JP2007529647A - Dyeing of modacrylic / aramid fiber blend - Google Patents
Dyeing of modacrylic / aramid fiber blend Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8271—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide and nitrile groups
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/242—Polyamides; Polyurethanes using basic dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/76—Material containing nitrile groups using basic dyes
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
- D10B2321/101—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide modacrylic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Coloring (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
カチオン染料と染色助剤を利用するモダクリル繊維とアラミド繊維との混紡の染色方法は、染浴1リットル当り15g以下の染色助剤の濃度を採用する。 A dyeing method for blending modacrylic fiber and aramid fiber using a cationic dye and a dyeing aid employs a concentration of dyeing aid of 15 g or less per liter of dyeing bath.
Description
本発明はモダクリル/アラミド繊維混紡の染色に関する。 The present invention relates to the dyeing of modacrylic / aramid fiber blends.
本発明は、耐炎性だけでなく1つもしくはそれ以上の追加の特性を備える布帛に特に有用な繊維混紡の染色に関する。追加の特性の例として、電気アークに対する抵抗、レベルの高い引張強さおよび耐摩耗性が挙げられる。 The present invention relates to dyeing fiber blends that are particularly useful for fabrics that have not only flame resistance but also one or more additional properties. Examples of additional properties include resistance to electric arcs, high levels of tensile strength and wear resistance.
特許文献1(ソイロン(Soiron)ら)は、ケトンを形成するカルボニル基を含有しないキャリヤーとアニオン助剤を含有する水性媒体中で、カチオン染料で芳香族ポリアミド繊維を染色もしくは捺染するプロセスを開示する。 U.S. Patent No. 6,057,049 (Soiron et al.) Discloses a process for dyeing or printing aromatic polyamide fibers with a cationic dye in an aqueous medium containing a carrier that does not contain a carbonyl group that forms a ketone and an anion aid. .
特許文献2(ルンドスフォード(Lundsford)ら)は、選択された染色助剤を用いて、難燃性化合物を含有するセルロース繊維を含有する耐炎性の混紡布帛を染色するプロセスを開示する。 U.S. Patent No. 6,099,056 (Lundsford et al.) Discloses a process for dyeing flame resistant blended fabrics containing cellulose fibers containing flame retardant compounds using selected dyeing aids.
染色手順だけが原因である過度の繊維収縮も過度の剛さも伴わないで、耐炎性繊維の固有な混紡を染色することが必要とされる。 It is necessary to dye the inherent blend of flame resistant fibers without excessive fiber shrinkage or excessive stiffness due solely to the dyeing procedure.
本発明は、カチオン染料と染色助剤を用いて、モダクリル繊維とアラミド繊維の混紡を染色する方法に関し、モダクリル繊維およびアラミド繊維を基準として、モダクリル繊維は、1〜99重量%の範囲で存在し、アラミド繊維は、99〜1重量%の範囲で存在する。その方法は、
70〜100℃の範囲の温度で、カチオン染料および染浴1リットル当り15g以下の量で存在する染色助剤を含有する水性染浴と、繊維混紡を接触させる工程を含んでなり、前記染色助剤は、アリールエーテル、ベンジルアルコール、N−シクロヘキシルピロリドン、N,N−ジブチルホルムアミド、N,N−ジエチルベンズアミド、ヘキサデシルトリメチルアンモニウム塩、N,N−ジメチルベンズアミド、N,N−ジエチル−m−トルアミド、N−オクチルピロリドン、N,N−ジメチルカプリルアミドとN,N−ジメチルカプルアミドの混紡、およびそれらの混合物よりなる群から選択される。
The present invention relates to a method for dyeing a blend of modacrylic fiber and aramid fiber using a cationic dye and a dyeing assistant, and the modacrylic fiber is present in the range of 1 to 99% by weight based on the modacrylic fiber and the aramid fiber. The aramid fiber is present in the range of 99 to 1% by weight. The method is
Contacting the fiber blend with an aqueous dyebath containing a cationic dye and a dyeing assistant present in an amount of not more than 15 g per liter of dyebath at a temperature in the range of 70-100 ° C. Agents are aryl ether, benzyl alcohol, N-cyclohexylpyrrolidone, N, N-dibutylformamide, N, N-diethylbenzamide, hexadecyltrimethylammonium salt, N, N-dimethylbenzamide, N, N-diethyl-m-toluamide , N-octylpyrrolidone, a blend of N, N-dimethylcaprylamide and N, N-dimethylcapuramide, and mixtures thereof.
本発明の染色手順のための出発材料は、モダクリル繊維とアラミド繊維の混紡である。通例、上記混紡は、糸としてまたは布帛に形成される糸として存在する繊維で染色されうる。しかしながら、繊維の混紡が、糸もしくは布帛などに形成される前に、染色されることは、染色手順の範囲内である。 The starting material for the dyeing procedure of the present invention is a blend of modacrylic and aramid fibers. Typically, the blends can be dyed with fibers that exist as yarns or as yarns that are formed into a fabric. However, it is within the scope of the dyeing procedure that the fiber blend is dyed before it is formed into yarn or fabric.
出発材料の組成は、モダクリル成分およびアラミド成分を基準として、1〜99重量%のモダクリル繊維と99〜1%の重量%のアラミドを含んでなるモダクリル/アラミド混紡である。これらの2種の成分を基準とする好適な範囲の例は、40〜70重量%のモダクリル繊維、5〜20重量パーセントのp−アラミド繊維および10〜40重量%のm−アラミド繊維である。好適な範囲の上記の例が、結果として、耐電気アーク性および防炎性を提供する糸および布帛に有用な混紡となる。 The composition of the starting material is a modacrylic / aramid blend comprising 1 to 99% by weight modacrylic fiber and 99 to 1% by weight aramid, based on the modacrylic and aramid components. Examples of suitable ranges based on these two components are 40-70% by weight modacrylic fiber, 5-20% by weight p-aramid fiber and 10-40% by weight m-aramid fiber. A suitable range of the above examples results in a blend that is useful for yarns and fabrics that provide electrical arc resistance and flame resistance.
「糸」は、連続したストランドを形成するように、紡績されたまたは一緒に撚った繊維の集まりを意味し、それは、製織、製編、製紐、または組編に使用されることができ、或いは、織編生地もしくは布帛に作製されうる。 “Yarn” means a collection of fibers spun or twisted together to form a continuous strand, which can be used for weaving, knitting, stringing, or braiding Alternatively, it can be made into a woven or knitted fabric or fabric.
モダクリル繊維は、主にアクリロニトリルを含んでなるポリマーから作製されるアクリル系合成繊維を意味する。該ポリマーは、30〜70重量パーセントのアクリロニトリルと70〜30重量パーセントのハロゲン含有のビニルモノマーとを含んでなるコポリマーであるのが好ましい。ハロゲン含有のビニルモノマーは、例えば、塩化ビニル、塩化ビニリデン、臭化ビニル、臭化ビニリデンなどから選択される少なくとも1種のモノマーである。共重合性ビニルモノマーの例は、アクリル酸、メタクリル酸、それらの酸の塩もしくはエステル、アクリルアミド、メチルアクリルアミド、および酢酸ビニルである。 Modacrylic fiber means acrylic synthetic fiber made from a polymer mainly comprising acrylonitrile. The polymer is preferably a copolymer comprising 30 to 70 weight percent acrylonitrile and 70 to 30 weight percent halogen containing vinyl monomer. The halogen-containing vinyl monomer is at least one monomer selected from, for example, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, and the like. Examples of copolymerizable vinyl monomers are acrylic acid, methacrylic acid, salts or esters of those acids, acrylamide, methyl acrylamide, and vinyl acetate.
本発明の好適なモダクリル繊維は、アクリロニトリルと塩化ビニリデンを組み合わせたコポリマーであり、該コポリマーは、改善された難熱性のために、さらに1種のまたは数種の酸化アンチモンを有する。上記の有用なモダクリル繊維として、2重量パーセントの三酸化アンチモンを有する米国特許第3,193,602号明細書に開示される繊維、少なくとも2重量パーセント、好ましくは8重量パーセント以下の量で存在する種々の酸化アンチモンで作製される米国特許第3,748,302号明細書に開示される繊維、および8〜40重量パーセントのアンチモン化合物を有する米国特許第5,208,105号明細書および同第5,506,042号明細書に開示される繊維が挙げられるが、それらに限定されない。 The preferred modacrylic fiber of the present invention is a copolymer of acrylonitrile and vinylidene chloride in combination, which further has one or several antimony oxides for improved heat resistance. Useful modacrylic fibers as described above are present in US Pat. No. 3,193,602 having 2 weight percent antimony trioxide, present in an amount of at least 2 weight percent, preferably no more than 8 weight percent. U.S. Pat. No. 5,208,105 having fibers disclosed in U.S. Pat. No. 3,748,302 made with various antimony oxides and 8 to 40 weight percent antimony compound. Examples include, but are not limited to, the fibers disclosed in US Pat. No. 5,506,042.
本明細書で使用される「アラミド」は、少なくとも85%のアミド結合(−CONH−)が、2個の芳香族環に直接結合するポリアミドを意味する。添加剤が、アラミドと一緒に使用されることが可能であり、実際、ほぼ10重量パーセントまでの他の高分子材料が、アラミドと混紡されることが可能であり、或いは、アラミドのジアミンで置換されたほぼ10パーセントの他のジアミン、またはアラミドの二酸クロリドで置換されたほぼ10パーセントの他の二酸クロリドを有するコポリマーを使用することが可能であることが判明されている。適切なアラミド繊維は、W.ブラックらの「人造繊維−科学と技術」2巻、章題 繊維形成芳香族ポリアミド、297頁(インターサイエンス・パブリッシャー、1968年)(Man−Made Fibers−Science and Technology,Volume 2,Section titled Fiber−Forming Aromatic Polyamides, page 297, W. Black et al.,Interscience Publishers,1968)に記載されている。アラミド繊維は、さらに、米国特許第4,172,938号明細書、同第3,869,429号明細書、同第3,819,587号明細書、同第3,673,143号明細書、同第3,354,127号明細書、および同第3,094,511号明細書に開示されている。M−アラミドは、アミド結合が互いに対してメタ位にあるアラミドであり、p−アラミドは、アミド結合が互いに対してパラ位にあるアラミドである。本発明の実施において、最も多く使用されるアラミドは、ポリ(パラフェニレンテレフタルアミド)およびポリ(メタフェニレンイソフタルアミド)である。 “Aramid” as used herein refers to a polyamide in which at least 85% of the amide bonds (—CONH—) are directly bonded to two aromatic rings. Additives can be used with aramids, in fact, up to nearly 10 weight percent of other polymeric materials can be blended with aramids, or substituted with aramid diamines It has been found that it is possible to use copolymers with approximately 10 percent of other diamines made, or approximately 10 percent of other diacid chlorides substituted with aramid diacid chloride. Suitable aramid fibers are those described in W.W. Black et al., “Artificial Fibers-Science and Technology”, Volume 2, Title: Fiber-forming aromatic polyamides, 297 (Interscience Publisher, 1968) (Man-Made Fibers-Science and Technology, Volume 2, Section title Fiber- Forming Aromatic Polyamides, page 297, W. Black et al., Interscience Publishers, 1968). Aramid fibers are further described in U.S. Pat. Nos. 4,172,938, 3,869,429, 3,819,587, and 3,673,143. No. 3,354,127 and US Pat. No. 3,094,511. M-aramid is an aramid in which the amide bonds are in the meta position relative to each other, and p-aramid is an aramid in which the amide bonds are in the para position relative to each other. The most commonly used aramids in the practice of the present invention are poly (paraphenylene terephthalamide) and poly (metaphenylene isophthalamide).
1種もしくはそれ以上の追加の繊維もしくは成分が、モダクリル繊維およびアラミド繊維と一緒に含まれてもよいことが理解される。2つの例は、耐摩耗性繊維と、繊維として存在しうる帯電防止成分である。 It is understood that one or more additional fibers or components may be included along with modacrylic fibers and aramid fibers. Two examples are anti-wear fibers and antistatic components that can exist as fibers.
耐摩耗性は、表面研削および摩耗に耐性がある繊維または布帛の能力を意味する。耐摩耗性繊維は、ナイロンであるのが好ましい。ナイロンとは、脂肪族ポリアミドポリマーから作られる繊維を意味し、ポリヘキサメチレンアジパミド(ナイロン66)は、好適なナイロンポリマーである。他のナイロン(例、ポリカプロラクタム(ナイロン6)、ポリブチロラクタム(ナイロン4)、ポリ(9−アミノノナン酸)(ナイロン9)、ポリエナントラクタム(ナイロン7)、ポリカプリルラクタム(ナイロン8)、ポリヘキサメチレンセバカミド(ナイロン6,10)など)は、適切である。耐摩耗性繊維は、存在する場合、通常、上記糸の2〜15重量パーセントを含んでなる。 Abrasion resistance refers to the ability of a fiber or fabric to resist surface grinding and abrasion. The abrasion resistant fiber is preferably nylon. Nylon means a fiber made from an aliphatic polyamide polymer, and polyhexamethylene adipamide (nylon 66) is a suitable nylon polymer. Other nylons (eg, polycaprolactam (nylon 6), polybutyrolactam (nylon 4), poly (9-aminononanoic acid) (nylon 9), polyenantolactam (nylon 7), polycapryl lactam (nylon 8), Polyhexamethylene sebacamide (such as nylon 6,10) is suitable. Abrasion resistant fibers, when present, typically comprise 2 to 15 weight percent of the yarn.
帯電防止成分の実例としては、スチール繊維、炭素繊維、または既存の繊維への炭素被覆である。炭素または金属(例、スチール等)の伝導性は、糸、布帛、または衣服に組み込まれた場合、静電気の連続的発生の防止を助けるように電気管路を提供する。静電気放電は、感度の高い電気設備で或いは可燃性蒸気の付近で作業する作業者にとって、危険となりうる。帯電防止成分は、使用されるならば、糸全体の1〜5重量パーセントの量で存在してもよい。 Illustrative examples of antistatic components are steel fibers, carbon fibers, or carbon coatings on existing fibers. The conductivity of carbon or metal (eg, steel, etc.) provides an electrical conduit to help prevent continuous generation of static electricity when incorporated into yarns, fabrics, or clothes. Electrostatic discharge can be dangerous for workers working in sensitive electrical equipment or near flammable vapors. If used, the antistatic component may be present in an amount of 1 to 5 weight percent of the total yarn.
本発明の糸は、当技術分野で一般的に知られている任意の紡糸技術、これに限定されないが、リング精紡、芯紡糸、およびエアジェット紡糸またはさらに高度な空気精紡技術(例、空気を用いて、ステープルファイバーを糸に撚る村田エアジェット精紡機など)により、製造されうる。通常、任意の一般的な技術により製造される単糸は、次に、布帛に変えられる前に、一緒に諸撚りされ、少なくとも2本の単糸を含んでなる諸撚糸を形成する。 The yarns of the present invention may be any spinning technique commonly known in the art, including but not limited to ring spinning, core spinning, and air jet spinning or more advanced air spinning techniques (e.g., Murata Air Jet Spinning Machine, etc., which uses air to twist staple fibers into yarn. Typically, a single yarn produced by any common technique is then twisted together to form a twisted yarn comprising at least two single yarns before being converted to a fabric.
用語「布帛」は、製織された、製編された、または1種もしくはそれ以上の別の種類の本発明の糸を用いて組み立てられた1つの層を意味する。布帛が、織布であるのが好ましい。本発明の布帛が、綾織であるのが最も好ましい。 The term “fabric” means a layer that is woven, knitted, or assembled with one or more other types of yarns of the present invention. The fabric is preferably a woven fabric. Most preferably, the fabric of the present invention is a twill.
耐炎性布帛の染色は、従来技術において公知である。しかしながら、本発明において、臨界が、キャリヤーを有するカチオン染料の使用において存在する。 The dyeing of flame resistant fabrics is known in the prior art. However, in the present invention, criticality exists in the use of cationic dyes with carriers.
カチオン染料の適切な開示は、米国特許第4,066,395号明細書に示される。カチオン染料として、慣例上、塩、塩化物、サルフェートまたは金属ハロゲン化物が挙げられ、例えば、塩化亜鉛、そのカチオン性が例えばカルボニウム、オキソニウム、スルホニウムまたはアンモニウム基に由来する塩である。発色団系の例は、アゾ染料、主にモノアゾまたはヒドラゾン染料、ジフェニルメタン、トリフェニルメタン、メチンまたはアゾメチン染料、クマリン、ケトン−イミン、シアニン、キサンテン、アジン、オキサジンまたはチアジン染料である。フタロシアニンまたは外(external)のオニウム基(例えばアルキルアンモニウムまたはシクロアンモニウム基)を有するアントラキノン系の染料塩、さらにシクロアンモニウム基を含有するベンゾ−1,2−ピラン染料塩の使用も可能である。上記の染料の混合物も使用されうる。 A suitable disclosure of cationic dyes is given in US Pat. No. 4,066,395. Cationic dyes conventionally include salts, chlorides, sulfates or metal halides, such as zinc chloride, salts whose cationic properties are derived from, for example, carbonium, oxonium, sulfonium or ammonium groups. Examples of chromophore systems are azo dyes, mainly monoazo or hydrazone dyes, diphenylmethane, triphenylmethane, methine or azomethine dyes, coumarins, ketone-imines, cyanines, xanthenes, azines, oxazines or thiazine dyes. It is also possible to use phthalocyanine or an anthraquinone dye salt having an external onium group (for example, an alkylammonium or cycloammonium group), and a benzo-1,2-pyran dye salt containing a cycloammonium group. Mixtures of the above dyes can also be used.
本発明において必要な成分は、染色助剤である。適切な染色助剤は、米国特許第6,547,835号明細書に開示されている。具体的には、これらの染色助剤は、N−シクロヘキシルピロリドン、ベンジルアルコール、N,N−ジブチルホルムアミド、N,N−ジエチルベンズアミド、ヘキサデシルトリメチルアンモニウム塩、N,N−ジメチルベンズアミド、N,N−ジエチル−m−トルアミド、N−オクチルピロリドン、アリールエーテル、N,N−ジメチルカプリルアミドとN,N−ジメチルカプルアミドのおよそ50/50の混紡、およびそれらの混合物である。 A necessary component in the present invention is a dyeing assistant. Suitable dyeing aids are disclosed in US Pat. No. 6,547,835. Specifically, these dyeing assistants include N-cyclohexylpyrrolidone, benzyl alcohol, N, N-dibutylformamide, N, N-diethylbenzamide, hexadecyltrimethylammonium salt, N, N-dimethylbenzamide, N, N -Diethyl-m-toluamide, N-octylpyrrolidone, aryl ether, approximately 50/50 blend of N, N-dimethylcaprylamide and N, N-dimethylcapuramide, and mixtures thereof.
水性浴中におけるカチオン染料と染色助剤での染色は、従来型の方法で行われうる。通常、上記染色は、70℃〜100℃の温度範囲で行われる。 Dyeing with cationic dyes and dyeing assistants in an aqueous bath can be done in a conventional manner. Usually, the said dyeing | staining is performed in the temperature range of 70 to 100 degreeC.
しかしながら、上記染色助剤が染浴1リットル当り15g以下の濃度で存在することは、本発明において、決定的である。好適な濃度は、1リットル当り12g以下、さらに好ましくは1リットル当り10g以下である。1リットル当り5g未満などのさらに低い濃度の染色助剤は、他の全ての染色法の条件が同一に維持されると仮定すると、さらに長い染色時間を意味する。 However, it is crucial in the present invention that the dyeing assistant is present at a concentration of 15 g or less per liter of dyeing bath. A suitable concentration is 12 g or less per liter, more preferably 10 g or less per liter. Lower concentrations of dyeing aids, such as less than 5 g per liter, mean longer dyeing times, assuming that all other dyeing conditions remain the same.
過度の量の染色キャリヤーは、2つの望ましくない特性を生じる結果となりうる。第一の特性は、糸および布帛の過度の収縮である。第二の特性は、糸および布帛の過度の剛さである。 Excessive amount of dye carrier can result in two undesirable properties. The first property is excessive shrinkage of the yarn and fabric. The second property is excessive stiffness of the yarn and fabric.
以下の実施例において、全ての部およびパーセントは、特に明記しない限り、重量部および重量パーセントであり、温度は、摂氏である。 In the following examples, all parts and percentages are parts by weight and percentages by weight unless otherwise specified, and temperatures are in degrees Celsius.
従来の方法におけるハンガー(Hunger)「L」、「a」、および「b」値を測定して、実施例の色彩および染色濃度を決定した。「L」色彩成分は、試料の黒さまたは白さの指標であり、「a」値は、試料の色が赤から緑の範囲内での指標であり、「b」値は、試料の色が青から黄色の範囲内での指標である。 Hunger “L”, “a”, and “b” values in a conventional method were measured to determine the color and staining density of the examples. The “L” color component is an index of the blackness or whiteness of the sample, the “a” value is an index when the color of the sample is in the range from red to green, and the “b” value is the color of the sample. Is an indicator in the range from blue to yellow.
一工程の浴プロセスにおいて、染料と染色助剤を用いて、70重量パーセントのモダクリル繊維、15重量パーセントのメタ−アラミド繊維、5重量パーセントのパラ−アラミド繊維、および10重量パーセントのナイロン繊維を含んでなる布帛を染色した。 In a one-step bath process, using dyes and dyeing assistants, including 70 weight percent modacrylic fiber, 15 weight percent meta-aramid fiber, 5 weight percent para-aramid fiber, and 10 weight percent nylon fiber The fabric consisting of was dyed.
工業用の染色プロセスに関して、以下の手順を記載する。しかしながら、以下にさらに説明される通り、上記の工業用染色プロセスが、さらに小型の染色装置のため、修正される。 The following procedure is described for an industrial dyeing process. However, as described further below, the above industrial dyeing process is modified for a more compact dyeing apparatus.
圧力ジェット染色槽に布帛を入れ、その染色槽内で、布帛は、布帛の端を一緒に縫い合わせることにより実現した連続ループで、開口ベンチュリ内を循環する。1リットル当り0.5gのメルポール(Merpol)(登録商標)HCS界面活性剤の水性溶液中で、60℃で10分間、布帛を精錬する。精錬後、染色槽の排水を行い、初期温度70℃で、染料、染色助剤、および水で染色槽を満たす。1分間に1℃の割合で浴温を上昇させながら、その布帛を10分間染色する。次に、酢酸を添加して、その溶液のpHをpH3〜4に調節する。その後、槽を追加の染料と染色助剤で満たし、80℃の一定温度を10分間保った後、浴温が98℃になるまで、1分間に1℃の割合で、温度を上昇させる。60分間、或いは染料を使い果たすまで、浴を98℃に保つ。その後、浴を60℃まで冷却させ、排水を行う。次に、1リットル当り2gのヒドロ亜硫酸ナトリウム、1リットル当り2gの炭酸ナトリウム、および水の溶液で槽を満たし、溶液を中和させる。浴温を1分間に1℃の割合で温度を60℃まで上昇させ、10分間循環させる。その後、槽の排水を行い、再び水を満たした後、水温を1分間に1℃の割合で60℃まで上昇させ、10分間循環させる。槽の排水を行い、布帛を乾燥させる。 The fabric circulates in the open venturi in a continuous loop realized by placing the fabric in a pressure jet dyeing bath and stitching the ends of the fabric together. The fabric is smelted in an aqueous solution of 0.5 g Merpol® HCS surfactant per liter at 60 ° C. for 10 minutes. After refining, the dyeing tank is drained, and the dyeing tank is filled with dye, dyeing assistant, and water at an initial temperature of 70 ° C. The fabric is dyed for 10 minutes while increasing the bath temperature at a rate of 1 ° C. per minute. Next, acetic acid is added to adjust the pH of the solution to pH 3-4. The bath is then filled with additional dye and dyeing aid and kept at a constant temperature of 80 ° C. for 10 minutes, then the temperature is increased at a rate of 1 ° C. per minute until the bath temperature reaches 98 ° C. The bath is kept at 98 ° C. for 60 minutes or until the dye is exhausted. Thereafter, the bath is cooled to 60 ° C. and drained. The bath is then filled with a solution of 2 g sodium hydrosulfite per liter, 2 g sodium carbonate per liter, and water to neutralize the solution. The bath temperature is increased to 60 ° C. at a rate of 1 ° C. per minute and circulated for 10 minutes. Then, after draining the tank and refilling it with water, the water temperature is increased to 60 ° C. at a rate of 1 ° C. per minute and circulated for 10 minutes. Drain the tank and dry the fabric.
下のデータを生成するために、さらに小型の染料器具を使用した。すなわち、アヒバ・ポルマット(Ahiba Polmat)ステンレス鋼キャニスター染料ユニット(カーボワックスの熱媒体を有する)を使用した。 A smaller dye apparatus was used to generate the data below. That is, an Ahiba Polmat stainless steel canister dye unit (having a carbowax heating medium) was used.
使用した染料は、
ビオクリルブルー(Viocryl Blue)RLS染料(ci−41) 布帛重量の0.6%
ビオクリルレッド(Viocryl Red)AGL染料(ci−29) 布帛重量の0.75%
ビオクリル(Yorocryl Yellow)6GL(ci−21) 布帛重量の0.15%であった。
The dye used was
Biocryl Blue RLS dye (ci-41) 0.6% of fabric weight
Biocryl Red AGL dye (ci-29) 0.75% of fabric weight
Biocryl Yellow 6GL (ci-21) It was 0.15% of the fabric weight.
上記に記載した布帛を、60℃で、布帛重量の0.5%でメルポール(Merpol)HCSと、布帛重量の3%でセコゲン(Cekogen)OX(酸化剤)を用いて、20分間前精錬した後、冷却し、排水し、水ですすいだ。 The fabric described above was pre-refined at 60 ° C. for 20 minutes using Merpol HCS at 0.5% of the fabric weight and Sekogen OX (oxidizer) at 3% of the fabric weight. After cooling, draining and rinsing with water.
98℃の最終温度で、60分間、布帛を染色した。1分間に約1℃の温度上昇で最終温度を達成した。染浴のpHは、約3〜4であった。アリールエーテルまたはベンジルアルコールを1リットル当り2、5、10、15、20および30gの量で使用した。染浴を約60℃まで冷却させ、排水した。 The fabric was dyed for 60 minutes at a final temperature of 98 ° C. The final temperature was achieved with a temperature increase of about 1 ° C. per minute. The pH of the dye bath was about 3-4. Aryl ether or benzyl alcohol was used in amounts of 2, 5, 10, 15, 20 and 30 g per liter. The dyebath was cooled to about 60 ° C. and drained.
染料溶液(2g/Lでヒドロ亜硫酸ナトリウムと炭酸ナトリウム)を中和させるために、染色した布帛を還元剤で、60℃で、20分間後精錬した後、溶液を冷却させ、排水した。 In order to neutralize the dye solution (sodium hydrosulfite and sodium carbonate at 2 g / L), the dyed fabric was post-refined with a reducing agent at 60 ° C. for 20 minutes, and then the solution was cooled and drained.
水分テラーユニット(moisture teller unit)内で熱風送風機を用いて、染色した布帛を乾燥させた。 The dyed fabric was dried using a hot air blower in a moisture teller unit.
以下のデータは、アリールエーテルとベンジルアルコールの染色助剤の様々な量での、布帛面積の%における収縮を表す。 The following data represents the shrinkage in% of fabric area for various amounts of aryl ether and benzyl alcohol dyeing aids.
高パーセントの染色助剤で染色した場合、布帛は、過度の収縮を示した。 When dyed with a high percentage of dyeing aid, the fabric exhibited excessive shrinkage.
20g/Lを超える染色助剤を使用した場合、布帛は、堅くなった。染料の取り込みは、以下の表の色測定により示唆される如く、高パーセントの染色助剤により、悪影響を受ける。 When dyeing aids above 20 g / L were used, the fabric became stiff. Dye uptake is adversely affected by high percentages of dyeing aids, as suggested by the color measurements in the table below.
Claims (11)
70〜100℃の範囲の温度で、カチオン染料および染浴1リットル当り15g以下の量で存在する染色助剤を含有する水性染浴と、繊維混紡を接触させる工程を含んでなり、染色助剤は、アリールエーテル、ベンジルアルコール、N−シクロヘキシルピロリドン、N,N−ジブチルホルムアミド、N,N−ジエチルベンズアミド、ヘキサデシルトリメチルアンモニウム塩、N,N−ジメチルベンズアミド、N,N−ジエチル−m−トルアミド、N−オクチルピロリドン、N,N−ジメチルカプリルアミドとN,N−ジメチルカプルアミドの混紡、およびそれらの混合物よりなる群から選択される方法。 A method for dyeing blends of modacrylic fibers and aramid fibers using a cationic dye and a dyeing assistant, wherein the modacrylic fibers are present in the range of 1 to 99% by weight based on the modacrylic fibers and the aramid fibers. Is present in the range of 99-1% by weight,
A dyeing aid comprising the step of contacting the fiber blend with an aqueous dyeing bath containing a cationic dye and a dyeing aid present in an amount of not more than 15 g per liter of dyeing bath at a temperature in the range of 70-100 ° C. Are aryl ether, benzyl alcohol, N-cyclohexylpyrrolidone, N, N-dibutylformamide, N, N-diethylbenzamide, hexadecyltrimethylammonium salt, N, N-dimethylbenzamide, N, N-diethyl-m-toluamide, A method selected from the group consisting of N-octylpyrrolidone, a blend of N, N-dimethylcaprylamide and N, N-dimethylcapuramide, and mixtures thereof.
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US10/803,382 US20050204487A1 (en) | 2004-03-18 | 2004-03-18 | Dyeing of modacrylic/aramid fiber blends |
PCT/US2005/008883 WO2006001857A2 (en) | 2004-03-18 | 2005-03-16 | Dyeing of modacrylic/aramid fiber blends |
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JP (1) | JP2007529647A (en) |
KR (1) | KR20060125901A (en) |
CN (1) | CN1934310A (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011149125A (en) * | 2010-01-21 | 2011-08-04 | Teijin Techno Products Ltd | Method for dyeing aramid textile fabric |
JP2015520808A (en) * | 2012-05-03 | 2015-07-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Process for obtaining low-residue aramid materials |
JP2020026595A (en) * | 2018-08-16 | 2020-02-20 | 帝人株式会社 | Fabric and protection product |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH707467B1 (en) | 2005-09-13 | 2014-07-15 | Lvmh Swiss Mft Sa | Watch with multifunctional display. |
US20080153372A1 (en) * | 2006-04-20 | 2008-06-26 | Southern Mills | Insect-Repellant Fabrics and Methods for Making Them |
CN100425759C (en) * | 2006-07-13 | 2008-10-15 | 吴江德伊时装面料有限公司 | Dyeing method of aramid fiber cloth |
JP2010502858A (en) * | 2006-09-08 | 2010-01-28 | サザンミルズ インコーポレイテッド | Method and system for providing stretchable and flame retardant dyed fabrics and garments |
WO2009089155A2 (en) | 2008-01-04 | 2009-07-16 | Southern Mills, Inc. | Flame resistant fabrics having improved resistance to surface abrasion or pilling and methods for making them |
US7744999B2 (en) * | 2008-07-11 | 2010-06-29 | E. I. Du Pont De Nemours And Company | Crystallized meta-aramid blends for improved flash fire and arc protection |
US8069642B2 (en) * | 2009-06-02 | 2011-12-06 | E.I. Du Pont De Nemours And Company | Crystallized meta-aramid blends for improved flash fire and superior arc protection |
KR101144261B1 (en) * | 2009-12-14 | 2012-05-11 | 지오콘다 주식회사 | Method for Preparing the Denim Fabric Consisting of Aramide Yarn |
US20120003472A1 (en) * | 2010-06-30 | 2012-01-05 | Coats American Inc. | Flame-resistant yarn |
GB2487553A (en) * | 2011-01-26 | 2012-08-01 | Nobel Biocare Services Ag | Locking device for dental components |
CN104721982A (en) * | 2015-03-06 | 2015-06-24 | 蔡晋晖 | Strap of fire protection trousers |
US10760189B2 (en) * | 2016-04-22 | 2020-09-01 | General Recycled | Protective fabric and process of manufacturing same |
US10253435B2 (en) * | 2016-09-01 | 2019-04-09 | E I Du Pont De Nemours And Company | Carbon-containing fiber blends including aramid and modacrylic fiber |
EP3536836B1 (en) * | 2016-11-01 | 2022-07-27 | Teijin Limited | Fabric, method for manufacturing same, and fiber product |
KR101962283B1 (en) * | 2017-08-10 | 2019-03-26 | 다이텍연구원 | Two bath dyeing method for modacrylic/meta-aramid/cotton blended fibers |
EP4152991A1 (en) * | 2020-05-20 | 2023-03-29 | Glen Raven, Inc. | Yarns and fabrics including elastomeric filaments |
US11946173B2 (en) | 2020-05-20 | 2024-04-02 | Glen Raven, Inc. | Yarns and fabrics including modacrylic fibers |
US20230175173A1 (en) * | 2020-05-20 | 2023-06-08 | Glen Raven, Inc. | Fabrics including a single-ply yarn and/or having low picks per inch or low courses per inch |
WO2022129486A1 (en) * | 2020-12-18 | 2022-06-23 | Archroma Ip Gmbh | Printing of fiber blends, woven and non-woven or knit fabric |
WO2022235999A1 (en) * | 2021-05-07 | 2022-11-10 | Glen Raven, Inc. | High visibility yarns and fabrics and methods relating thereto |
KR20230077150A (en) | 2021-11-25 | 2023-06-01 | 대한방직 주식회사 | Process Of Dyeing Fabrics Containing Modacrylic Fiber For Industrial Safety Clothings |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5178885A (en) * | 1974-12-02 | 1976-07-09 | Ciba Geigy | |
JPH04257376A (en) * | 1990-09-28 | 1992-09-11 | Springs Ind Inc | Method for dyeing fiber material |
US5306312A (en) * | 1990-10-31 | 1994-04-26 | Burlington Industries, Inc. | Dye diffusion promoting agents for aramids |
JPH073662A (en) * | 1990-05-18 | 1995-01-06 | Springs Ind Inc | Method for dyeing of textile material |
JPH1060787A (en) * | 1996-08-12 | 1998-03-03 | Kanebo Ltd | Production of cotton, sliver and fibrous product containing para-based aramide fiber |
US6547835B1 (en) * | 1998-04-20 | 2003-04-15 | Southern Mills, Inc. | Flame and shrinkage resistant fabric blends and method for making same |
JP2003201643A (en) * | 2002-01-07 | 2003-07-18 | Teijin Ltd | Highly flame-retardant dyed textile structural product |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3094511A (en) * | 1958-11-17 | 1963-06-18 | Du Pont | Wholly aromatic polyamides |
US3193602A (en) * | 1962-08-13 | 1965-07-06 | Monsanto Co | Process for the production of flame retarded acrylic fibers |
US3354127A (en) * | 1966-04-18 | 1967-11-21 | Du Pont | Aromatic copolyamides |
US3819587A (en) * | 1969-05-23 | 1974-06-25 | Du Pont | Wholly aromatic carbocyclic polycarbonamide fiber having orientation angle of less than about 45{20 |
US3673143A (en) * | 1970-06-24 | 1972-06-27 | Du Pont | Optically anisotropic spinning dopes of polycarbonamides |
US3869429A (en) * | 1971-08-17 | 1975-03-04 | Du Pont | High strength polyamide fibers and films |
US3748302A (en) * | 1971-11-17 | 1973-07-24 | Du Pont | Flame-retarded acrylonitrile fibers |
CH556943A (en) * | 1972-10-23 | 1974-12-13 | ||
JPS53294A (en) * | 1976-06-23 | 1978-01-05 | Teijin Ltd | Preparation of aromatic polyamide with high degree of polymerization |
US5208105A (en) * | 1984-10-05 | 1993-05-04 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Flame-retarded composite fiber |
EP0183014B1 (en) * | 1984-10-05 | 1994-02-02 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Flame-retarded fiber blend |
US6787228B2 (en) * | 2001-05-09 | 2004-09-07 | Glen Raven, Inc. | Flame-resistant and high visibility fabric and apparel formed therefrom |
US6946412B2 (en) * | 2001-05-09 | 2005-09-20 | Glen Raven, Inc. | Flame-resistant, high visibility, anti-static fabric and apparel formed therefrom |
-
2004
- 2004-03-18 US US10/803,382 patent/US20050204487A1/en not_active Abandoned
-
2005
- 2005-03-16 EP EP05795136A patent/EP1725709A2/en not_active Withdrawn
- 2005-03-16 KR KR1020067019021A patent/KR20060125901A/en not_active Application Discontinuation
- 2005-03-16 BR BRPI0508163-7A patent/BRPI0508163A/en not_active IP Right Cessation
- 2005-03-16 CA CA002557379A patent/CA2557379A1/en not_active Abandoned
- 2005-03-16 JP JP2007504099A patent/JP2007529647A/en active Pending
- 2005-03-16 CN CNA2005800087574A patent/CN1934310A/en active Pending
- 2005-03-16 WO PCT/US2005/008883 patent/WO2006001857A2/en not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5178885A (en) * | 1974-12-02 | 1976-07-09 | Ciba Geigy | |
JPH073662A (en) * | 1990-05-18 | 1995-01-06 | Springs Ind Inc | Method for dyeing of textile material |
JPH04257376A (en) * | 1990-09-28 | 1992-09-11 | Springs Ind Inc | Method for dyeing fiber material |
US5306312A (en) * | 1990-10-31 | 1994-04-26 | Burlington Industries, Inc. | Dye diffusion promoting agents for aramids |
JPH1060787A (en) * | 1996-08-12 | 1998-03-03 | Kanebo Ltd | Production of cotton, sliver and fibrous product containing para-based aramide fiber |
US6547835B1 (en) * | 1998-04-20 | 2003-04-15 | Southern Mills, Inc. | Flame and shrinkage resistant fabric blends and method for making same |
JP2003201643A (en) * | 2002-01-07 | 2003-07-18 | Teijin Ltd | Highly flame-retardant dyed textile structural product |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011149125A (en) * | 2010-01-21 | 2011-08-04 | Teijin Techno Products Ltd | Method for dyeing aramid textile fabric |
JP2015520808A (en) * | 2012-05-03 | 2015-07-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Process for obtaining low-residue aramid materials |
JP2020026595A (en) * | 2018-08-16 | 2020-02-20 | 帝人株式会社 | Fabric and protection product |
Also Published As
Publication number | Publication date |
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CN1934310A (en) | 2007-03-21 |
KR20060125901A (en) | 2006-12-06 |
BRPI0508163A (en) | 2007-08-07 |
WO2006001857A2 (en) | 2006-01-05 |
CA2557379A1 (en) | 2006-01-05 |
WO2006001857A3 (en) | 2006-04-06 |
EP1725709A2 (en) | 2006-11-29 |
US20050204487A1 (en) | 2005-09-22 |
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