Graft polymerization process)
In the graft polymerization step, the radically polymerizable monomer is graft polymerized onto the yarn by heating the yarn. The heating temperature is preferably set to 80 ° C to 150 ° C. By setting it to 80 degreeC or more, while superposing | polymerizing speed becomes large and it can obtain sufficient graft ratio, it can suppress that the termination reaction of superposition | polymerization occurs by the coupling | bonding of graft chains by setting it as 150 degreeC or less. Among them, in the graft polymerization step, it is particularly preferable to heat the yarn at a temperature exceeding 100 ° C. and not more than 150 ° C.

グラフト重合工程において、加熱槽５内で前記糸の巻き取りを行いつつ糸を加熱することによってラジカル重合性モノマー４を糸にグラフト重合させるのが好ましい。この時、糸の巻き取りの巻密度は０．３ｇ／ｃｍ³〜０．７ｇ／ｃｍ³の範囲に設定するのが好ましい。 In the graft polymerization step, the radical polymerizable monomer 4 is preferably graft polymerized onto the yarn by heating the yarn while winding the yarn in the heating tank 5. At this time, the winding density of the winding of the yarn is preferably set in the range of ^{^{0.3g / cm 3 ~0.7g / cm 3}} .

本発明において、各工程での不活性雰囲気としては、酸素濃度が５００ｐｐｍ以下の不活性雰囲気を採用するのが好ましい。 In the present invention, it is preferable to employ an inert atmosphere having an oxygen concentration of 500 ppm or less as the inert atmosphere in each step.

次に、本発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

＜実施例１＞
図１に示すように、容器４０の給糸部４０Ａ内で４００デシテックスのＰＥＴ（ポリエチレンテレフタレート）製マルチフィラメント糸（原糸）１の糸ロール（糸の巻き取り状態）から糸１の巻き出しを行って１２６ｍ／分の速度で搬送し（給糸工程）、次いでこの糸１を電子線照射装置２の電子線照射領域２０内で３往復移動させることによって（図２参照）、糸１に１００ｋＧｙの電子線を照射した（電子線照射工程）。電子線照射装置２の最大処理能力は１８００ｋＧｙ・ｍ／分である。次いで前記電子線照射後の糸１Ａを接触処理槽３内のラジカル重合性モノマー液（５０質量％のアクリル酸水溶液）４に浸漬通過させる（ディップ法でモノマー液を接触させる）ことによって、糸１Ａにラジカル重合性モノマー４を接触させて表面に付着せしめた（接触工程）。次いで、前記接触工程後の糸１Ｂを加熱槽５内に搬送し該加熱槽５内において１２０℃で加熱を行いつつ、巻密度０．４ｇ／ｃｍ³で糸の巻き取り（ソフトアップ）を行うことによってラジカル重合性モノマーを糸にグラフト重合させた（グラフト重合工程）。 <Example 1>
As shown in FIG. 1, the yarn 1 is unwound from a yarn roll (yarn winding state) of 400 dtex multifilament yarn (raw yarn) 1 in a yarn feeding section 40A of the container 40. The yarn 1 is conveyed at a speed of 126 m / min (yarn feeding step), and then the yarn 1 is moved 3 times in the electron beam irradiation area 20 of the electron beam irradiation device 2 (see FIG. 2), whereby 100 kGy is applied to the yarn 1. The electron beam was irradiated (electron beam irradiation process). The maximum processing capacity of the electron beam irradiation apparatus 2 is 1800 kGy · m / min. Next, the yarn 1A after the electron beam irradiation is passed through a radically polymerizable monomer solution (50% by mass of acrylic acid aqueous solution) 4 in the contact treatment tank 3 (the monomer solution is brought into contact by a dipping method), whereby the yarn 1A The radical polymerizable monomer 4 was brought into contact with and adhered to the surface (contact process). Next, the yarn 1B after the contacting step is conveyed into the heating tank 5 and heated (120 ° C.) in the heating tank 5 while being wound (soft-up) at a winding density of 0.4 g / cm ^3. As a result, the radically polymerizable monomer was graft polymerized onto the yarn (graft polymerization step).

なお、前記給糸工程から前記電子線照射工程、前記接触工程を経て前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）４０内で窒素雰囲気（酸素濃度は４００ｐｐｍ）で連続工程で実施した。即ち、前記給糸工程、前記電子線照射工程、前記接触工程および前記グラフト重合工程は、いずれも不活性雰囲気で実施した。 In addition, a nitrogen atmosphere (oxygen concentration is 400 ppm) in a 50 m ³ sealable container (stainless steel container) 40 in which the processes from the yarn feeding process to the electron beam irradiation process, the contact process, and the graft polymerization process are continued. ) In a continuous process. That is, the yarn feeding step, the electron beam irradiation step, the contact step, and the graft polymerization step were all performed in an inert atmosphere.

次に、前記グラフト重合工程を経て得られた、糸を巻き取ってなるチーズに対してチーズ染色機を用いて１００℃の熱水で洗浄を行った後、１２０℃で１２時間乾燥を行うことによって、改質糸を得た。 Next, after washing with 100 ° C. hot water using a cheese dyeing machine for the cheese obtained by winding the yarn obtained through the graft polymerization step, drying is performed at 120 ° C. for 12 hours. As a result, a modified yarn was obtained.

＜実施例２＞
４００デシテックスのＰＥＴ製マルチフィラメント糸に代えて、５２／２番手のウール糸を用いた以外は、実施例１と同様にして改質糸を得た。 <Example 2>
A modified yarn was obtained in the same manner as in Example 1 except that a 52 / 2st wool yarn was used instead of the 400 dtex multifilament yarn made of PET.

＜実施例３＞
４００デシテックスのＰＥＴ製マルチフィラメント糸に代えて、３００デシテックスのナイロン製マルチフィラメント糸を用いた以外は、実施例１と同様にして改質糸を得た。 <Example 3>
A modified yarn was obtained in the same manner as in Example 1 except that 300 dtex multifilament yarn made of nylon was used instead of 400 dtex multifilament yarn made of PET.

＜実施例４＞
給糸工程の雰囲気を、窒素雰囲気（酸素濃度は４００ｐｐｍ）に代えて、空気雰囲気とした以外は、実施例１と同様にして改質糸を得た。 <Example 4>
A modified yarn was obtained in the same manner as in Example 1 except that the atmosphere in the yarn supplying step was changed to an air atmosphere instead of a nitrogen atmosphere (oxygen concentration was 400 ppm).

＜実施例５＞
容器４０の給糸部４０Ａ内で４００デシテックスのＰＥＴ（ポリエチレンテレフタレート）製マルチフィラメント糸（原糸）１の糸ロール（糸の巻き取り状態）から糸１の巻き出しを行って１２６ｍ／分の速度で搬送し（給糸工程）、次いでこの糸を接触処理槽内のラジカル重合性モノマー液（５０質量％のアクリル酸水溶液）に浸漬通過させる（ディップ法でモノマー液を接触させる）ことによって、糸にラジカル重合性モノマーを接触させて表面に付着せしめた（接触工程）。次いで前記接触工程後の糸を電子線照射装置２の電子線照射領域内で３往復移動させることによって、糸に１００ｋＧｙの電子線を照射した（電子線照射工程）。電子線照射装置２の最大処理能力は１８００ｋＧｙ・ｍ／分である。前記電子線照射後の糸を加熱槽内に搬送し該加熱槽内において１２０℃で加熱を行いつつ、巻密度０．４ｇ／ｃｍ³で糸の巻き取り（ソフトアップ）を行うことによってラジカル重合性モノマーを糸にグラフト重合させた（グラフト重合工程）。 <Example 5>
The yarn 1 is unwound from a yarn roll (winding state) of a 400-dtex multifilament yarn (raw yarn) 1 made of PET (polyethylene terephthalate) in the yarn feeding section 40A of the container 40, and a speed of 126 m / min. (Yarn feeding step), and then the yarn is immersed in a radically polymerizable monomer solution (50% by mass acrylic acid aqueous solution) in the contact treatment tank (the monomer solution is brought into contact with the dip method). The radically polymerizable monomer was brought into contact with and adhered to the surface (contact process). Next, the yarn after the contact step was reciprocated three times in the electron beam irradiation region of the electron beam irradiation device 2 to irradiate the yarn with an electron beam of 100 kGy (electron beam irradiation step). The maximum processing capacity of the electron beam irradiation apparatus 2 is 1800 kGy · m / min. Radical polymerization by conveying the yarn after irradiation with the electron beam into a heating tank and winding the yarn at a winding density of 0.4 g / cm ³ (soft-up) while heating at 120 ° C. in the heating tank. The graft monomer was graft polymerized onto the yarn (graft polymerization step).

なお、前記給糸工程から前記接触工程、前記電子線照射工程を経て前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）内で窒素雰囲気（酸素濃度は４００ｐｐｍ）で連続工程で実施した。即ち、前記給糸工程、前記接触工程、前記電子線照射工程及び前記グラフト重合工程は、いずれも不活性雰囲気で実施した。 In addition, nitrogen atmosphere (oxygen concentration is 400 ppm) in a 50 m ³ hermetically sealable container (stainless steel container) from the yarn feeding process to the contact process, the electron beam irradiation process and the graft polymerization process. In a continuous process. That is, the yarn feeding step, the contact step, the electron beam irradiation step, and the graft polymerization step were all performed in an inert atmosphere.

＜実施例６＞
給糸工程の雰囲気を、窒素雰囲気（酸素濃度は４００ｐｐｍ）に代えて、空気雰囲気とした以外は、実施例５と同様にして改質糸を得た。 <Example 6>
A modified yarn was obtained in the same manner as in Example 5 except that the atmosphere in the yarn supplying step was changed to an air atmosphere instead of a nitrogen atmosphere (oxygen concentration was 400 ppm).

＜実施例７＞
糸１への電子線照射線量を４０ｋＧｙに設定した以外は、実施例１と同様にして改質糸を得た。 <Example 7>
A modified yarn was obtained in the same manner as in Example 1, except that the electron beam irradiation dose to the yarn 1 was set to 40 kGy.

＜実施例８＞
糸の搬送速度を１８ｍ／分に設定すると共に、電子線照射工程において糸１を電子線照射装置２の電子線照射領域２０内で往復させることなく単に１回通過させることによって、糸１に１００ｋＧｙの電子線を照射した以外は、実施例１と同様にして改質糸を得た。 <Example 8>
The yarn conveyance speed is set to 18 m / min, and the yarn 1 is passed through the electron beam irradiation region 20 of the electron beam irradiation device 2 in the electron beam irradiation process without being reciprocated once, thereby allowing the yarn 1 to pass 100 kGy. A modified yarn was obtained in the same manner as in Example 1 except that the electron beam was irradiated.

＜実施例９＞
糸に対するラジカル重合性モノマー液（５０質量％のアクリル酸水溶液）の接触を、ディップ法に代えて、ローラーでモノマー液を糸に塗布するコーティング法で行った以外は、実施例１と同様にして改質糸を得た。 <Example 9>
Except that the contact of the radically polymerizable monomer solution (50% by mass of acrylic acid aqueous solution) with the yarn was performed by a coating method in which the monomer solution was applied to the yarn with a roller instead of the dipping method, the same as in Example 1. A modified yarn was obtained.

＜実施例１０＞
糸に対するラジカル重合性モノマー液（５０質量％のアクリル酸水溶液）の接触を、ディップ法に代えて、モノマー液を糸にスプレー状に塗布するスプレー法で行った以外は、実施例１と同様にして改質糸を得た。 <Example 10>
Similar to Example 1, except that the contact of the radically polymerizable monomer liquid (50% by mass of acrylic acid aqueous solution) with the yarn was carried out by a spray method in which the monomer liquid was applied to the yarn in a spray form instead of the dipping method. Modified yarn was obtained.

＜実施例１１＞
グラフト重合工程における糸の巻き取りの巻密度を０．８ｇ／ｃｍ³に設定した以外は、実施例１と同様にして改質糸を得た。 <Example 11>
A modified yarn was obtained in the same manner as in Example 1 except that the winding density for winding the yarn in the graft polymerization step was set to 0.8 g / cm ³ .

＜実施例１２＞
グラフト重合工程における糸の加熱温度を８０℃に設定した以外は、実施例１と同様にして改質糸を得た。 <Example 12>
A modified yarn was obtained in the same manner as in Example 1 except that the heating temperature of the yarn in the graft polymerization step was set to 80 ° C.

＜実施例１３＞
前記給糸工程から前記電子線照射工程、前記接触工程を経て前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）４０内で酸素濃度１５００ｐｐｍの窒素雰囲気で実施した以外は、実施例１と同様にして改質糸を得た。 <Example 13>
The processing from the yarn feeding process to the electron beam irradiation process, the contact process, and the graft polymerization process was carried out in a continuous 50 m ³ sealable container (stainless steel container) 40 in a nitrogen atmosphere with an oxygen concentration of 1500 ppm. Except for the above, a modified yarn was obtained in the same manner as in Example 1.

＜実施例１４＞
糸の搬送速度を９１８ｍ／分に設定すると共に、電子線照射工程において糸１を電子線照射装置２の電子線照射領域２０内で２５往復移動させた以外は、実施例１と同様にして改質糸を得た。なお、糸１への電子線照射量は１００ｋＧｙであった。 <Example 14>
The yarn conveyance speed was set to 918 m / min, and the yarn 1 was reciprocated 25 times within the electron beam irradiation region 20 of the electron beam irradiation device 2 in the electron beam irradiation step. A textured yarn was obtained. In addition, the electron beam irradiation amount to the thread | yarn 1 was 100 kGy.

＜比較例１＞
前記給糸工程から前記電子線照射工程、前記接触工程を経て前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）４０内で空気雰囲気（酸素濃度２００００ｐｐｍ）で実施した以外は、実施例１と同様にして改質糸を得た。 <Comparative Example 1>
The process from the yarn feeding process to the electron beam irradiation process, the contact process, and the graft polymerization process is performed in an air atmosphere (oxygen concentration 20000 ppm) in a 50 m ³ sealable container (stainless steel container) 40. A modified yarn was obtained in the same manner as in Example 1 except that.

＜比較例２＞
４００デシテックスのＰＥＴ（ポリエチレンテレフタレート）製マルチフィラメント糸（原糸）１の糸ロール（チーズ状態）に対し、窒素雰囲気（酸素濃度は４００ｐｐｍ）下で１００ｋＧｙの電子線を照射した（電子線照射工程）。次いで、電子線照射後の糸ロールから糸の巻き出しを行って１２６ｍ／分の速度で搬送し（給糸工程）、糸を接触処理槽３内のラジカル重合性モノマー液（５０質量％のアクリル酸水溶液）４に浸漬通過させる（ディップ法でモノマー液を接触させる）ことによって、糸にラジカル重合性モノマー４を接触させて表面に付着せしめた（接触工程）。次いで、前記接触工程後の糸を加熱槽５内に搬送し該加熱槽５内において１２０℃で加熱を行いつつ、巻密度０．４ｇ／ｃｍ³で糸の巻き取り（ソフトアップ）を行うことによってラジカル重合性モノマーを糸にグラフト重合させた（グラフト重合工程）。 <Comparative Example 2>
A 400 dcitex PET (polyethylene terephthalate) multifilament yarn (raw yarn) 1 yarn roll (cheese state) was irradiated with a 100 kGy electron beam in a nitrogen atmosphere (oxygen concentration 400 ppm) (electron beam irradiation step). . Next, the yarn is unwound from the yarn roll after electron beam irradiation and conveyed at a speed of 126 m / min (yarn feeding step), and the yarn is radically polymerizable monomer liquid (50% by mass of acrylic in the contact treatment tank 3). The aqueous solution (acid solution) 4 was immersed and passed (the monomer solution was brought into contact with the dip method) to bring the radical polymerizable monomer 4 into contact with the yarn and attached to the surface (contact process). Next, the yarn after the contacting step is conveyed into the heating tank 5 and wound (soft-up) at a winding density of 0.4 g / cm ³ while heating at 120 ° C. in the heating tank 5. The radical polymerizable monomer was graft polymerized onto the yarn by the above (graft polymerization step).

なお、前記電子線照射工程、給糸工程、前記接触工程、前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）内で窒素雰囲気（酸素濃度は４００ｐｐｍ）で実施した。即ち、前記給糸工程、前記電子線照射工程、前記接触工程および前記グラフト重合工程は、いずれも不活性雰囲気で実施した。 The electron beam irradiation process, the yarn feeding process, the contact process, and the graft polymerization process were performed in a continuous 50 m ³ sealable container (stainless steel container) in a nitrogen atmosphere (oxygen concentration 400 ppm). did. That is, the yarn feeding step, the electron beam irradiation step, the contact step, and the graft polymerization step were all performed in an inert atmosphere.

＜比較例３＞
グラフト重合工程における糸の加熱温度を５０℃に設定した以外は、実施例１と同様にして改質糸を得た。 <Comparative Example 3>
A modified yarn was obtained in the same manner as in Example 1 except that the heating temperature of the yarn in the graft polymerization step was set to 50 ° C.

＜比較例４＞
前記給糸工程から前記電子線照射工程、前記接触工程を経て前記グラフト重合工程までの処理を連続した５０ｍ³の密閉可能な容器（ステンレス製容器）４０内で空気雰囲気（酸素濃度２００００ｐｐｍ）で実施した以外は、実施例５と同様にして改質糸を得た。 <Comparative Example 4>
The process from the yarn feeding process to the electron beam irradiation process, the contact process, and the graft polymerization process is performed in an air atmosphere (oxygen concentration 20000 ppm) in a 50 m ³ sealable container (stainless steel container) 40. A modified yarn was obtained in the same manner as in Example 5 except that.

＜比較例５＞
グラフト重合工程における糸の加熱温度を５０℃に設定した以外は、実施例５と同様にして改質糸を得た。 <Comparative Example 5>
A modified yarn was obtained in the same manner as in Example 5 except that the heating temperature of the yarn in the graft polymerization step was set to 50 ° C.

上記のようにして得られた改質糸のグラフト率を下記評価法に基づいて評価した。その結果を表２、３に示す。 The graft ratio of the modified yarn obtained as described above was evaluated based on the following evaluation method. The results are shown in Tables 2 and 3.

＜グラフト率評価法＞
前記洗浄、乾燥を行った後のチーズ状態の改質糸における内層部５１、中層部５２、外層部５３（図１参照）の糸をそれぞれ検尺用繰返機で一定の長さ（２００ｍ）採取し、これら採取糸を１２０℃で２時間乾燥した後、その質量を測定し、下記算出式よりグラフト率を求めた。 <Graft rate evaluation method>
Each of the yarns of the inner layer portion 51, the middle layer portion 52, and the outer layer portion 53 (see FIG. 1) of the modified yarn in the cheese state after the washing and drying has a fixed length (200 m) with a measuring repeater. The collected yarns were dried at 120 ° C. for 2 hours, then their masses were measured, and the graft ratio was determined from the following calculation formula.

グラフト率（質量％）＝｛（Ｍ−Ｎ）÷Ｎ｝×１００
Ｍ：採取糸（２００ｍ）の質量
Ｎ：処理前の原糸（２００ｍ）の質量。 Graft ratio (mass%) = {(MN) ÷ N} × 100
M: Mass of the collected yarn (200 m)
N: Mass of raw yarn (200 m) before treatment.

グラフト率の平均値が１０％以上であるものを「◎」とし、５％以上１０％未満であるものを「○」、２％以上５％未満であるものを「△」、０％以上２％未満であるものを「×」とした。 The case where the average graft ratio is 10% or more is “◎”, the case where it is 5% or more and less than 10% is “◯”, the case where it is 2% or more and less than 5% is “Δ”, and the case where 0% or more is 2 What was less than% was made into "x".

表２、３から明らかなように、本発明の製造方法で得られた実施例１〜１４の改質糸は、糸の素材としてポリエステル、ポリアミド又はウールを用いているにもかかわらず、高いグラフト率が得られており、十分に改質された改質糸を高速で製造することができた。 As is apparent from Tables 2 and 3, the modified yarns of Examples 1 to 14 obtained by the production method of the present invention are highly grafted despite using polyester, polyamide or wool as the yarn material. The yield was obtained, and a sufficiently modified yarn could be produced at high speed.

これに対し、全工程を空気雰囲気で実施した比較例１、４では、グラフト率は格段に低く、糸の改質が殆どなされていない。また、グラフト重合工程での糸の加熱温度を５０℃に設定した比較例３、５では、グラフト率は格段に低く、糸の改質が殆どなされていない。また、非連続で製造した比較例２では、グラフト率は格段に低く、糸の改質が殆どなされていない。 On the other hand, in Comparative Examples 1 and 4 in which all steps were performed in an air atmosphere, the graft ratio was remarkably low, and the yarn was hardly modified. Further, in Comparative Examples 3 and 5 in which the heating temperature of the yarn in the graft polymerization step was set to 50 ° C., the graft ratio was remarkably low, and the yarn was hardly modified. Moreover, in the comparative example 2 manufactured discontinuously, the graft rate is remarkably low, and the yarn is hardly modified.

本発明の製造方法で得られた改質糸は、グラフト重合反応により改質（難燃性付与、抗菌性付与、吸湿性付与、吸水性付与、制電性付与、防汚性付与等）がなされていて高機能性であるので、例えば編物、織物、不織布等を構成する糸として用いられる。 The modified yarn obtained by the production method of the present invention is modified by graft polymerization reaction (improving flame retardancy, imparting antibacterial properties, imparting moisture absorption, imparting water absorption, imparting antistatic properties, imparting antifouling properties, etc.). Since it is made and has high functionality, it is used, for example, as a yarn constituting knitted fabrics, woven fabrics, nonwoven fabrics, and the like.

１…糸
１Ａ…電子線照射糸
１Ｂ…接触工程後の糸
２…電子線照射装置
３…接触処理槽
４…ラジカル重合性モノマー
５…加熱槽
２０…電子線照射領域 DESCRIPTION OF SYMBOLS 1 ... Yarn 1A ... Electron beam irradiation yarn 1B ... Yarn 2 after contact process ... Electron beam irradiation apparatus 3 ... Contact treatment tank 4 ... Radical polymerizable monomer 5 ... Heating tank 20 ... Electron beam irradiation area

Claims

An electron beam irradiation step of irradiating an electron beam to a yarn which is a yarn selected from the group consisting of polyester yarn, polyamide yarn and wool yarn and is being conveyed;
A contact step of bringing a radical polymerizable monomer into contact with the carrier yarn after irradiation with the electron beam;
A graft polymerization step of graft-polymerizing the radical polymerizable monomer onto the yarn by heating the yarn after the contacting step at a temperature of 80 ° C. or more,
The electron beam irradiation step, the contact step and the graft polymerization step are continuously performed in an inert atmosphere ,
In the graft polymerization step, the production method of the modified thread, wherein Rukoto by graft polymerizing the radical polymerizable monomer to the yarn by heating the yarn while performing winding of the yarn in the heating bath.

2. The yarn feeding step according to claim 1, further comprising unwinding the wound yarn and transferring the unwound yarn to the electron beam irradiation step in an inert atmosphere before the electron beam irradiation step. A method for producing a modified yarn.

A contact step of bringing a radical polymerizable monomer into contact with a yarn that is selected from the group consisting of a polyester yarn, a polyamide yarn, and a wool yarn and is being conveyed;
An electron beam irradiation step of irradiating an electron beam to the carrier yarn after the contact step;
A graft polymerization step of graft-polymerizing the radical polymerizable monomer onto the yarn by heating the yarn after the electron beam irradiation at a temperature of 80 ° C. or higher,
The contact step, the electron beam irradiation step and the graft polymerization step are continuously performed in an inert atmosphere ,
In the graft polymerization step, the production method of the modified thread, wherein Rukoto by graft polymerizing the radical polymerizable monomer to the yarn by heating the yarn while performing winding of the yarn in the heating bath.

The modified yarn according to claim 3, further comprising a yarn feeding step of unwinding the wound yarn and transferring the unwound yarn to the contacting step in an inert atmosphere before the contacting step. Production method.

The processing from the yarn feeding step to the graft polymerization step is performed in a sealable container in which the internal space is communicated from the yarn feeding step to the graft polymerization step and the internal space is an inert atmosphere. A method for producing the modified yarn according to 1.

The method for producing a modified yarn according to any one of claims 1 to 5, wherein, in the graft polymerization step, the yarn is heated at a temperature exceeding 100 ° C and not more than 150 ° C.

Reforming yarn according to any one of claims 1 to 6 for retracting the yarn as the winding density of the yarn is 0.3g / cm ^³ ~0.7g / cm ³ in the heating chamber Manufacturing method.

In the electron beam irradiation step, the total distance (mm) that the yarn moves within the electron beam irradiation region is set to “L”, the irradiation capability (kGy · m / min) of the electron beam irradiation device is set to “P”, and the yarn is conveyed. When the speed (m / min) is “S” and the irradiation width (mm) in the yarn conveyance direction is “d”,
{P × (L / d)} / S ≧ 50 (kGy)
Method for producing a modified fiber according to any one of claims 1 to 7, the relationship is characterized in that hold.

The method for producing a modified yarn according to any one of claims 1 to 8 , wherein a conveying speed of the yarn is set to 100 m / min to 1000 m / min.

The method for producing a modified yarn according to any one of claims 1 to 9 , wherein in the contacting step, the radical polymerizable monomer is brought into contact with the yarn using a dip method, a spray method, or a coating method.

The method for producing a modified yarn according to any one of claims 1 to 10 , wherein the inert atmosphere is an inert atmosphere having an oxygen concentration of 500 ppm or less.

As the radical polymerizable monomer, one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a perfluoroalkyl group, a silanol group, a phosphate ester group, a glycidyl group, and an N-alkylamide group The method for producing a modified yarn according to any one of claims 1 to 11 , wherein at least a radical polymerizable monomer having a functional group is used.