JP2009068139A - Method for modifying synthetic fiber or fiber product and apparatus therefor - Google Patents
Method for modifying synthetic fiber or fiber product and apparatus therefor Download PDFInfo
- Publication number
- JP2009068139A JP2009068139A JP2007237709A JP2007237709A JP2009068139A JP 2009068139 A JP2009068139 A JP 2009068139A JP 2007237709 A JP2007237709 A JP 2007237709A JP 2007237709 A JP2007237709 A JP 2007237709A JP 2009068139 A JP2009068139 A JP 2009068139A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- carbon
- light
- compound
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
本発明は、合成繊維を含む、繊維又は繊維製品の改質方法とこれを実施するための装置に関するものである。 The present invention relates to a method for modifying a fiber or a fiber product including synthetic fibers and an apparatus for carrying out the method.
現在、合成繊維やこれを含む混紡繊維等は、衣料品等の原料として広く大量に用いられている。これらの繊維製品では、一般に、原料自体に不足している染色加工性等の性能を付与するための改質がなされている（例えば、非特許文献１、２参照）。 At present, synthetic fibers and blended fibers containing the same are widely used in large quantities as raw materials for clothing. These fiber products are generally modified to give performances such as dyeing processability that are lacking in the raw materials themselves (see, for example, Non-Patent Documents 1 and 2).
しかし、これらの改質の多くは高温処理により行われているため、大量のエネルギーを要する多消費型プロセスとなっており、多量の二酸化炭素の放出を伴い、また、装置を始動してからの温度が高温で安定する迄に長時間要し、その間に無駄なエネルギーを要するという問題があった。 However, since many of these reforms are performed by high-temperature treatment, it is a multi-consumption type process that requires a large amount of energy, which involves the release of a large amount of carbon dioxide. There was a problem that it took a long time for the temperature to stabilize at a high temperature, and wasteful energy was required during that time.
また、これらの改質法では各種樹脂類、塩類、金属類、有機化合物などの機能性物質を物理的に付与することが多いため、長期間の使用や洗浄等により機能性物質が繊維や繊維製品から脱離し、その効果が十分に発現しないという問題もあった。 Also, these modification methods often physically apply functional substances such as various resins, salts, metals, organic compounds, etc., so that the functional substances may become fibers or fibers after long-term use or washing. There was also a problem that it was detached from the product and the effect was not fully exhibited.
そのため、繊維に対する化学反応により改質して機能付与することも行われているが、この化学反応は通常高温処理やプラズマや電子線等の物理的手段により行われる場合が多く、いずれの場合もエネルギー多消費型プロセスとなり、また大型の装置や高真空等の特殊な条件も時には必要とするといった難点があった。 For this reason, it is also carried out by modifying and imparting a function by a chemical reaction to the fiber, but this chemical reaction is usually carried out by physical means such as high temperature treatment or plasma or electron beam, and in any case This is an energy intensive process, and there are also disadvantages that special conditions such as large equipment and high vacuum are sometimes required.
一方、十分な染色が困難である合成繊維に関してはその染色性の改善が強く望まれている。たとえば、ナイロン類は他の合成繊維に比べて親水性が高く、また繊維構造も緻密でないために、酸性染料によりナイロンの末端アミノ基がイオン結合することにより染色ができるものの、他の種類の染料では十分な染色ができないという難点がある。 On the other hand, for synthetic fibers that are difficult to dye sufficiently, improvement of the dyeability is strongly desired. For example, nylons have higher hydrophilicity than other synthetic fibers and the fiber structure is not dense, so that dyes can be dyed by ionic bonding of the terminal amino groups of nylon with acid dyes, but other types of dyes. However, there is a problem that sufficient dyeing cannot be performed.
また、繊維製品として大量に用いられているポリエステル繊維は、疎水性で結晶性が高く、またその構造が緻密であるために、分散染料でしか染色できず、しかもその染色性も十分でない場合も多い。また、アクリル繊維の場合はアクリロニトリルのホモポリマーは殆ど染色できないため、アニオン性或いはカチオン性コモノマーに改質しないと染色できない。 Polyester fibers used in large quantities as textile products are hydrophobic and highly crystalline, and because their structures are dense, they can only be dyed with disperse dyes, and their dyeability may not be sufficient. Many. In the case of acrylic fiber, acrylonitrile homopolymer can hardly be dyed, and therefore, it cannot be dyed unless it is modified to an anionic or cationic comonomer.
このような合成繊維や繊維製品の染色性を改善するために、これまでに各種の提案がなされている（非特許文献１〜３参照）。
例えば、ナイロン類を強酸性にすることにより、主鎖アミドも酸性染料で染色できる手法が提案されている。また、金属錯塩染料を用いることも可能であるが、その廃液中には強酸や有害金属が含まれるために、その廃液処理が困難になるという問題が生じる。
また、ポリエステル繊維の場合は、高温高圧染色法、オルトフェニルフェノールなどのポリエステルに対して可塑性のある化合物を用いるキャリヤー染色法や高温処理を要するサーモゾル染色法等も提案されているが、高温高圧染色法やサーモゾル染色法ではエネルギーを大量に消費する等という問題があり、キャリヤー染色法でもオルトフェニルフェノール等の環境に負荷を与える化合物を用いる必要があるという難点がある。
In order to improve the dyeability of such synthetic fibers and fiber products, various proposals have been made so far (see Non-Patent Documents 1 to 3).
For example, a method has been proposed in which a main chain amide can be dyed with an acidic dye by making nylons strongly acidic. Metal complex dyes can also be used, but the waste liquid contains a strong acid and a toxic metal, which causes a problem that the waste liquid treatment becomes difficult.
In the case of polyester fibers, high-temperature and high-pressure dyeing methods, carrier dyeing methods that use plastic compounds such as orthophenylphenol, and thermosol dyeing methods that require high-temperature treatment have also been proposed. The method and the thermosol dyeing method have a problem of consuming a large amount of energy, and the carrier dyeing method also has a drawback that it is necessary to use a compound that imposes an environment load such as orthophenylphenol.
本発明は、このような問題点を克服するためになされたものであって、省エネルギー型であり、室温でかつ簡便な操作で安全に、合成繊維を含む繊維や繊維製品の改質を容易とする方法およびそのための装置を提供することを目的とする。 The present invention has been made to overcome such problems, is energy-saving, and facilitates the modification of fibers and fiber products including synthetic fibers safely at room temperature and with simple operation. It is an object to provide a method and an apparatus therefor.
本発明者らは、かかる従来技術の難点を解消するために鋭意検討した結果、合成繊維を含む繊維や繊維製品を、光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合に結合した炭素−炭素二重結合を有する化合物の存在下で光照射する方法が極めて有効であることを見出し、この知見に基づき本発明をなすに至った。 As a result of intensive investigations to solve the problems of the prior art, the present inventors have found that fibers and fiber products containing synthetic fibers have a carbon-carbon dioxygen-containing compound and an electron-withdrawing group directly generated by light irradiation. It has been found that a method of irradiating light in the presence of a compound having a carbon-carbon double bond bonded to a heavy bond is extremely effective, and the present invention has been made based on this finding.
すなわち、この出願によれば、以下の発明が提供される。
〈１〉光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物の存在下、合成繊維を含む繊維又は繊維製品に対し、光照射することを特徴とする合成繊維を含む繊維又は繊維製品の改質方法。
〈２〉光照射によりラジカルを発生する化合物の存在下、合成繊維を含む繊維又は繊維製品に対し、光照射した後に、前記該炭素−炭素二重結合を有する化合物と処理することを特徴とする合成繊維を含む繊維又は繊維製品の改質方法。
〈３〉光照射によりラジカルを発生する化合物を、合成繊維を含む繊維又は繊維製品の一部だけに付与して光照射することを特徴とする〈１〉又は〈２〉に記載の繊維又は繊維製品の改質方法。
〈４〉光照射によりラジカルを発生する化合物が過酸化物であることを特徴とする〈１〉から〈３〉のいずれかに記載の繊維又は繊維製品の改質方法。
〈５〉光ビームまたはマスクを通して光照射を行うことを特徴とする〈１〉から〈４〉のいずれかに記載の繊維又は繊維製品の改質方法。
〈６〉〈１〉から〈５〉のいずれかに記載の方法での光照射後に繊維及び繊維製品を還元剤で処理することを特徴とする繊維及び繊維製品の改質方法。
〈７〉繊維又は繊維製品の改質が染色性の改善にあることを特徴とする〈１〉から〈６〉のいずれかに記載の繊維又は繊維製品の改質方法。
〈８〉〈１〉、〈３〉から〈７〉のいずれかに記載の方法を行うための改質装置であって、光源とともに光照射によりラジカルを発生する化合物と前記該炭素−炭素二重結合を有する化合物の存在下で合成繊維を含む、繊維又は繊維製品に光照射する手段を備えていることを特徴とする繊維又は繊維製品の改質装置。
〈９〉〈２〉から〈７〉のいずれかに記載の方法を行うための改質装置であって、光源とともに、光照射によりラジカルを発生する化合物の存在下で合成繊維を含む、繊維又は繊維製品に光照射する手段と、光照射した後に該炭素−炭素二重結合を有する化合物と処理する手段を備えていることを特徴とする繊維又は繊維製品の改質装置。
That is, according to this application, the following invention is provided.
<1> A fiber containing a synthetic fiber in the presence of a compound that generates radicals upon light irradiation and a compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon atom that forms a carbon-carbon double bond Alternatively, a method for modifying a fiber or a fiber product including synthetic fibers, wherein the fiber product is irradiated with light.
<2> In the presence of a compound that generates radicals by light irradiation, a fiber or a fiber product including a synthetic fiber is irradiated with light and then treated with the compound having the carbon-carbon double bond. A method for modifying a fiber or fiber product containing synthetic fiber.
<3> The fiber or fiber according to <1> or <2>, wherein the compound that generates radicals by light irradiation is applied to only a part of the fiber or fiber product including the synthetic fiber and irradiated with light. Product modification method.
<4> The method for modifying a fiber or fiber product according to any one of <1> to <3>, wherein the compound that generates radicals upon irradiation with light is a peroxide.
<5> The method for modifying a fiber or fiber product according to any one of <1> to <4>, wherein light irradiation is performed through a light beam or a mask.
<6> A method for modifying a fiber and a fiber product, wherein the fiber and the fiber product are treated with a reducing agent after the light irradiation in the method according to any one of <1> to <5>.
<7> The method for modifying a fiber or fiber product according to any one of <1> to <6>, wherein the modification of the fiber or the fiber product is to improve dyeability.
<8> A reformer for performing the method according to any one of <1> and <3> to <7>, wherein the compound that generates radicals by light irradiation together with a light source and the carbon-carbon double An apparatus for modifying a fiber or a fiber product, comprising means for irradiating light to the fiber or the fiber product including a synthetic fiber in the presence of a compound having a bond.
<9> A reformer for performing the method according to any one of <2> to <7>, comprising a synthetic fiber in the presence of a light source and a compound that generates radicals by light irradiation, or An apparatus for modifying a fiber or a textile product, comprising: means for irradiating a fiber product with light; and means for treating with a compound having a carbon-carbon double bond after the light irradiation.
本発明の方法と装置によれば、合成繊維を含む繊維又は繊維製品の改質を室温で簡便な装置を用いて安全に行うことができ、また、上記繊維及び繊維製品の改質範囲を拡大して新たな機能の発現や染色性の改善等を実現することができる。また、本発明の方法と装置は、持続的な社会の発展に必要な、省資源、省エネルギー、環境負荷低減技術として多いに寄与するものである。 According to the method and apparatus of the present invention, modification of fibers or fiber products containing synthetic fibers can be performed safely at room temperature using a simple apparatus, and the modification range of the fibers and fiber products is expanded. Thus, it is possible to realize the expression of new functions and the improvement of dyeability. In addition, the method and apparatus of the present invention greatly contributes to resource saving, energy saving, and environmental load reduction technologies necessary for sustainable social development.
本発明の対象となる合成繊維とは、合成繊維のみならず半合成繊維も包含される。また、本発明でいう、合成繊維を含む繊維とは、上述した合成繊維単独の他、複数の合成繊維からなる繊維を意味する。また、合成繊維以外の繊維の１種類以上と、合成繊維の１種類以上とが混合した繊維も含む。ここで、合成繊維以外の繊維とは、綿、麻、羊毛、絹等の天然繊維、レーヨン等の再生繊維を指すものとする。 The synthetic fiber which is the subject of the present invention includes not only synthetic fibers but also semi-synthetic fibers. Moreover, the fiber containing a synthetic fiber as used in the field of this invention means the fiber which consists of a several synthetic fiber other than the synthetic fiber mentioned above. Moreover, the fiber which mixed 1 or more types of fibers other than a synthetic fiber and 1 or more types of synthetic fibers is also included. Here, fibers other than synthetic fibers refer to natural fibers such as cotton, hemp, wool and silk, and regenerated fibers such as rayon.
本発明で用いられる合成繊維としては、たとえば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ベンゾエート、コーデル、チタノセンテレフタレート等の各種ポリエステル繊維、ナイロン６やナイロン６６等の各種ナイロン繊維、ノメックスやケブラーなどの各種アラミド繊維、ポリアクリロニトリル等の各種アクリル系繊維、ポリビニルアルコール等のビニロン繊維、各種ポリウレタン繊維、ポリ塩化ビニル繊維、各種ビニリデン繊維、ポリエチレンやポリプロピレン等の各種ポリオレフィン繊維、ポリテトラフルオロエチレン等の各種フッ素繊維、ノボロイド等のフェノール系繊維、及び各種共重合繊維等が例示される。
半合成繊維としては、トリアセテートやジアセテート等のセルロース系、及びプロミックス等のタンパク質系等の各種半合性繊維が例示される。
Examples of the synthetic fiber used in the present invention include various polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, benzoate, cordel and titanocene terephthalate, various nylon fibers such as nylon 6 and nylon 66, and various aramid fibers such as Nomex and Kevlar. , Various acrylic fibers such as polyacrylonitrile, vinylon fibers such as polyvinyl alcohol, various polyurethane fibers, polyvinyl chloride fibers, various vinylidene fibers, various polyolefin fibers such as polyethylene and polypropylene, various fluorine fibers such as polytetrafluoroethylene, and novoloid Examples thereof include phenol-based fibers, various copolymer fibers, and the like.
Examples of semisynthetic fibers include various semi-synthetic fibers such as celluloses such as triacetate and diacetate, and proteins such as promix.
また、合成繊維を含む繊維としては、綿ポリエステル混紡等が例示される。
合成繊維を含む繊維製品としては、糸、織物、衣服、各種容器、装飾品等、主に合成繊維や半合性繊維からなる製品以外にも、他の素材との複合体等からなる製品にも合成繊維や半合性繊維に由来する繊維が含まれている場合にはこれらの任意のものを用いることができる。
In addition, examples of the fibers including synthetic fibers include cotton polyester blends.
Textile products containing synthetic fibers include products made of composites with other materials, in addition to products made mainly of synthetic fibers and semi-synthetic fibers, such as yarns, fabrics, clothes, various containers, and ornaments. In the case where fibers derived from synthetic fibers and semi-synthetic fibers are included, any of these can be used.
本発明でいう、合成繊維を含む繊維又は繊維製品の改質とは、該繊維及び繊維製品が本来有する機能、性能、性質等とは異なる新たな機能、性能、性質等を付与することを意味し、新たな機能、性能、性質等が付与されていれば、本来有する機能、性能、性質等を併せ持っていてもよい。
繊維及び繊維製品の具体的な改質態様としては、染色性、濃色性、深色性、風合い、防縮性、親水性、撥水性、防水性、親油性、形状記憶性、導電性、しわ加工性、防しわ性、難燃性、樹脂加工性、防虫性、妨カビ性、消臭性、加工性、減量加工、グラフト性、架橋、ＳＲ性、電磁波シールド性、メッキ性、芳香性、芳香徐放性等が挙げられるが、これらの機能、性質等に限定されるものではなく、該繊維や繊維製品が本来有する機能、性能、性質等とは異なる新たな機能、性能、性質等を付与するものであればよい。
In the present invention, the modification of a fiber or a fiber product containing a synthetic fiber means that a new function, performance, property, etc. different from the function, performance, property, etc. inherent to the fiber and the fiber product are imparted. However, as long as new functions, performances, properties, and the like are given, the functions, performances, properties, and the like that are originally included may be included.
Specific modifications of fibers and textile products include dyeability, darkness, deep color, texture, shrinkage resistance, hydrophilicity, water repellency, waterproofness, lipophilicity, shape memory, conductivity, wrinkles Processability, wrinkle resistance, flame retardancy, resin processability, insect resistance, mold prevention, deodorization, processability, weight loss processing, grafting, cross-linking, SR, electromagnetic wave shielding, plating, aromatic, Examples include, but are not limited to, these functions, properties, etc., and new functions, performances, properties, etc. that are different from the functions, performances, properties, etc. inherent to the fibers and fiber products. What is necessary is just to give.
本発明において用いる照射光としては目的として付与することによる機能、性能、性質や、付与のための効率等を考慮して選択してよいが、一般的には、１２０〜８００ｎｍの、好ましくは１９０〜６００ｎｍの紫外線や可視光（以下、紫外可視光ともいう）を用いることが望ましい。紫外可視光源としては特に制限はなく、連続光でもパルス光でもよく、低圧水銀灯、高圧水銀灯、キセノン灯、ブラックライト、各種ＬＥＤ、各種エキシマランプ等の通常の光源を用いることができるが、これらに限定されるものではなく従来公知の光源を適宜に用いることができる。照射光強度にも特に制限は無いが、紫外可視光の連続光源としては０．１ｍＷ〜１０ｋＷの光源が適している。 The irradiation light used in the present invention may be selected in consideration of the function, performance, properties, efficiency for application, etc. provided by the purpose, but in general, it is 120 to 800 nm, preferably 190. It is desirable to use ultraviolet light or visible light (hereinafter also referred to as ultraviolet visible light) of ˜600 nm. The UV-visible light source is not particularly limited and may be continuous light or pulsed light, and ordinary light sources such as low-pressure mercury lamp, high-pressure mercury lamp, xenon lamp, black light, various LEDs, and various excimer lamps can be used. It is not limited and a conventionally well-known light source can be used suitably. Although there is no restriction | limiting in particular in irradiation light intensity, as a continuous light source of ultraviolet visible light, a light source of 0.1 mW-10 kW is suitable.
また光源として各種レーザーを用いることができ、レーザー光はパルス光でも連続照射光でもよいが、エキシマレーザー（ＡｒＦエキシマレーザー、ＫｒＦエキシマレーザー、ＸｅＣｌエキシマレーザー、ＸｅＦエキシマレーザー等）、アルゴンイオンレーザー、クリプトンイオンレーザー、ＹＡＧレーザーの第２、及び第３高調波等を用いることができるが、これらに限定されるものではなく従来公知のレーザーを適宜に用いることができる。
紫外可視レーザー光としては、特別な制約はないが、波長が１４０〜８００ｎｍ、好ましくは１９０〜６００ｎｍ程度のものを用いることが望ましい。
レーザー照射光強度にも特に制限は無いが、パルス光では０．１ｍＪ／パルス〜１ｋＪ／パルス、連続光は０．１ｍＷ〜１０ｋＷの光源が適している。
Various lasers can be used as the light source, and the laser light may be pulsed light or continuous irradiation light, but excimer laser (ArF excimer laser, KrF excimer laser, XeCl excimer laser, XeF excimer laser, etc.), argon ion laser, krypton The second and third harmonics of an ion laser and a YAG laser can be used, but the present invention is not limited to these, and a conventionally known laser can be used as appropriate.
Although there is no special restriction | limiting as an ultraviolet-visible laser beam, It is desirable to use a wavelength about 140-800 nm, Preferably about 190-600 nm.
Although there is no restriction | limiting in particular also in laser irradiation light intensity | strength, 0.1 mJ / pulse-1 kJ / pulse is suitable for pulsed light, and 0.1 mW-10 kW light source is suitable for continuous light.
光照射には光ビームを用いることができる。このような光ビームとしては各種レーザーの使用が適しているが、通常の光源を用いて各種レンズやミラー類等の光学系を用いて光を特定の方向に照射できるものであればビームが平行光線でなくても用いることができる。これらの光ビームを各種ミラー類等の光学系を用いることにより移動しながら対象となる合成繊維を含む繊維または繊維製品に照射することができる。 A light beam can be used for light irradiation. As such a light beam, use of various lasers is suitable. However, if an ordinary light source can be used to irradiate light in a specific direction using various optical systems such as lenses and mirrors, the beams are parallel. Even if it is not a light beam, it can be used. These light beams can be irradiated to a fiber or a fiber product including a target synthetic fiber while moving by using an optical system such as various mirrors.
また、マスクを通して光照射を行うこともできる。マスクを用いて光照射を行う場合には、マスクは光源と対象となる合成繊維を含む繊維または繊維製品の間の何れの位置に置いても良く、光源としては上記の光源の何れをも用いることができる。また、光源とマスクの間、及び／又はマスクと対象となる合成繊維を含む繊維または繊維製品の間に各種レンズやミラー類等の光学系を設置して、マスクのパターンを縮小、拡大、変形することもできる Moreover, light irradiation can also be performed through a mask. When performing light irradiation using a mask, the mask may be placed at any position between the light source and the fiber or fiber product containing the target synthetic fiber, and any of the above light sources is used as the light source. be able to. In addition, an optical system such as various lenses and mirrors is installed between the light source and the mask and / or between the mask and the fiber or fiber product containing the target synthetic fiber to reduce, enlarge, or deform the mask pattern. Can also
また、通常の光照射、光ビームによる光照射、及びマスクを用いる光照射において、光源の特性、及び／又は各種レンズやミラー類等の光学系を用いることにより光照射面内の光強度に強弱を付けることにより合成繊維を含む繊維または繊維製品の改質の度合いにグラデーションを付けることもできる。 Also, in normal light irradiation, light irradiation with a light beam, and light irradiation using a mask, the intensity of the light in the light irradiation surface is enhanced by using the characteristics of the light source and / or optical systems such as various lenses and mirrors. It is also possible to add gradation to the degree of modification of the fiber or fiber product containing synthetic fiber.
光照射時間は、布の種類、厚さ、形態、溶液の種類と濃度、更には、照射紫外可視光の種類や光強度等を考慮することにより適宜定められるが、定常光源の場合は通常１秒〜１２０分、各種レーザーを用いた場合には連続レーザーでは通常１μ秒〜３０分、パルスレーザーでは通常１〜１０００パルスもあれば充分であるが、これらの照射時間に関わらず必要な改質が起こるのに必要な時間光照射を行えばよい。 The light irradiation time is appropriately determined by considering the type of cloth, thickness, form, type and concentration of solution, and the type and intensity of irradiated ultraviolet-visible light. When using various lasers, it is usually sufficient to use 1 μsec to 30 minutes for a continuous laser and usually 1 to 1000 pulses for a pulsed laser. Light irradiation may be performed for a time necessary for the occurrence of the above.
本発明において用いる光照射によりラジカルを発生する化合物としては、好ましくは各種過酸化物、各種光重合開始剤、等が挙げられ、特に過酸化水素や過酸類が好ましいが、これらに限定されるものではなく、該化合物が光照射により単独、或いは他の化合物との相互作用により、ラジカル、ラジカルカチオン、或いはラジカルアニオンを発生するものであればよい。 Examples of the compound that generates radicals upon irradiation with light used in the present invention include various peroxides and various photopolymerization initiators, and hydrogen peroxide and peracids are particularly preferable. Instead, it is sufficient that the compound generates radicals, radical cations, or radical anions by light irradiation alone or by interaction with other compounds.
本発明において用いる電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物は芳香族化合物も含み、光照射による繊維及び繊維製品の改質を著しく阻害するものでなければ従来公知の電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物が全て使用できる。また、該炭素−炭素二重結合が分子内に複数有る化合物、該炭素−炭素二重結合を有する化合物が高分子化合物である化合物、該炭素−炭素二重結合を有する部位が高分子化合物にグラフトされた化合物等も該炭素−炭素二重結合を有する化合物として用いることができる。また、これらの該炭素−炭素二重結合を有する化合物のいずれかを単独で用いてもよいが、複数の該炭素−炭素二重結合を有する化合物からなる混合系を用いることもできる。 The compound having a carbon-carbon double bond in which an electron-withdrawing group used in the present invention is directly bonded to a carbon atom that forms a carbon-carbon double bond includes an aromatic compound, and modification of fibers and fiber products by light irradiation. Any compound having a carbon-carbon double bond in which a conventionally known electron-withdrawing group is directly bonded to a carbon atom forming a carbon-carbon double bond can be used. In addition, a compound having a plurality of carbon-carbon double bonds in the molecule, a compound in which the compound having the carbon-carbon double bond is a polymer compound, and a site having the carbon-carbon double bond in the polymer compound A grafted compound or the like can also be used as the compound having the carbon-carbon double bond. In addition, any of these compounds having a carbon-carbon double bond may be used alone, but a mixed system composed of a compound having a plurality of the carbon-carbon double bonds may also be used.
ここで用いる電子吸引性基が直接結合した炭素−炭素二重結合の置換基数や置換基の種類にも制限は無く、他の置換基として水素、電子供与性基、電子吸引性基のいずれの特性を有する炭化水素基、各種官能基を有する炭化水素基、各種官能基等、全て用いることができる。
電子吸引性基としては、ＮＲ３ ＋、ＳＲ２ ＋、ＮＨ３ ＋、ＮＯ２、ＳＯ２Ｒ、ＣＮ、ＳＯ２Ａｒ、ＣＯＯＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＯＡｒ、ＣＯＯＲ、ＯＲ、ＣＯＲ、ＳＨ、ＳＲ、ＯＨ、Ａｒ、アルキン、アルケン（ここでＡｒは芳香族基を表す）等が挙げられる（非特許文献４参照）が、これらに限定されるものではない。
There is no limitation on the number of substituents and the type of substituents of the carbon-carbon double bond to which the electron-withdrawing group is directly bonded, and any other substituents such as hydrogen, electron-donating group, and electron-withdrawing group can be used. A hydrocarbon group having characteristics, a hydrocarbon group having various functional groups, various functional groups, and the like can all be used.
As the electron-withdrawing group, NR 3 + , SR 2 + , NH 3 + , NO 2 , SO 2 R, CN, SO 2 Ar, COOH, F, Cl, Br, I, OAr, COOR, OR, COR, SH, SR, OH, Ar, alkyne, alkene (where Ar represents an aromatic group) and the like can be mentioned (see Non-Patent Document 4), but are not limited thereto.
電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物としては、アクリル酸やメタクリル酸等の炭素−炭素二重結合と共役したカルボン酸類、およびこれらのカルボン酸の各種エステルやアミド、アクリロニトリル、フマロニトリル等の炭素−炭素二重結合と共役したニトリル類、ビニルヘキシルエーテル等の各種アルキルエノールエーテル類、メチルビニルケトン、ビタミンＫ、ビタミンＣ等の炭素−炭素二重結合と共役したカルボニル化合物類、ニトロエチレン等の炭素−炭素二重結合と共役したニトロオレフィン類、ビニルスルホン酸等の炭素−炭素二重結合と共役したスルホン酸、及びそれらの各種エステル、テストステロン等のステロイド類、スチレン、シクロヘキサジエン、ブタジエン、ヘキサトリエン、各種カロテン、ビタミンＡ等の共役した炭素−炭素二重結合を有する化合物、フラーレン、アントラセン、等の多核芳香族化合物類、ヒノキチオール等の複数の電子吸引性基が炭素−炭素二重結合と共役したもの、等が挙げられるがこれらに限定されるものではなく、炭素−炭素二重結合に直接電子吸引性基が結合した炭素−炭素二重結合を有する化合物であればよい。 Examples of the compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon atom forming a carbon-carbon double bond include carboxylic acids conjugated with a carbon-carbon double bond such as acrylic acid and methacrylic acid. , And various esters and amides of these carboxylic acids, nitriles conjugated with carbon-carbon double bonds such as acrylonitrile and fumaronitrile, various alkyl enol ethers such as vinyl hexyl ether, methyl vinyl ketone, vitamin K, vitamin C, etc. Carbonyl compounds conjugated with carbon-carbon double bonds of the above, nitroolefins conjugated with carbon-carbon double bonds such as nitroethylene, sulfonic acids conjugated with carbon-carbon double bonds such as vinyl sulfonic acid, and the like Various esters, steroids such as testosterone, styrene, cyclohexadiene, Compounds having a conjugated carbon-carbon double bond such as tadiene, hexatriene, various carotenes, vitamin A, polynuclear aromatic compounds such as fullerene and anthracene, and a plurality of electron-withdrawing groups such as hinokitiol Examples thereof include, but are not limited to, those conjugated with a heavy bond, and any compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon-carbon double bond may be used.
また、該炭素−炭素二重結合が分子内に複数有る化合物としては、先に挙げたアラキドン酸等、が挙げられ、該炭素−炭素二重結合を有する化合物が高分子化合物である化合物、該炭素−炭素二重結合を有する部位が高分子化合物にグラフトされた化合物としてはポリビニルアルコールのポリアクリル酸エステルやポリメタクリル酸エステル等が挙げられるが、これらに限定されるものではなく、該炭素−炭素二重結合が分子内に複数有る化合物、該炭素−炭素二重結合を有する化合物が高分子化合物である化合物、該炭素−炭素二重結合を有する部位が高分子化合物にグラフトされた化合物等であればよい。 Examples of the compound having a plurality of carbon-carbon double bonds in the molecule include arachidonic acid and the like mentioned above, a compound in which the compound having the carbon-carbon double bond is a polymer compound, Examples of the compound in which a site having a carbon-carbon double bond is grafted to a polymer compound include polyacrylic acid ester and polymethacrylic acid ester of polyvinyl alcohol, but are not limited thereto. A compound having a plurality of carbon double bonds in the molecule, a compound in which the compound having the carbon-carbon double bond is a polymer compound, a compound in which a site having the carbon-carbon double bond is grafted to the polymer compound, etc. If it is.
また、本発明においては、改質により付与された新たな機能、性能、性質等の安定化等や、該機能、性能、性質等の更なる改質のために、光照射後に繊維及び繊維製品を還元剤で処理する方法も採ることもできる。
還元剤としては、特に制約はなく従来公知の還元剤の任意のものを使用できる。このような還元剤としては、チオ硫酸ナトリウム、ハイドロサルファイト、水素化ホウ素ナトリウム、ロンガリット、亜硫酸ナトリウム、亜硫酸水素ナトリウム、ヒドラジン等、或いは還元性を有するビタミンＣ、各種アルデヒド類、ギ酸等の有機化合物を挙げることができるが、これらに限定されるものではなく還元性を有するものであればよい。また、これらの還元剤のいずれかを単独で用いてもよいが、複数の還元剤からなる混合物を用いることもできる
Further, in the present invention, fibers and fiber products after light irradiation are used for stabilization of new functions, performances, properties, etc. imparted by the modification, and for further modifications of the functions, performances, properties, etc. It is also possible to adopt a method of treating with a reducing agent.
The reducing agent is not particularly limited and any conventionally known reducing agent can be used. Examples of such reducing agents include sodium thiosulfate, hydrosulfite, sodium borohydride, Rongalite, sodium sulfite, sodium hydrogen sulfite, hydrazine and the like, or organic compounds such as vitamin C having a reducing property, various aldehydes, formic acid, etc. However, the present invention is not limited to these, and any material having reducibility may be used. Any one of these reducing agents may be used alone, but a mixture of a plurality of reducing agents can also be used.
本発明の光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物の、繊維又は繊維製品に対する作用についてであるが、光照射により発生したラジカル（ラジカル、ラジカルカチオン、ラジカルアニオン）種により上記繊維または繊維製品の表面上にラジカルが発生し、この様に発生したラジカル種が該炭素−炭素二重結合と反応して結合を形成することにより改質が起こるものと考えられる。あるいは、光照射により発生したラジカル種により、該炭素−炭素二重結合を有する化合物の重合が上記繊維または繊維製品上で起こり、その結果生じた高分子化合物が上記繊維または繊維製品に物理的に付着することにより改質が起こることも考えられる。さらには、光照射により発生したラジカル種により上記繊維または繊維製品にラジカルが発生し、このラジカルと上記繊維または繊維製品で起こった該炭素−炭素二重結合を有する化合物の重合物中の炭素−炭素二重結合との反応により、該炭素−炭素二重結合を有する化合物の重合体を上記繊維または繊維製品にラジカル反応により結合することによる改質も起こるものと考えられる。このようなラジカルの炭素−炭素二重結合への付加反応は、電子吸引性基を有する炭素−炭素二重結合を有する化合物について広く起こることが有機化学的に知られている（例えば、非特許文献５参照）。また、このような炭素−炭素二重結合を分子内に一つ有する化合物ばかりではなく、分子内に複数有する化合物においても同様のラジカル反応が起こると考えることは合理的である。
しかし、本発明方法では、上記の推定反応機構に関わらず、光照射によりラジカルを発生する化合物の存在下で、セルロース系繊維又は動物性繊維を含む、繊維や繊維製品が光照射を受けることにより改質が起こればよいことは勿論である。
About the effect | action with respect to the fiber or textiles of the compound which generate | occur | produces a radical by light irradiation of this invention, and the compound which has a carbon-carbon double bond which the electron withdrawing group couple | bonded with the carbon atom which directly forms a carbon-carbon double bond However, radicals (radicals, radical cations, radical anions) generated by light irradiation generate radicals on the surface of the fiber or fiber product, and the generated radicals are the carbon-carbon double bonds. It is considered that the modification occurs by forming a bond by reacting with. Alternatively, polymerization of the compound having a carbon-carbon double bond occurs on the fiber or fiber product due to radical species generated by light irradiation, and the resulting polymer compound is physically added to the fiber or fiber product. It is also conceivable that modification occurs due to adhesion. Furthermore, a radical is generated in the fiber or the fiber product by the radical species generated by light irradiation, and the carbon in the polymer of the compound having the carbon-carbon double bond generated in the fiber or the fiber product is generated. It is considered that modification by bonding a polymer of a compound having a carbon-carbon double bond to the fiber or fiber product by a radical reaction is caused by the reaction with the carbon double bond. It is known from organic chemistry that such an addition reaction of a radical to a carbon-carbon double bond occurs widely for a compound having a carbon-carbon double bond having an electron-withdrawing group (for example, non-patent Reference 5). In addition, it is reasonable to consider that the same radical reaction occurs not only in a compound having one carbon-carbon double bond in the molecule but also in a compound having a plurality of carbon-carbon double bonds in the molecule.
However, in the method of the present invention, regardless of the estimated reaction mechanism described above, in the presence of a compound that generates radicals by light irradiation, fibers or fiber products including cellulosic fibers or animal fibers are irradiated with light. Of course, it is sufficient that the reforming occurs.
本発明の実施の態様に特別な制限はないが、好ましい実施の態様としては、合成繊維を含む繊維又は繊維製品を、光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合に結合した炭素−炭素二重結合を有する化合物を含む薬液に浸漬或いは懸濁させて光照射する方法、あるいは該薬液に浸して引き上げた所に光照射する方法、もしくは該薬液を上記繊維または繊維製品に塗布、吹きつけ等を行い光照射する方法等が挙げられるが、これらに限定されるものではない。
特に該薬液を上記繊維または繊維製品に塗布、吹きつけ等を行う際にはエアーブラシやブラシ類等を用いて上記繊維または繊維製品全体に該薬液を付与するばかりではなく、対象物の一部に付与することにより部分的な改質を起こすことも可能で、この部分的な改質により文字、図表等の形態を有する改質を起こすことができる。また、これらの光照射は上記繊維または繊維製品が静置している状態、或いは移動している状態で行うことができる。
Although there is no particular limitation on the embodiment of the present invention, as a preferable embodiment, a fiber or a fiber product containing a synthetic fiber is directly bonded to a compound that generates radicals by light irradiation and an electron-withdrawing group is directly carbon-carbon. A method of irradiating light by immersing or suspending in a chemical solution containing a compound having a carbon-carbon double bond bonded to a heavy bond, or a method of irradiating the chemical solution with light, or a method of irradiating the chemical solution with the above-mentioned fiber Alternatively, a method of applying, spraying, or the like to a fiber product and irradiating with light may be used, but the method is not limited thereto.
In particular, when applying or spraying the chemical liquid onto the fiber or fiber product, not only applying the chemical liquid to the entire fiber or fiber product using an air brush or brushes, but also part of the object It is also possible to cause partial reforming by applying to, and by this partial reforming, it is possible to cause reforming having a form such as a character, a chart or the like. Moreover, these light irradiation can be performed in the state which the said fiber or textiles left still, or the state which is moving.
光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物を含む薬液で同時に処理する代わりに、光照射によりラジカルを発生する化合物で処理した繊維又は繊維製品に光照射を行う操作と、この様に処理した繊維又は繊維製品を該炭素−炭素二重結合を有する化合物と処理する操作を分けて行うこともでき、それぞれの操作において上記同時処理で用いる手法を使用することができる。 Instead of simultaneously treating with a chemical solution containing a compound that generates radicals by light irradiation and a compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon atom that forms a carbon-carbon double bond, light irradiation is performed. The operation of irradiating the fiber or fiber product treated with the compound that generates radicals by the above and the operation of treating the fiber or fiber product treated in this way with the compound having the carbon-carbon double bond are performed separately. It is also possible to use the technique used in the above simultaneous processing in each operation.
光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物はそれらの溶液で有ってもよく、その場合の溶媒としては、照射光を殆ど吸収しないで光照射による繊維及び繊維製品の改質を著しく阻害するものでなければ特に制約はなく従来公知の溶媒を適宜に使用することができる。
このような溶媒としては、たとえは、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミドなどの極性溶媒の他に、デカン、ドデカン、テトラデカン等の脂肪族炭化水素や、トルエン、キシレン等の芳香族炭化水素（分子内に脂肪族基を有する芳香族炭化水素も含む）等の無極性溶媒、プロピルアミン、エチレンジアミン、各種カルボン酸、各種ポリカルボン酸、などのプロトン性溶媒等を挙げることができるが、これらに限定されるものではない。
また、これらの溶媒のいずれかを単独で用いてもよいが、複数の溶媒からなる混合溶媒を用いることもできる。
A compound that generates a radical by light irradiation and a compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon atom that forms a carbon-carbon double bond may be in their solution. The solvent in this case is not particularly limited as long as it hardly absorbs irradiation light and remarkably inhibits modification of fibers and fiber products by light irradiation, and a conventionally known solvent can be appropriately used.
Examples of such solvents include, in addition to polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide, aliphatic hydrocarbons such as decane, dodecane, and tetradecane, and aromatic hydrocarbons such as toluene and xylene (intramolecular Non-polar solvents such as aromatic hydrocarbons having aliphatic groups), and protic solvents such as propylamine, ethylenediamine, various carboxylic acids, and various polycarboxylic acids, but are not limited thereto. It is not something.
Any one of these solvents may be used alone, but a mixed solvent composed of a plurality of solvents may be used.
また、光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物、あるいはその溶液の繊維及び繊維製品への浸透性を高める為に界面活性剤を共存させることもできる。
界面活性剤としては、光照射による繊維及び繊維製品の改質を著しく阻害するものでなければ従来公知の界面活性剤の任意のものを使用できる。このような界面活性剤としては、たとえば、高級脂肪酸アルカリ塩、アルキル硫酸塩、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、スルホコハク酸エステル塩などの陰イオン界面活性剤、高級アミンハロゲン酸塩、ハロゲン化アルキルピリジニウム、第四アンモニウム塩などの陽イオン界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリドなどの非イオン界面活性剤、アミノ酸などの両性表面活性剤などが例示される。
In addition, a compound having a carbon-carbon double bond in which a compound that generates radicals by light irradiation and an electron-withdrawing group are directly bonded to a carbon atom that forms a carbon-carbon double bond, or a fiber and a fiber product of the solution In order to increase the permeability of the surfactant, a surfactant may be allowed to coexist.
As the surfactant, any conventionally known surfactant can be used as long as it does not significantly inhibit the modification of fibers and fiber products by light irradiation. Examples of such surfactants include anionic surfactants such as higher fatty acid alkali salts, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, higher amine halogenates, halogens, and the like. Illustrative examples include cationic surfactants such as alkyl pyridinium fluoride and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, and amphoteric surfactants such as amino acids. Is done.
また、これらの界面活性剤のいずれかを単独で用いてもよいが、複数の界面活性剤からなる混合物を用いることもできる。
また、それらの界面活性剤の溶液を用いることもできるが、このような溶媒としては、水、アルコール類、鎖状または環状の炭化水素類、エーテル類等の単独溶媒あるいはこれらの混合溶媒が挙げられる。界面活性剤の含有量は溶媒に対する界面活性剤の飽和濃度以下であれば特に制限はないが、好ましくは溶媒に対して、０．０００１〜５０重量％、より好ましくは０．０１〜１０重量％とするのが適当である。
Further, any of these surfactants may be used alone, but a mixture of a plurality of surfactants can also be used.
A solution of these surfactants can also be used. Examples of such a solvent include water, alcohols, chain or cyclic hydrocarbons, single solvents such as ethers, and mixed solvents thereof. It is done. The surfactant content is not particularly limited as long as it is equal to or lower than the saturation concentration of the surfactant with respect to the solvent, but is preferably 0.0001 to 50% by weight, more preferably 0.01 to 10% by weight, based on the solvent. Is appropriate.
つぎに、本発明方法を実施するための代表的な改質装置の幾つかを以下に例示するが、本装置はこれらに限定されるものではない。 Next, some typical reforming apparatuses for carrying out the method of the present invention are exemplified below, but the present apparatus is not limited to these.
図１の装置は、糸状または織物状の合成繊維を含む繊維や繊維製品を改質するために好ましく用いられる改質装置の例である。図１の装置の概要は、合成繊維を含む繊維や繊維製品の全体に、薬液槽で光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物を付与し、該繊維や繊維製品全体に光照射を行い、その後で洗浄槽に於いて過剰な薬液などを除去するものである。
この装置によれば、上記繊維または繊維製品を薬液に浸漬し、引き上げた所に光照射することができる。
The apparatus shown in FIG. 1 is an example of a reforming apparatus that is preferably used to modify a fiber or a fiber product containing a synthetic fiber in the form of a thread or a woven fabric. The outline of the apparatus shown in FIG. 1 is that a compound that generates radicals upon irradiation with light in a chemical tank and a carbon atom in which an electron-withdrawing group directly forms a carbon-carbon double bond in a fiber or a fiber product including synthetic fibers. A compound having a bonded carbon-carbon double bond is imparted, and the fiber or the entire fiber product is irradiated with light, and then an excessive chemical solution or the like is removed in a washing tank.
According to this apparatus, the fiber or the fiber product can be immersed in a chemical solution and irradiated to the place where it is pulled up.
図２の装置は、糸状または織物状の合成繊維を含む繊維や繊維製品の改質するために好ましく用いられる改質装置の他の例である。図２の装置は、合成繊維を含む繊維や繊維製品の全体に、薬液槽で光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物を付与し、光ビームにより該繊維や繊維製品の一部に光照射を行い、その後で洗浄槽に於いて過剰な薬液などを除去し、その後、還元処理槽で還元剤によって処理するものである。
この装置によれば、上記繊維または繊維製品を薬液に浸漬し、引き上げた所に光学系を用いて光ビームを動かす光照射を行うことにより、必要な箇所に任意のパターンを伴う改質が可能となる。還元剤で処理することによって、光照射時に発生したカルボニル基や過酸化物などの不安定物質をアルコールなどの安定した化合物に変換することができる。
The apparatus shown in FIG. 2 is another example of a reforming apparatus that is preferably used for modifying a fiber or a fiber product containing a synthetic fiber in the form of a thread or a woven fabric. In the apparatus of FIG. 2, a compound that generates radicals by light irradiation in a chemical solution tank and an electron-withdrawing group are directly bonded to carbon atoms forming a carbon-carbon double bond in a fiber or a fiber product including synthetic fibers. A compound having a carbon-carbon double bond is applied, and light or light is irradiated to a part of the fiber or fiber product, and then an excess chemical solution is removed in a washing tank, and then a reduction treatment tank. It treats with a reducing agent.
According to this device, the above-mentioned fiber or textile product is immersed in a chemical solution, and light irradiation is performed by moving the light beam using an optical system at the pulled-up position, so that modification with an arbitrary pattern is possible at a required location. It becomes. By treating with a reducing agent, unstable substances such as carbonyl groups and peroxides generated during light irradiation can be converted into stable compounds such as alcohol.
図３の装置は、糸状または織物状の合成繊維を含む繊維や繊維製品の改質するために好ましく用いられる改質装置の更に他の例である。図３の装置は、光照射によりラジカルを発生する化合物と電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物により満たされている薬液槽に、合成繊維を含む繊維や繊維製品を投入し、該薬液と合成繊維を含む繊維や繊維製品を撹拌しながら光照射を行うものである。
この装置によれば、上記繊維または繊維製品を薬液に浸漬し、必要に応じ薬液を注入しながら撹拌中で光照射を行うことにより、取り扱いが煩雑な小さな上記繊維または繊維製品の改質を容易とする。
The apparatus shown in FIG. 3 is still another example of a reforming apparatus that is preferably used for modifying a fiber or a fiber product containing a synthetic fiber in the form of a thread or a woven fabric. The apparatus of FIG. 3 is a chemical solution filled with a compound that generates radicals upon light irradiation and a compound having a carbon-carbon double bond in which an electron-withdrawing group is directly bonded to a carbon atom that forms a carbon-carbon double bond. A fiber or fiber product containing synthetic fiber is put into a tank, and light irradiation is performed while stirring the chemical solution and fiber or fiber product containing synthetic fiber.
According to this apparatus, it is easy to modify the above-mentioned small fiber or fiber product, which is difficult to handle, by immersing the fiber or fiber product in a chemical solution and performing light irradiation while stirring while injecting the chemical solution as necessary. And
図４の装置は、織物状又は成形された合成繊維を含む繊維や繊維製品の改質するために好ましく用いられる改質装置例である。図４の装置は、合成繊維を含む繊維や繊維製品の一部にスプレー等により光照射によりラジカルを発生する化合物を部分的に付与し、光ビームにより該繊維や繊維製品の一部に光照射を行い、その後で洗浄槽に於いて過剰な薬液などを除去した後、薬液槽で電子吸引性基が直接炭素−炭素二重結合を形成する炭素原子に結合した炭素−炭素二重結合を有する化合物による処理を行うものである。
この装置によれば、薬液を対象とする上記繊維または繊維製品に吹き付けてから光照射を行うため、光照射によりラジカルを発生する化合物の吹きつけにロボットアーム等の可動機能を付与することにより上記繊維または繊維製品の形態に関係なく必要な箇所に薬液を付与することができ、また、三次元的な光照射の制御を行うことにより、上記繊維または繊維製品の形態に関係なく必要な箇所の改質が可能となる。
The apparatus shown in FIG. 4 is an example of a reforming apparatus that is preferably used for modifying a fiber or a fiber product including a woven or molded synthetic fiber. The apparatus shown in FIG. 4 partially applies a compound that generates radicals by light irradiation to a part of a fiber or fiber product including synthetic fiber by spraying or the like, and irradiates a part of the fiber or fiber product by a light beam. After removing excess chemical solution in the washing tank, the electron-withdrawing group has a carbon-carbon double bond directly bonded to a carbon atom forming a carbon-carbon double bond in the chemical solution tank. A treatment with a compound is performed.
According to this apparatus, in order to perform light irradiation after spraying the above-mentioned fiber or fiber product targeted for a chemical solution, the above-mentioned function is given by adding a movable function such as a robot arm to spraying a compound that generates radicals by light irradiation. A chemical solution can be applied to a necessary place regardless of the form of the fiber or the fiber product, and by controlling the three-dimensional light irradiation, the necessary place can be obtained regardless of the form of the fiber or the fiber product. Modification is possible.
次に実施例に基づき、本発明を更に詳細に説明する。 Next, based on an Example, this invention is demonstrated still in detail.
実施例１
ポリエステル布を３ｍｏｌ／Ｌのアクリル酸と５％の過酸化水素を含む水溶液に含浸させ、引き上げた所に１５Ｗの低圧水銀灯照射を６０分行い、水、メタノール、水、中性洗剤、水の順で洗浄した後、一晩減圧乾燥した。得られた布を鑑別染料（カヤスティン）により染色したところ、未処理のポリエステル布と比べて光照射面は僅かな濃色化が起こったことより、ポリエステルの表面構造が変化しポリエステル布の改質が起きたことが判明したが、裏面は殆ど変化が無かった。
Example 1
A polyester cloth is impregnated with an aqueous solution containing 3 mol / L acrylic acid and 5% hydrogen peroxide. The pulled-up place is irradiated with a 15 W low-pressure mercury lamp for 60 minutes, followed by water, methanol, water, neutral detergent, and water. And then dried under reduced pressure overnight. When the resulting fabric was dyed with a differential dye (Kayastin), the light-irradiated surface slightly darkened compared to the untreated polyester fabric, resulting in a change in the surface structure of the polyester and modification of the polyester fabric. However, the back side was almost unchanged.
実施例２
ポリエステル布を０．９ｍｏｌ／Ｌのメタクリル酸と５％の過酸化水素を含む水溶液に含浸させ、引き上げた所に１５Ｗの低圧水銀灯照射を６０分行い、水、メタノール、水、中性洗剤、水の順で洗浄した後、一晩減圧乾燥した。得られた布を鑑別染料（カヤスティン）により染色したところ、未処理のポリエステル布と比べて光照射面は僅かな濃色化が起こったことより、ポリエステルの表面構造が変化しポリエステル布の改質が起きたことが判明したが、裏面は殆ど変化が無かった。
Example 2
A polyester cloth is impregnated with an aqueous solution containing 0.9 mol / L methacrylic acid and 5% hydrogen peroxide. The pulled-up place is irradiated with a 15 W low-pressure mercury lamp for 60 minutes, and water, methanol, water, neutral detergent, water After washing in this order, it was dried under reduced pressure overnight. When the resulting fabric was dyed with a differential dye (Kayastin), the light-irradiated surface slightly darkened compared to the untreated polyester fabric, resulting in a change in the surface structure of the polyester and modification of the polyester fabric. However, the back side was almost unchanged.
実施例３
ポリエステル布を０．０５ｍｏｌ／Ｌのフマール酸と５％の過酸化水素を含む水溶液に含浸させ、引き上げた所に１５Ｗの低圧水銀灯照射を６０分行い、水、メタノール、水、中性洗剤、水の順で洗浄した後、一晩減圧乾燥した。得られた布を鑑別染料（カヤスティン）により染色したところ、未処理のポリエステル布と比べて光照射面は顕著な濃色化が起こったことより、ポリエステルの表面構造が変化しポリエステル布の改質が起きたことが判明したが、裏面は殆ど変化が無かった。
Example 3
A polyester cloth is impregnated with an aqueous solution containing 0.05 mol / L fumaric acid and 5% hydrogen peroxide. The pulled-up place is irradiated with a 15 W low-pressure mercury lamp for 60 minutes, and water, methanol, water, neutral detergent, water After washing in this order, it was dried under reduced pressure overnight. When the resulting fabric was dyed with a differential dye (Kayastin), the light-irradiated surface was significantly darkened compared to the untreated polyester fabric, which changed the surface structure of the polyester and modified the polyester fabric. However, the back side was almost unchanged.
実施例４
ポリエステル布を０．３ｍｏｌ／Ｌのマレイン酸と５％の過酸化水素を含む水溶液に含浸させ、引き上げた所に１５Ｗの低圧水銀灯照射を６０分行い、水、メタノール、水、中性洗剤、水の順で洗浄した後、一晩減圧乾燥した。得られた布を鑑別染料（カヤスティン）により染色したところ、未処理のポリエステル布と比べて光照射面は僅かな濃色化が起こったことより、ポリエステルの表面構造が変化しポリエステル布の改質が起きたことが判明したが、裏面は殆ど変化が無かった。
Example 4
A polyester cloth is impregnated with an aqueous solution containing 0.3 mol / L maleic acid and 5% hydrogen peroxide, and the pulled-up place is irradiated with a 15 W low-pressure mercury lamp for 60 minutes. Water, methanol, water, neutral detergent, water After washing in this order, it was dried under reduced pressure overnight. When the resulting fabric was dyed with a differential dye (Kayastin), the light-irradiated surface slightly darkened compared to the untreated polyester fabric, resulting in a change in the surface structure of the polyester and modification of the polyester fabric. However, the back side was almost unchanged.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007237709A JP5152713B2 (en) | 2007-09-13 | 2007-09-13 | Method and apparatus for modifying synthetic fibers or fiber products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007237709A JP5152713B2 (en) | 2007-09-13 | 2007-09-13 | Method and apparatus for modifying synthetic fibers or fiber products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009068139A true JP2009068139A (en) | 2009-04-02 |
| JP5152713B2 JP5152713B2 (en) | 2013-02-27 |
Family
ID=40604696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007237709A Expired - Fee Related JP5152713B2 (en) | 2007-09-13 | 2007-09-13 | Method and apparatus for modifying synthetic fibers or fiber products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5152713B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009068145A (en) * | 2007-09-13 | 2009-04-02 | National Institute Of Advanced Industrial & Technology | Method for modifying fiber or fiber product and apparatus therefor |
| CN112160157A (en) * | 2020-08-20 | 2021-01-01 | 西安理工大学 | Hydrophilic polyester fiber and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57199866A (en) * | 1981-06-04 | 1982-12-07 | Teijin Ltd | Production of padding |
| JPH0284524A (en) * | 1988-07-20 | 1990-03-26 | Kanebo Ltd | Moisture absorption processing of woven and knitted fabric of wool |
| JPH04202865A (en) * | 1990-11-29 | 1992-07-23 | Toray Ind Inc | Production of colored yarn structure |
| JPH04308275A (en) * | 1990-12-20 | 1992-10-30 | Minnesota Mining & Mfg Co <3M> | Nonwoven polyester article and manufacture thereof |
| JPH08109228A (en) * | 1993-09-18 | 1996-04-30 | Hitoshi Kanazawa | Method of surface-modifying polymeric material |
| JPH11269759A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Treatment of polyester fiber |
| JPH11350350A (en) * | 1998-06-02 | 1999-12-21 | Teijin Ltd | Method for patterning polyester textile fabric |
| JP2006016719A (en) * | 2004-06-30 | 2006-01-19 | Daio Paper Corp | Method for producing absorptive composite |
| JP2008240171A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for photo-modifying synthetic fiber and apparatus therefor |
-
2007
- 2007-09-13 JP JP2007237709A patent/JP5152713B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57199866A (en) * | 1981-06-04 | 1982-12-07 | Teijin Ltd | Production of padding |
| JPH0284524A (en) * | 1988-07-20 | 1990-03-26 | Kanebo Ltd | Moisture absorption processing of woven and knitted fabric of wool |
| JPH04202865A (en) * | 1990-11-29 | 1992-07-23 | Toray Ind Inc | Production of colored yarn structure |
| JPH04308275A (en) * | 1990-12-20 | 1992-10-30 | Minnesota Mining & Mfg Co <3M> | Nonwoven polyester article and manufacture thereof |
| JPH08109228A (en) * | 1993-09-18 | 1996-04-30 | Hitoshi Kanazawa | Method of surface-modifying polymeric material |
| JPH11269759A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Treatment of polyester fiber |
| JPH11350350A (en) * | 1998-06-02 | 1999-12-21 | Teijin Ltd | Method for patterning polyester textile fabric |
| JP2006016719A (en) * | 2004-06-30 | 2006-01-19 | Daio Paper Corp | Method for producing absorptive composite |
| JP2008240171A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for photo-modifying synthetic fiber and apparatus therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009068145A (en) * | 2007-09-13 | 2009-04-02 | National Institute Of Advanced Industrial & Technology | Method for modifying fiber or fiber product and apparatus therefor |
| CN112160157A (en) * | 2020-08-20 | 2021-01-01 | 西安理工大学 | Hydrophilic polyester fiber and preparation method and application thereof |
| CN112160157B (en) * | 2020-08-20 | 2023-04-07 | 马孔多(北京)文化有限公司 | Hydrophilic polyester fiber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5152713B2 (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shahidi et al. | Surface modification methods for improving the dyeability of textile fabrics | |
| CN105980624B (en) | The corona treatment of coloring for textile | |
| WO2008057759A2 (en) | Treatment of fibrous materials using atmospheric pressure plasma polymerization | |
| CN103319747B (en) | Grafting treatment apparatus and grafting treatment method for battery diaphragm material | |
| JP5263752B2 (en) | Method and apparatus for modifying fiber or fiber product | |
| Samanta et al. | Environment-friendly textile processing using plasma and UV treatment | |
| JP5152713B2 (en) | Method and apparatus for modifying synthetic fibers or fiber products | |
| CN100453732C (en) | Method for bleaching fibrous articles | |
| JP5019439B2 (en) | Synthetic fiber photo-modification method and apparatus | |
| Eren et al. | Ozone: an alternative oxidant for textile applications | |
| JP4929180B2 (en) | Continuous fiber processing method and apparatus therefor | |
| Shahidi et al. | Radiation effects in textile materials | |
| JP5145491B2 (en) | Natural fiber photo-modification method and apparatus | |
| JP5019440B2 (en) | Photoreforming method and apparatus for recycled fiber | |
| JP7245619B2 (en) | Polarizing film manufacturing method and polarizing film manufacturing apparatus | |
| JP3265102B2 (en) | Cloth bleaching method and apparatus | |
| JP5246463B2 (en) | Method and apparatus for modifying cellulose and cellulose derivatives | |
| JPH1143862A (en) | Method and device for continuous bleaching of fabric | |
| Khalil et al. | Advanced Technology in Textile Dyeing | |
| Babu | Overview on Significant Approaches to Waterless Dyeing Technology | |
| JP7340325B2 (en) | Polarizing film manufacturing method and polarizing film manufacturing device | |
| Babu | 10 Overview on Significant | |
| KR20170120386A (en) | UV Photografting padding liquor and Method of dyeing using the same | |
| CS200578B1 (en) | Method of finishing webs,especially textile fabrics | |
| BR112016023817B1 (en) | Process for bleaching textile cloths with dye by treatment with a bleaching solution that more or less destroys the dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100317 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120119 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120124 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120326 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120911 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121031 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121120 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121126 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151214 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |