JP2008013877A

JP2008013877A - Acrylic synthetic fiber excellent in dyeability

Info

Publication number: JP2008013877A
Application number: JP2006186182A
Authority: JP
Inventors: Masaaki Miyoshi; 正明三好; Sohei Nishida; 宗平西田
Original assignee: Kaneka Corp
Current assignee: Kaneka Corp
Priority date: 2006-07-06
Filing date: 2006-07-06
Publication date: 2008-01-24

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic synthetic fiber which is processed into piles forming easily extendable crimps and excellent in processability and hand, and can be dyed at low temperature. <P>SOLUTION: This acrylic synthetic fiber is produced by wet-spinning a polymer composition including an acrylonitrile-based polymer having a small content of a sulfonic group-containing monomer and a polymer having a large content of the sulfonic group-containing monomer. The acrylic synthetic fiber can be dyed at a low temperature of 60 to 90°C, and prevents thermal crimp set, when dyed. The fibers are used to form a pile fabric which easily extends crimps, when processed into piles, and is excellent in processability and hand. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、低温で染色可能なアクリル系合成繊維に関し、さらに詳しくは、低温で染色可能なことから、パイル布帛の製造に用いた際にクリンプが伸び易く加工性がよく、また風合に優れたパイル布帛を得ることができるアクリル系合成繊維及びこのアクリル系合成繊維から製造されるパイル布帛に関するものである。 The present invention relates to an acrylic synthetic fiber that can be dyed at a low temperature, and more specifically, since it can be dyed at a low temperature, when used in the manufacture of a pile fabric, the crimp is easy to stretch and has good workability and excellent texture. The present invention relates to an acrylic synthetic fiber from which a pile fabric can be obtained and a pile fabric produced from the acrylic synthetic fiber.

アクリル系合成繊維は、そのソフト感等の風合及び加工の容易さから、ハイパイル、ボアー、シール、フリース等のパイル分野に広く使用されている。このアクリル系合成繊維はパイルのデザイン等に応じて、様々な色に染色されて使用されることが多い。染色の方法としては、例えば紡糸原液に着色剤を添加する、いわゆる原液着色等の紡糸工程において着色する方法、紡糸後、所定の長さに切断した短繊維をオーバーマイヤー染色機等により染色する方法、パイルの原反を浸染あるいは捺染する方法などがある。これらの染色方法の中でも、短繊維を染色する方法が、少量で多彩なデザインに対応しやすいことから、よく利用されている。しかし、この染色方法は、少量で多彩なデザインに対応しやすい反面、クリンプを付与して切断した後の短繊維を染色するものであることから、染色時の加熱によりクリンプがセット（クリンプ形状が固定）され、パイル仕上げ工程でクリンプが伸びにくく、良好な風合のものが得られにくいという欠点があった。それを改良するべく、紡糸における延伸を紡糸浴及び水洗浴のみで行い、さらに２０〜２５％の弛緩熱処理を行う方法が提案されている（特許文献１参照。）。しかしこの方法は、高い緩和率を必要とするため、生産性が低下する等の欠点があった。また、スルホン酸基含有モノマーを多く含有する重合体を原料とし、通常、沸騰に近い温度で行う染色を低温で行い、クリンプがセットされるのを抑える方法が提案されている（特許文献２）。しかし、単にスルホン酸基含有モノマーの含有量を増やしただけでは低温での染色性の向上は期待できず、しかも低温での染色性を向上させるべくスルホン酸基含有モノマーの含有量をあまり多くすると繊維の製造コストが高くなるうえ、紡糸性が低下するという問題もあった。
特開平１１−３１５４１６号公報特開２００３−６４５６０号公報 Acrylic synthetic fibers are widely used in pile fields such as high piles, bores, seals, and fleeces due to their soft feel and ease of processing. This acrylic synthetic fiber is often used after being dyed in various colors according to the design of the pile. As a dyeing method, for example, a colorant is added to a spinning stock solution, a method of coloring in a spinning process such as so-called stock solution coloring, a method of dyeing short fibers cut to a predetermined length after spinning with an overmeier dyeing machine, etc. There are also methods such as dyeing or printing the original pile. Among these dyeing methods, the method of dyeing short fibers is often used because it is easy to deal with various designs with a small amount. However, this dyeing method is easy to deal with a variety of designs in a small amount, but on the other hand, because the short fibers after being cut by applying a crimp are dyed, the crimp is set by heating at the time of dyeing (the crimp shape is Fixed) and the crimp finishing process is difficult to extend, and it is difficult to obtain a good texture. In order to improve this, there has been proposed a method in which stretching in spinning is performed only in a spinning bath and a washing bath, and a relaxation heat treatment of 20 to 25% is further performed (see Patent Document 1). However, since this method requires a high relaxation rate, there are drawbacks such as a reduction in productivity. Further, a method has been proposed in which a polymer containing a large amount of sulfonic acid group-containing monomers is used as a raw material, and dyeing usually performed at a temperature close to boiling is performed at a low temperature to suppress the setting of crimp (Patent Document 2). . However, simply increasing the content of the sulfonic acid group-containing monomer cannot be expected to improve the dyeability at low temperatures, and if the content of the sulfonic acid group-containing monomer is increased too much in order to improve the dyeability at low temperatures. In addition to the high manufacturing cost of the fibers, there are also problems that the spinnability is lowered.
JP-A-11-315416 JP 2003-64560 A

本発明の目的は、低温で染色可能な染色性に優れたアクリル系合成繊維を提供し、さらにこの染色性に優れたアクリル系合成繊維を用いることにより、染色時のクリンプのセットを抑え、パイルを作成する際にクリンプが伸び易く加工性に優れ、また風合に優れたパイル布帛を提供せんとするものである。 An object of the present invention is to provide an acrylic synthetic fiber excellent in dyeability that can be dyed at a low temperature, and further, by using this acrylic synthetic fiber excellent in dyeability, a set of crimps at the time of dyeing is suppressed, and a pile It is an object of the present invention to provide a pile fabric that is easily stretched when crimped, has excellent workability, and is excellent in texture.

前記のように、単独のアクリロニトリル系重合体でスルホン酸基含有モノマーの含有量を増やしていくと染色性は向上するものの、８０℃未満での染色性は不十分であるだけでなく、紡糸性も低下する傾向にある。しかし、本発明者らは、鋭意研究の結果、アクリル系合成繊維に一般に使用されているスルホン酸基含有モノマーを含まないアクリロニトリル系重合体やスルホン酸基含有モノマーの含有率が比較的少ないアクリロニトリル系重合体と、それよりスルホン酸基含有モノマーを多く含有する重合体を混合した重合体組成物を湿式紡糸することにより、６０〜９０℃の低温でも染色可能であり、染色時の熱によるクリンプセットが抑えられた繊維が得られることを知見した。本発明によれば、スルホン酸基含有モノマー量の異なる２種類の重合体を混合することにより、繊維中のスルホン酸基含有モノマーの総含有量が少なくても、大幅に低温染色性が向上し、パイル製造時の加工性がよく、また、紡糸性も低下しない。また、繊維を構成する重合体の親水性は抜染性とも大きな相関があり、親水性を向上させることで抜染性も大きく向上することが分かった。スルホン酸基含有モノマーを多く含有する重合体は親水性が高く、これを混合した重合体組成物からなる繊維は抜染性が良好である。 As described above, when the content of the sulfonic acid group-containing monomer is increased with a single acrylonitrile-based polymer, the dyeability is improved, but not only the dyeability at 80 ° C. is insufficient, but also the spinnability. Tend to decrease. However, as a result of intensive studies, the present inventors have found that acrylonitrile polymers not containing sulfonic acid group-containing monomers generally used for acrylic synthetic fibers and acrylonitrile-based polymers having a relatively low content of sulfonic acid group-containing monomers. By wet spinning a polymer composition in which a polymer and a polymer containing a larger amount of a sulfonic acid group-containing monomer are mixed, it is possible to dye at a low temperature of 60 to 90 ° C., and a crimp set by heat during dyeing. It has been found that a fiber with reduced squeezing can be obtained. According to the present invention, by mixing two types of polymers having different amounts of sulfonic acid group-containing monomers, the low-temperature dyeability is greatly improved even if the total content of sulfonic acid group-containing monomers in the fiber is small. The processability at the time of pile production is good, and the spinnability is not lowered. Further, it was found that the hydrophilicity of the polymer constituting the fiber has a great correlation with the dischargeability, and that the dischargeability is greatly improved by improving the hydrophilicity. A polymer containing a large amount of a sulfonic acid group-containing monomer has high hydrophilicity, and a fiber made of a polymer composition obtained by mixing this has good dischargeability.

すなわち、アクリロニトリル４０〜９５重量％、スルホン酸基含有モノマー０〜３重量％、その他共重合可能なモノマー５〜６０重量％を合計１００重量％となるように含有する重合体（Ａ）６０〜９９重量％と、アクリロニトリル５〜９０重量％、（メタ）アクリル酸及びそれらの塩類、（メタ）アクリル酸エステル類、（メタ）アクリルアミド、酢酸ビニルから選ばれる１種以上のモノマー９〜９４重量％、スルホン酸基含有モノマー１〜４０重量％を合計１００重量％となるように含有する重合体であって、該重合体中にスルホン酸基含有モノマーを前記重合体（Ａ）よりも多量に含有する重合体（Ｂ）１〜４０重量％を、前記重合体（Ａ）と重合体（Ｂ）との合計が１００重量％となるように混合した重合体組成物を湿式紡糸することにより、本発明の目的である低温で染色可能なアクリル系合成繊維が得られる。 That is, the polymer (A) 60 to 99 containing 40 to 95% by weight of acrylonitrile, 0 to 3% by weight of a sulfonic acid group-containing monomer, and 5 to 60% by weight of other copolymerizable monomers to a total of 100% by weight. 5% to 90% by weight of acrylonitrile, 9 to 94% by weight of one or more monomers selected from (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylamide and vinyl acetate, A polymer containing 1 to 40% by weight of a sulfonic acid group-containing monomer in a total amount of 100% by weight, wherein the polymer contains a larger amount of the sulfonic acid group-containing monomer than the polymer (A). Wet spinning a polymer composition in which 1 to 40% by weight of the polymer (B) is mixed so that the total of the polymer (A) and the polymer (B) is 100% by weight. Accordingly, dyeable acrylic synthetic fiber is obtained at low temperatures is an object of the present invention.

スルホン酸基含有モノマーは、前記重合体（Ａ）中に０〜１．５重量％、前記重合体（Ｂ）中に３〜３０重量％含有することがより好ましい。さらには、重合体（Ａ）及び（Ｂ）の混合物中におけるスルホン酸基含有モノマーの総含有量が０．５〜３重量％であることが好ましい。 The sulfonic acid group-containing monomer is more preferably contained in the polymer (A) in an amount of 0 to 1.5% by weight and in the polymer (B) in an amount of 3 to 30% by weight. Furthermore, it is preferable that the total content of the sulfonic acid group-containing monomer in the mixture of the polymers (A) and (B) is 0.5 to 3% by weight.

本発明に係るアクリル系合成繊維は、８０℃の染色相対飽和値は０．５以上、沸水に３０分浸漬した時の収縮率は５％以下となる。また、本発明に係るアクリル系合成繊維は、先染め繊維を白色抜染した後の白度がＷ値で７０以上となる抜染性を有する。さらに、本発明に係るアクリル系合成繊維は、６０〜９０℃の温度で染色した際の、染色前後での、動的粘弾性測定のｔａｎδが最大値を示す温度の変化が７℃以下となる。 The acrylic synthetic fiber according to the present invention has a dyeing relative saturation value at 80 ° C. of 0.5 or more and a shrinkage rate of 5% or less when immersed in boiling water for 30 minutes. In addition, the acrylic synthetic fiber according to the present invention has a dischargeability such that the whiteness after white dyeing of the pre-dyed fiber is 70 or more in terms of W value. Furthermore, when the acrylic synthetic fiber according to the present invention is dyed at a temperature of 60 to 90 ° C., the change in temperature at which tan δ of dynamic viscoelasticity measurement reaches the maximum value before and after dyeing is 7 ° C. or less. .

重合体（Ａ）と（Ｂ）の混合物からなる重合体組成物を含む紡糸原液を紡糸する方法としては、通常のアクリル系合成繊維の湿式紡糸と同様な方法により、ノズルより紡出後、数段の浴槽を通し、順次延伸、水洗、乾燥、熱処理を行えばよい。また、クリンプの付与は、スタフィングボックス、ギアクリンパー等、既知の方法により行うことが出来る。クリンプ付与後は、所定長さに切断し、短繊維とする。 As a method for spinning a spinning stock solution containing a polymer composition composed of a mixture of the polymers (A) and (B), after spinning from a nozzle by the same method as that for wet spinning of ordinary acrylic synthetic fibers, It is only necessary to perform stretching, washing with water, drying, and heat treatment sequentially through a stepped bathtub. Further, the crimping can be performed by a known method such as a stuffing box or a gear crimper. After crimping, cut to a predetermined length to make short fibers.

染色については、使用する染料や染色時間等は任意であるが、染色温度は、クリンプのセットを抑えるため、９０℃以下で行うのが好ましい。好ましくは６０〜９０℃である。 For dyeing, the dye to be used, the dyeing time, and the like are arbitrary, but the dyeing temperature is preferably 90 ° C. or lower in order to suppress crimping. Preferably it is 60-90 degreeC.

染色後、スライバー作成し、編み機にてパイルを編み上げる。編み上がったパイルを、バックコーテイング工程でパイル裏面に糊付けを行い、その後、ポリシャーにより、クリンプを伸ばし、パイルを仕上げる。 After dyeing, a sliver is created and the pile is knitted with a knitting machine. The pile that has been knitted is glued to the back of the pile in the back coating process, and then the crimp is stretched by a polisher to finish the pile.

さらに、本発明に係るアクリル系合成繊維は、抜染性にも優れている。抜染用途に用いる際には、染色は各種還元性抜染剤により還元されるカチオン染料によることが好ましく、一般的には染料構造中にアゾ基（−Ｎ＝Ｎ−）を発色団として１個以上有するカチオン染料が用いられる。 Furthermore, the acrylic synthetic fiber according to the present invention is excellent in dischargeability. When used for discharging, dyeing is preferably performed with a cationic dye that is reduced by various reducing discharging agents, and generally one or more azo groups (—N═N—) as a chromophore in the dye structure. The cationic dye which has is used.

一般のボイル染色している繊維は、染色時にクリンプがセットされてクリンプが伸びにくく、ポリシャーをかける回数が多く必要である。これに対し、本発明に係るアクリル系合成繊維は、例えば６０〜９０℃の低温でも染色可能なため、染色時のクリンプセットが抑えられ、パイルを作成する際に、クリンプが伸びやすく、ポリシャーの回数が少なくてすみ、加工性に優れる。また、クリンプの伸びが良好なため、良好な風合のパイルが得られる。さらに、低温でも染色可能なことから、染色に要するエネルギー（熱量）を低減できる。 In general, a fiber dyed by boil dyeing requires a large number of times of applying a polisher because a crimp is set at the time of dyeing and the crimp is not easily stretched. On the other hand, the acrylic synthetic fiber according to the present invention can be dyed even at a low temperature of, for example, 60 to 90 ° C., so that the crimp set at the time of dyeing is suppressed. The number of times is small and the processability is excellent. In addition, since the elongation of the crimp is good, a pile with a good texture can be obtained. Furthermore, since dyeing is possible even at a low temperature, energy (heat amount) required for dyeing can be reduced.

また、本発明に係るアクリル系合成繊維は、抜染に必要な蒸熱処理時間が短く、本発明のアクリル系合成繊維を用いると、抜染時の蒸熱処理の時間が１０〜１５分以内で十分であり、パイル製造時の加工性に優れる。さらに、抜染後の白度が優れていると共に、ソフトな風合を保持している。このため、抜染加工を施した多様なデザインとソフトな風合とを兼ね備えたパイル布帛が出来、衣料、ぬいぐるみ、インテリア用途等、幅広く展開することが出来る。 In addition, the acrylic synthetic fiber according to the present invention has a short steaming time required for discharging, and when the acrylic synthetic fiber of the present invention is used, the steaming time during discharging is sufficient within 10 to 15 minutes. Excellent workability when manufacturing piles. Furthermore, the whiteness after discharging is excellent and the soft texture is maintained. For this reason, a pile fabric having a variety of designs subjected to discharge printing and a soft texture can be produced, and can be widely used for clothing, stuffed animals, interior use, and the like.

本発明における重合体（Ａ）は、アクリロニトリル４０〜９５重量％、スルホン酸基含有モノマー０〜３重量％、好ましくは２重量％以下、さらに好ましくは１．５重量％以下、及びその他共重合可能なモノマー５〜６０重量％からなるアクリル系重合体である。スルホン酸基含有モノマーとしては、アリルスルホン酸、メタリルスルホン酸、ｐ−スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、イソプレンスルホン酸及びこれらのアルカリ金属塩等が挙げられる。また、その他共重合可能なモノマーとしては、（メタ）アクリル酸等の酸類及びそれらの塩類、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ヘキシル（メタ）アクリレート等の（メタ）アクリル酸エステル類、（メタ）アクリルアミド、酢酸ビニル、塩化ビニル、塩化ビニリデン、臭化ビニル、臭化ビニリデン等が挙げられる。これらは単独で用いてもよいし、併用してもよい。 The polymer (A) in the present invention is 40 to 95% by weight of acrylonitrile, 0 to 3% by weight of a sulfonic acid group-containing monomer, preferably 2% by weight or less, more preferably 1.5% by weight or less, and other copolymerizable. It is an acrylic polymer composed of 5 to 60% by weight of a monomer. Examples of the sulfonic acid group-containing monomer include allyl sulfonic acid, methallyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, isoprene sulfonic acid, and alkali metal salts thereof. Other copolymerizable monomers include acids such as (meth) acrylic acid and their salts, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hexyl (meth) acrylate and the like ( And (meth) acrylic acid esters, (meth) acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide and the like. These may be used alone or in combination.

本発明における重合体（Ｂ）は、アクリロニトリル５〜９０重量％、スルホン酸基含有モノマー１〜４０重量％、好ましくは３〜３０重量％、（メタ）アクリル酸及びそれらの塩類、（メタ）アクリル酸エステル類、（メタ）アクリルアミド、酢酸ビニルから選ばれる１種以上のモノマー９〜９４重量部からなる。スルホン酸基含有モノマーとしては、前記重合体（Ａ）の場合と同様のものが挙げられる。また、（メタ）アクリル酸エステル類としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ヘキシル（メタ）アクリレート等が挙げられる。これらは単独で用いてもよいし、併用してもよい。 The polymer (B) in the present invention comprises 5 to 90% by weight of acrylonitrile, 1 to 40% by weight of a sulfonic acid group-containing monomer, preferably 3 to 30% by weight, (meth) acrylic acid and salts thereof, and (meth) acrylic. It consists of 9 to 94 parts by weight of one or more monomers selected from acid esters, (meth) acrylamide and vinyl acetate. Examples of the sulfonic acid group-containing monomer are the same as those in the case of the polymer (A). Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hexyl (meth) acrylate, and the like. These may be used alone or in combination.

また、重合体（Ａ）と重合体（Ｂ）との混合物中のスルホン酸基含有モノマーの総含有量は、０．５〜３重量％が好ましく、より好ましくは０．５〜２．５重量％である。スルホン酸基含有モノマーの総含有量が少ないと低温染色性が低下する。またスルホン酸基含有モノマーの総含有量が多くなると繊維の製造コストが高くなるうえに、紡糸性が低下する傾向がある。 The total content of sulfonic acid group-containing monomers in the mixture of the polymer (A) and the polymer (B) is preferably 0.5 to 3% by weight, more preferably 0.5 to 2.5% by weight. %. If the total content of the sulfonic acid group-containing monomer is small, the low-temperature dyeability is lowered. Further, when the total content of the sulfonic acid group-containing monomer is increased, the production cost of the fiber is increased and the spinnability tends to be lowered.

本発明における重合体（Ａ）、（Ｂ）は、重合開始剤として既知の化合物、例えば、パーオキシド系化合物、アゾ径化合物、または各種のレドックス系化合物を用い、懸濁重合、乳化重合、溶液重合等一般的なビニル重合方法により得ることができる。 Polymers (A) and (B) in the present invention are known compounds as polymerization initiators, such as peroxide compounds, azo diameter compounds, or various redox compounds, and are used for suspension polymerization, emulsion polymerization, solution polymerization. It can be obtained by a general vinyl polymerization method.

本発明に係るアクリル系合成繊維は、重合体（Ａ）６０〜９９重量％と、重合体（Ｂ）１〜４０重量％とを、合計が１００重量％となるように混合し、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、アセトン等の有機溶剤、ロダン塩、硝酸、塩化亜鉛等の無機溶剤に溶解させて、紡糸原液とする。この紡糸原液を用いて、通常のアクリル系合成繊維の湿式紡糸と同様な方法により、ノズルより紡出後、数段の浴槽を通し、順次延伸、水洗、乾燥、熱処理を行い、アクリル系合成繊維を得る。 The acrylic synthetic fiber according to the present invention is prepared by mixing 60 to 99% by weight of the polymer (A) and 1 to 40% by weight of the polymer (B) so that the total becomes 100% by weight, dimethylformamide, Dissolve in an organic solvent such as dimethylacetamide, dimethyl sulfoxide, and acetone, or an inorganic solvent such as rhodan salt, nitric acid, and zinc chloride to obtain a spinning dope. Using this spinning dope, after spinning from the nozzle in the same way as normal wet spinning of acrylic synthetic fibers, passing through several tubs, drawing, washing, drying and heat treatment in order, acrylic synthetic fibers Get.

次いで、こうして得られた合成繊維に、クリンプを付与する。クリンプ付与は、例えばスタフィングボックスやギアクリンパー等を用いた方法等の公知の方法で行う。クリンプを付与する際の温度は、７０〜９９℃、好ましくは７０〜９５℃とする。また、クリンプ山数が５〜１４個／インチになるようにスタッフィングボックス圧を０．１〜０．４ＭＰａに調整することが好ましい。クリンプ山数が多すぎると、良好な風合のパイルを得る点では不利である。一方、クリンプ山数が５個／インチ未満では、スライバー強度が弱くなり、スライバー作成、スライバーニッティングなどの加工性の点からは不利である。 Next, crimp is imparted to the synthetic fiber thus obtained. The crimping is performed by a known method such as a method using a stuffing box or a gear crimper. The temperature for applying the crimp is 70 to 99 ° C, preferably 70 to 95 ° C. Further, it is preferable to adjust the stuffing box pressure to 0.1 to 0.4 MPa so that the number of crimps is 5 to 14 / inch. When there are too many crimps, it is disadvantageous in obtaining a pile with good texture. On the other hand, when the number of crimp ridges is less than 5 / inch, the sliver strength becomes weak, which is disadvantageous in terms of workability such as sliver creation and sliver knitting.

クリンプ付与後は、所定の長さに切断して短繊維とする。通常、短繊維の繊維長は２０〜１７０ｍｍである。 After crimping, the fiber is cut into a predetermined length to form a short fiber. Usually, the fiber length of a short fiber is 20-170 mm.

ついで、短繊維は、染色工程に付される。本発明に係るアクリル系合成繊維は、一般に使用されるカチオン染料により染色が可能であり、重合体（Ａ）のみからなるアクリル系合成繊維に比べて、低温での染料吸尽性能に優れている。使用する染料や染色時間等は任意であるが、染色温度については、クリンプのセットを抑えるため、９０℃以下で行うのが好ましい。染色温度は、好ましくは６０〜９０℃であり、更に好ましくは６０〜８０℃である。 The short fibers are then subjected to a dyeing process. The acrylic synthetic fiber according to the present invention can be dyed with a commonly used cationic dye, and is excellent in dye exhaustion performance at a low temperature as compared with an acrylic synthetic fiber composed only of the polymer (A). . The dye to be used, the dyeing time, and the like are arbitrary, but the dyeing temperature is preferably 90 ° C. or lower in order to suppress crimp setting. The dyeing temperature is preferably 60 to 90 ° C, more preferably 60 to 80 ° C.

染色した短繊維は、ローラーカード等に通してスライバー作成し、編み機によりパイルを編み上げる。編み上げたパイルをバックコーテイング工程に通し、糊付けを行う。その後、通常のパイル仕上げと同様に、高温から３段階程度の温度のポリシャーをかけ、シャーリング機によるカットを行い、パイルを仕上げる。その後、ポリシャーかけにより仕上げる。通常のアクリル系繊維の場合、仕上げに６〜１０程度のポリッシャーかけが必要であるが、本発明の低温染色した繊維は４〜６回のポリシャーかけにより仕上げることが出来る。 The dyed short fibers are passed through a roller card or the like to make a sliver, and a pile is knitted by a knitting machine. The knitted pile is passed through the back coating process and glued. After that, in the same way as normal pile finishing, a polisher having a temperature of about three stages is applied, and cutting with a shearing machine is performed to finish the pile. Then finish with a polisher. In the case of ordinary acrylic fibers, polishing of about 6 to 10 is necessary for finishing, but the low-temperature dyed fibers of the present invention can be finished by polishing 4 to 6 times.

さらに、デザイン性向上等を目的としてパイルの毛先の抜染を行う際には、還元可能なカチオン染料を用いて染色し、上記と同様の手順でパイル布帛を作成後、ジンクホルムアルデヒドスルホキシレート等の亜鉛系抜染剤あるいは塩化第一錫等の錫系抜染剤等を含む一般に使用される抜染糊を使用して抜染する。抜染糊をパイル表面に印捺後、９０℃以上の飽和水蒸気あるいは加熱水蒸気雰囲気中で１０〜４０分の蒸熱処理を行い、抜染を行う。さらに、水洗洗浄、乾燥、仕上げを経て、最終パイルが出来上がる。 Furthermore, when discharging the pile hair tips for the purpose of improving design, etc., dyeing with a reducible cationic dye, creating a pile fabric in the same procedure as described above, zinc formaldehyde sulfoxylate, etc. Are discharged using a commonly used discharge paste containing a zinc discharge agent or a tin discharge agent such as stannous chloride. After printing the discharging paste on the surface of the pile, steaming is performed for 10 to 40 minutes in a saturated steam atmosphere or a heated steam atmosphere at 90 ° C. or higher to perform discharging. Furthermore, the final pile is completed after washing with water, drying and finishing.

以下に実施例を示し、本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例の記載に先立って、評価法について説明する。なお、以下の記載で「部」は重量基準である。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Prior to the description of the examples, the evaluation method will be described. In the following description, “part” is based on weight.

（染色相対飽和値）
染色相対飽和値は、繊維の染料吸尽性能の指標であり、繊維を６０℃、７０℃、８０℃、９０℃、１００℃で６０分間、濃度が５％ｏｍｆのマラカイトグリーンを用いて染色し飽和染着量を求め、飽和染着量より相対飽和値を求めた。飽和染着量、相対飽和値は下記の式より求めた。
飽和染着量＝（（Ａｏ−Ａ）／Ａｏ）×５）
Ａ：染色後の染浴の吸光度（６１８ｎｍ）
Ａｏ：染色前の染浴の吸光度（６１８ｎｍ）
相対飽和値＝飽和染着量×４００／４６３ (Staining relative saturation value)
The dyeing relative saturation value is an index of the dye exhaust performance of the fiber. The fiber is dyed with malachite green having a concentration of 5% omf at 60 ° C., 70 ° C., 80 ° C., 90 ° C., 100 ° C. for 60 minutes. The saturated dyeing amount was determined, and the relative saturation value was determined from the saturated dyeing amount. The saturated dyeing amount and the relative saturation value were obtained from the following formula.
Saturated dyeing amount = ((Ao−A) / Ao) × 5)
A: Absorbance of dye bath after dyeing (618 nm)
Ao: Absorbance of dye bath before dyeing (618 nm)
Relative saturation value = saturated dyeing amount × 400/463

（沸水収縮率）
沸水収縮率は、沸水処理前の長さをＬ０、沸水処理（９８℃で３０分間）後の長さをＬ１とし、下記式より求めた。
沸水収縮率（％）＝（（Ｌ０−Ｌ１）／Ｌ０）×１００ (Boiling water shrinkage)
The boiling water shrinkage was determined from the following formula, assuming that the length before boiling water treatment was L0 and the length after boiling water treatment (98 ° C. for 30 minutes) was L1.
Boiling water shrinkage rate (%) = ((L0−L1) / L0) × 100

（抜染性評価）
（１）先染め方法染色機（オーバーマイヤー）に繊維をセットし、ウルトラリン酸（ウルトラＭＴ−１１０：御弊島化学製）にてｐＨ約３．５に調整した染色浴を仕立て、染色機を稼動させつつ５０℃に昇温した。さらに下記染料処方にて計量した染料を７０℃温水で溶解して投入した。次いで９０℃まで１分間に１℃の速度で昇温し、９０℃にて６０分間保ち、染色を行った。その後、５℃／分の速度で５０℃まで冷却し、通常の水洗、乾燥を経て染色された繊維を得た。
ＣａｔｈｉｌｏｎＤｉｓｃｈａｒｇｅＹｅｌｌｏｗＮＬＨ：０．４９％ｏｍｆ
ＣａｔｈｉｌｏｎＲｅｄＣＤ−ＦＧＬＨ：０．１９％ｏｍｆ
ＣａｔｈｉｌｏｎＢｌｕｅＧＲＬＨ（２００％）：０．１１％ｏｍｆ
（いずれも保土谷化学社製） (Dischargeability evaluation)
(1) Pre-dyeing method Fibers are set in a dyeing machine (Over Meyer) and a dyeing bath adjusted to pH about 3.5 with ultraphosphoric acid (Ultra MT-110: manufactured by Gogashima Chemical) is used. The temperature was raised to 50 ° C. while operating. Further, the dye measured according to the following dye formulation was dissolved in 70 ° C. warm water and added. Next, the temperature was raised to 90 ° C. at a rate of 1 ° C. per minute and kept at 90 ° C. for 60 minutes for dyeing. Then, it cooled to 50 degreeC at the speed | rate of 5 degree-C / min, and obtained the dyed fiber through normal water washing and drying.
Cathilon Discharge Yellow NLH: 0.49% omf
Cathilon Red CD-FGLH: 0.19% omf
Cathilon Blue GRLH (200%): 0.11% omf
(Both manufactured by Hodogaya Chemical Co., Ltd.)

（２）白色抜染処方と抜染性評価
（２−１）短繊維の白色抜染処方と抜染速度、白度評価
抜染剤として塩化第一錫（キシダ化学製）１０部、水９０部を混合して抜染剤溶液を調製した。この抜染剤溶液２００ｍｌをポット染色機にセットして昇温し、沸騰後、先染めした短繊維２ｇを投入し、抜染を行った。短繊維の抜染速度を評価するため、短繊維を投入後、５、１０、１５、２０、２５、３０、４０分間経過したものをそれぞれ得て、各々水洗−乾燥を行った。この繊維を十分に開繊して２ｇ量り取り、直径３０ｍｍの試料台にいれて標準光源Ｃのもとで色差計タイプΣ９０（日本電色工業製）を使用して抜染処理後の白度を測定した。なお本実施例、比較例では、４０分経過後のハンター白度Ｗ値が７０以上を合格とし、Ｗ値が７０以上になった短繊維投入後の経過時間を抜染時間とし、その時間が短いほど抜染性に優れると評価した。 (2) White discharge prescription and dischargeability evaluation (2-1) White fiber discharge prescription and discharge speed, whiteness evaluation As a discharge agent, 10 parts of stannous chloride (manufactured by Kishida Chemical) and 90 parts of water are mixed. A discharge agent solution was prepared. 200 ml of this discharging agent solution was set in a pot dyeing machine and heated, and after boiling, 2 g of pre-dyed short fibers were added to perform discharging. In order to evaluate the discharging speed of the short fibers, those after 5, 10, 15, 20, 25, 30, and 40 minutes had been obtained after feeding the short fibers, and each was washed with water and dried. This fiber is fully opened and weighed 2 g, put in a sample table with a diameter of 30 mm, and using a color difference meter type Σ90 (manufactured by Nippon Denshoku Industries Co., Ltd.) under a standard light source C, the whiteness after the discharge process is measured. It was measured. In this example and the comparative example, the Hunter whiteness W value after 40 minutes passed is 70 or more, and the elapsed time after the short fiber is fed when the W value is 70 or more is set as the discharge time, and the time is short. It was evaluated that the dischargeability was excellent.

（２−２）パイル原反の白色抜染処方と抜染性評価
抜染剤として塩化第一錫（キシダ化学製）１０部、糊剤としてローカストビーン系糊ＭｅｙｐｒｏＧｕｍＮＰ−２５（３０％濃度：Ｍｅｙｈａｌｌ社製）４０部、酒石酸０．１部、水４９．９部を用い、抜染用捺染糊の粘度がＢ型粘度計で８０００〜１００００ｃｐになるように調整した。この抜染用捺染糊をローラー捺染機を用いて２００〜３００ｇ／ｍ²の印捺量でハイパイル原反のパイル面に印捺し、約９８℃の蒸し機内で蒸熱処理を１５分間実施した後、水洗−乾燥を行った。次いで、ハイパイル原反のパイル乱れ及び風合いを改善するために、ポリッシング−シャーリング処理を行い、ハイパイル生地を最終製品の形態に整えた。このようにして得られた抜染品を、汚染用カラースケール（５級が最も良く、１級が最も悪い）を用いて評価した。 (2-2) Pile raw fabric white discharge prescription and discharge evaluation 10 parts of stannous chloride (manufactured by Kishida Chemical) as discharge agent, locust bean paste Meypro Gum NP-25 (30% concentration: Mayhall) as paste 40 parts, tartaric acid 0.1 part and water 49.9 parts were used, and the viscosity of the printing paste for discharging was adjusted to 8000 to 10,000 cp with a B-type viscometer. This printing paste for printing is printed on a pile surface of a high-pile raw fabric at a printing amount of 200 to 300 g / m ² using a roller printing machine, steamed in a steamer at about 98 ° C. for 15 minutes, and then washed with water. -Dried. Next, in order to improve the pile disturbance and texture of the high-pile raw fabric, a polishing-shearing process was performed to arrange the high-pile dough into a final product form. The discharge product thus obtained was evaluated using a color scale for contamination (grade 5 was the best and grade 1 was the worst).

（動的粘弾性ｔａｎδ測定）
測定には、染色前の短繊維及び染色後の短繊維を用いた。
セイコー電子工業（株）製ＴＭＡ／ＳＳ１５０Ｃを用い、ＪＩＳ−Ｋ７１９８を参考に試料長１０ｍｍ、トータルデニール３３ｄｔｅｘ、昇温速度３℃／ｍｉｎ、測定温度範囲３０℃〜２００℃、空気中、周波数０．０５Ｈｚ、初荷重３０ｍｇ／ｄｔｅｘで１５ｍｇ／ｄｔｅｘの荷重を与え正弦波モードにより引っ張り振動をさせながら測定を行った。 (Dynamic viscoelasticity tan δ measurement)
For the measurement, short fibers before dyeing and short fibers after dyeing were used.
Using TMA / SS150C manufactured by Seiko Denshi Kogyo Co., Ltd., with reference to JIS-K7198, sample length 10 mm, total denier 33 dtex, heating rate 3 ° C./min, measuring temperature range 30 ° C. to 200 ° C., in air, frequency 0. The measurement was performed while applying a load of 15 mg / dtex at an initial load of 30 mg / dtex at 05 Hz and causing tensile vibration in the sine wave mode.

（パイルの加工性及び風合評価）
得られたアクリル系合成繊維を、オーバーマイヤー染色機を用い、ＣａｔｈｉｌｏｎＤｉｓｃｈａｒｇｅＹｅｌｌｏｗＮＬＨ：０．４９％ｏｍｆ、ＣａｔｈｉｌｏｎＲｅｄＣＤ−ＦＧＬＨ：０．１９％ｏｍｆ、ＣａｔｈｉｌｏｎＢｌｕｅＧＲＬＨ（２００％）：０．１１％ｏｍｆの染料を用いて６０〜１００℃で６０分間染色を行い、乾燥後、ローラーカードを通しスライバーを作成した。次いでハイパイル編織機でスライバーニッテイングを行い、その後、１２０℃でプレポリッシング処理とプレシャーリングを行い、パイル長を１３ｍｍに揃えた後、パイル裏面にアクリル酸エステル系接着剤でバックコーテイングを行った。その後、ポリシャーを５回の場合は、１５５℃、１５０℃、１３５℃、１２０℃、１００℃のポリッシング、ポリシャーを６回の場合は、１５５℃、１５０℃、１３５℃、１２０℃、１１０℃、１００℃のポリッシング、ポリシャーを８回の場合は、１５５℃、１５５℃、１４５℃、１３５℃、１３０℃、１２０℃、１１０℃、１００℃のポリッシングを行い、ブラッシング、シャーリングと組み合わせ、パイルのクリンプを伸ばし、１５ｍｍのパイル長を有するパイルを作成した。 (Pile workability and texture evaluation)
The obtained acrylic synthetic fiber was used with an Overmeier dyeing machine, Cathilon Discharge Yellow NLH: 0.49% omf, Cathilon Red CD-FGLH: 0.19% omf, Cathilon Blue GRLH (200%): 0.11 Dyeing was performed at 60 to 100 ° C. for 60 minutes using a dye of% omf, and after drying, a sliver was created through a roller card. Next, sliver knitting was performed with a high pile weaving machine, and then pre-polishing and pre-shearing were performed at 120 ° C., and the pile length was adjusted to 13 mm, and then back coating was performed with an acrylic ester adhesive on the back of the pile. Thereafter, in the case of 5 times of polisher, polishing at 155 ° C., 150 ° C., 135 ° C., 120 ° C., 100 ° C., in the case of 6 times of polisher, 155 ° C., 150 ° C., 135 ° C., 120 ° C., 110 ° C., Polishing at 100 ° C and polisher 8 times, polishing at 155 ° C, 155 ° C, 145 ° C, 135 ° C, 130 ° C, 120 ° C, 110 ° C, 100 ° C, combining with brushing and shearing, pile crimp A pile having a pile length of 15 mm was prepared.

パイルの風合評価は、５名の判定者により、以下の基準で評価し、最も多数を得た評価をそのパイルの評価結果とした。
◎：パイルのクリンプがゆるやかに伸び、毛さばきに優れ、ソフトで獣毛ライクな風合を有する。
○：パイルのクリンプの伸びが概ね良好で、ソフトな風合を有する。
△：パイルのクリンプの伸びがやや不十分で、ややガサツク風合である。
×：パイルのクリンプの伸びが不十分で、ガサツク風合である The pile texture evaluation was evaluated by the following five criteria based on the following criteria, and the evaluation obtained most was used as the evaluation result of the pile.
A: The pile crimp gently stretches, has excellent hair handling, and has a soft and animal hair-like texture.
○: Pile crimp elongation is generally good and has a soft texture.
(Triangle | delta): The elongation of the crimp of a pile is a little insufficiency and it is a slightly rough feeling.
×: Pile crimp is not sufficiently stretched and has a rough texture

（実施例１）
内容積２０Ｌの耐圧重合反応装置にイオン交換水２００部、ラウリル硫酸ナトリウム０．９部、亜硫酸０．４３部、亜硫酸水素ナトリウム０．２２部、硫酸鉄０．００１部、アクリロニトリル（ＡＮ）４．９部、塩化ビニル（ＶＣ）５１．５部を投入し、窒素置換した。重合反応装置内温度を５０℃に調整し、開始剤として過硫酸アンモニウム０．０３５部を投入し、重合を開始した。途中、アクリロニトリル４３．１部、スチレンスルホン酸ナトリウム（３Ｓ）０．５部、過硫酸アンモニウム０．２３部を追加しながら、重合時間５時間１０分で重合した。その後、未反応の塩化ビニルを回収し、ラテックスを重合機より払い出し、塩析、熱処理、ろ過、水洗、脱水、乾燥し、本発明の重合体（Ａ）に該当する重合体１を得た。得られた共重合体の組成は、アクリロニトリル５０重量％、スチレンスルホン酸ナトリウム０．５重量％、塩化ビニル４９．５重量％であった。 (Example 1)
3. 200 parts of ion-exchanged water, 0.9 part of sodium lauryl sulfate, 0.43 part of sodium sulfite, 0.22 part of sodium hydrogen sulfite, 0.001 part of iron sulfate, acrylonitrile (AN) 4. 9 parts and 51.5 parts of vinyl chloride (VC) were added, and the atmosphere was replaced with nitrogen. The temperature in the polymerization reaction apparatus was adjusted to 50 ° C., 0.035 part of ammonium persulfate was added as an initiator, and polymerization was started. On the way, polymerization was performed in 5 hours and 10 minutes while adding 43.1 parts of acrylonitrile, 0.5 part of sodium styrenesulfonate (3S) and 0.23 part of ammonium persulfate. Thereafter, unreacted vinyl chloride was recovered, the latex was discharged from the polymerization machine, and salting out, heat treatment, filtration, washing with water, dehydration, and drying were performed to obtain a polymer 1 corresponding to the polymer (A) of the present invention. The composition of the obtained copolymer was 50% by weight of acrylonitrile, 0.5% by weight of sodium styrenesulfonate, and 49.5% by weight of vinyl chloride.

次に、内容積５Ｌの耐圧重合反応装置にアセトン１８７部、水４７部、アクリロニトリル４５部、アクリル酸メチル４５部、２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム（以下ＳＡＭと記す。）１０部を投入し、窒素置換した。重合反応装置内温度を６５℃に調整し、開始剤として２，２´−アゾビス（２，４−ジメチルバレロニトリル）（ＡＩＶＮ）を０．５部投入し重合を開始した。途中、ＡＩＶＮを１．０部追加しながら２時間重合し、その後、７０℃に昇温し２時間重合させ、重合体濃度３０％の本発明の重合体（Ｂ）に該当する重合体２の溶液を得た。得られた共重合体の組成は、アクリロニトリル４５重量％、アクリル酸メチル４５重量％、ＳＡＭ１０重量％であった。 Next, 187 parts of acetone, 47 parts of water, 45 parts of acrylonitrile, 45 parts of methyl acrylate, and 10 parts of sodium 2-acrylamido-2-methylpropanesulfonate (hereinafter referred to as SAM) in a pressure-resistant polymerization reactor having an internal volume of 5 L. Was replaced with nitrogen. The polymerization reactor internal temperature was adjusted to 65 ° C., and 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) (AIVN) was added as an initiator to initiate polymerization. During the course of polymerization, 1.0 part of AIVN was added for 2 hours, and then the temperature was raised to 70 ° C. for 2 hours to polymerize the polymer 2 corresponding to the polymer (B) of the present invention having a polymer concentration of 30%. A solution was obtained. The composition of the obtained copolymer was 45% by weight of acrylonitrile, 45% by weight of methyl acrylate, and 10% by weight of SAM.

重合体１が３０重量％になるようにアセトンを加えて溶解した重合体１の溶液に、重合体２の溶液を、重合体の重量比が重合体１：重合体２＝９２：８の比率になるように混合して紡糸原液とした。得られた紡糸原液を、孔径０．１ｍｍ、ホール数１０，０００のノズルを通して、アセトン／水＝３０／７０、２５℃の凝固浴に紡出し、８５℃の熱水中にて３倍に延伸し、さらに乾燥後、１３０℃にて２倍延伸し、さらに１５０℃にて緩和熱処理を行い、３．３ｄｔｅｘの繊維を得た。続いて得られた繊維にクリンプを付与した後、繊維長を３８ｍｍに切断して短繊維を得た。 A solution of the polymer 2 is added to a solution of the polymer 1 dissolved by adding acetone so that the polymer 1 is 30% by weight, and the weight ratio of the polymer is a ratio of polymer 1: polymer 2 = 92: 8. To obtain a spinning dope. The obtained spinning solution was spun into a coagulation bath of acetone / water = 30/70, 25 ° C. through a nozzle having a hole diameter of 0.1 mm and a hole number of 10,000, and stretched 3 times in hot water at 85 ° C. After drying, the film was stretched twice at 130 ° C. and further subjected to relaxation heat treatment at 150 ° C. to obtain 3.3 dtex fibers. Subsequently, after crimping the obtained fiber, the fiber length was cut to 38 mm to obtain a short fiber.

得られた短繊維について、染色相対飽和値を評価した。この染色相対飽和値の評価結果をもとに、６０℃で６０分間染色を行い、染色前後における動的粘弾性ｔａｎδを測定した。また、抜染用先染めを行った後、短繊維の抜染を行い、抜染時間及び抜染後のＷ値を評価した。さらに、染色した繊維を、（パイルの加工法及び風合評価）に記載した手順によりポリシャーを５回かけ、パイルを作成し、評価を行った。 About the obtained short fiber, the dyeing | staining relative saturation value was evaluated. Based on the evaluation result of the staining relative saturation value, staining was performed at 60 ° C. for 60 minutes, and the dynamic viscoelasticity tan δ before and after the staining was measured. Moreover, after performing pre-dyeing for discharging, short fibers were discharged, and the discharging time and the W value after discharging were evaluated. Further, the dyed fiber was subjected to a polisher 5 times by the procedure described in (Pile processing method and feel evaluation), and a pile was created and evaluated.

（実施例２）
実施例１における重合体１を得た方法と同様の方法により、アクリロニトリル５２重量％、スチレンスルホン酸ナトリウム１重量％、塩化ビニル４７重量％の重合体３を得た。さらに、実施例１における重合体２を得た方法と同様の方法によりアクリロニトリル４５重量％、アクリル酸メチル３５重量％、ＳＡＭ２０重量％の重合体４を得た。重合体３：重合体４の重量比が９５：５の比率になるように混合したものを紡糸原液とし、実施例１と同様の方法で短繊維を得、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに７０℃で６０分間染色した繊維を用いて（パイル加工法及び風合評価）手順によりポリシャーを５回かけ、パイルを作成し、評価を行った。 (Example 2)
By a method similar to the method for obtaining the polymer 1 in Example 1, a polymer 3 comprising 52% by weight of acrylonitrile, 1% by weight of sodium styrenesulfonate and 47% by weight of vinyl chloride was obtained. Further, a polymer 4 of 45% by weight of acrylonitrile, 35% by weight of methyl acrylate, and 20% by weight of SAM was obtained by the same method as that for obtaining the polymer 2 in Example 1. A mixture of polymer 3 and polymer 4 in a weight ratio of 95: 5 is used as a spinning dope, and short fibers are obtained in the same manner as in Example 1, and dyeing is carried out in the same manner as in Example 1. Property, dynamic viscoelasticity tan δ, dischargeability, and using a fiber dyed at 70 ° C for 60 minutes (pile processing method and texture evaluation), applying a polisher 5 times according to the procedure, creating a pile, and evaluating went.

（実施例３）
内容積２０Ｌの耐圧重合反応装置にイオン交換水２００部、ラウリル硫酸ナトリウム１．１部、亜硫酸０．１３部、硫酸水素ナトリウム０．１７部、硫酸鉄０．００２部、アクリロニトリル１０．７部、塩化ビニリデン４．４部を投入し、窒素置換した。重合反応装置内温を５５℃に調整し、開始剤として過硫酸アンモニウム０．０１２部を投入し、重合を開始した。途中、アクリロニトリル４５．７部、塩化ビニリデン３７．７部、スチレンスルホン酸ナトリウム１．５部、過硫酸アンモニウム０．１３５部を追加しながら、重合時間６時間１０分で重合した。その後、ラテックスを重合反応装置より払い出し、塩析、熱処理、ろ過、水洗、脱水、乾燥し、本発明の重合体（Ａ）に該当する重合体５を得た。得られた共重合体の組成は、アクリロニトリル５２重量％、スチレンスルホン酸ナトリウム１．５重量％、塩化ビニリデン４６．５重量％であった。さらに、実施例１における重合体２を得た方法と同様の方法によりアクリロニトリル５０重量％、アクリル酸メチル４５重量％、ＳＡＭ５重量％の重合体６を得た。重合体５：重合体６の重量比が８５：１５の比率になるように混合した物を紡糸原液とし、実施例１と同様の方法で短繊維を得た。 (Example 3)
In a pressure-resistant polymerization reactor having an internal volume of 20 L, 200 parts of ion-exchanged water, 1.1 parts of sodium lauryl sulfate, 0.13 parts of sodium sulfite, 0.17 parts of sodium hydrogen sulfate, 0.002 parts of iron sulfate, 10.7 parts of acrylonitrile, 4.4 parts of vinylidene chloride was added and replaced with nitrogen. The internal temperature of the polymerization reactor was adjusted to 55 ° C., and 0.012 part of ammonium persulfate was added as an initiator to initiate polymerization. In the middle of the polymerization, polymerization was performed for 6 hours and 10 minutes while adding 45.7 parts of acrylonitrile, 37.7 parts of vinylidene chloride, 1.5 parts of sodium styrenesulfonate, and 0.135 parts of ammonium persulfate. Thereafter, the latex was discharged from the polymerization reactor, and salting out, heat treatment, filtration, washing with water, dehydration and drying were performed to obtain a polymer 5 corresponding to the polymer (A) of the present invention. The composition of the obtained copolymer was 52% by weight of acrylonitrile, 1.5% by weight of sodium styrenesulfonate, and 46.5% by weight of vinylidene chloride. Further, a polymer 6 having 50% by weight of acrylonitrile, 45% by weight of methyl acrylate, and 5% by weight of SAM was obtained by the same method as that for obtaining the polymer 2 in Example 1. Short fibers were obtained in the same manner as in Example 1 using a mixture of polymer 5: polymer 6 in a weight ratio of 85:15 as a spinning dope.

得られた短繊維について、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに８０℃で６０分間染色した繊維を用いて（パイル加工法及び風合評価）手順によりポリシャーを５回かけ、パイル作成し、評価を行った。 The obtained short fibers were evaluated for dyeability, dynamic viscoelasticity tan δ, and dischargeability in the same manner as in Example 1, and further using fibers dyed at 80 ° C. for 60 minutes (pile processing method and feel evaluation) ) According to the procedure, a polisher was applied 5 times, a pile was created and evaluated.

（実施例４）
実施例１における重合体１を得た方法と同様の方法により、アクリロニトリル４９重量％、スチレンスルホン酸ナトリウム０．５重量％、塩化ビニル５０．５重量％の重合体７を得た。さらに、実施例１における重合体２を得た方法と同様の方法によりアクリロニトリル３０重量％、アクリル酸メチル４０重量％、ＳＡＭ３０重量％の重合体８を得た。重合体７：重合体８の重量比が９８．５：１．５の比率になるように混合したものを紡糸原液とし、実施例１と同様の方法で短繊維を得た。 Example 4
By a method similar to the method for obtaining the polymer 1 in Example 1, a polymer 7 containing 49% by weight of acrylonitrile, 0.5% by weight of sodium styrenesulfonate, and 50.5% by weight of vinyl chloride was obtained. Further, a polymer 8 having 30% by weight of acrylonitrile, 40% by weight of methyl acrylate, and 30% by weight of SAM was obtained by the same method as that for obtaining the polymer 2 in Example 1. Short fibers were obtained in the same manner as in Example 1 using a mixture of polymer 7: polymer 8 in a weight ratio of 98.5: 1.5 as a spinning dope.

得られた短繊維について、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに９０℃で６０分間染色した繊維を用いて（パイル加工法及び風合評価）手順によりポリシャーを５回かけ、パイル作成し、評価を行った。 The obtained short fibers were evaluated for dyeability, dynamic viscoelasticity tan δ and dischargeability in the same manner as in Example 1, and further using fibers dyed at 90 ° C. for 60 minutes (pile processing method and feel evaluation) ) According to the procedure, a polisher was applied 5 times, a pile was created and evaluated.

（実施例５）
内容積２０Ｌの耐圧重合反応装置にジメチルホルムアミド（ＤＭＦ）２３３部、アクリロニトリル９０部、アクリル酸メチル９．５部、２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム０．５部を投入し、窒素置換した。重合機内温を６５℃に調整し、開始剤として２，２−アゾビス（２，４−ジメチルバレロニトリル）（ＡＩＶＮ）を０．５部投入し重合を開始した。途中、ＡＩＶＮを１．０部追加しながら２時間重合し、その後７０℃に昇温して１０時間重合させ、本発明の重合体（Ａ）に該当する重合体９を得た。得られた共重合体の組成は、アクリロニトリル９０重量％、メタリルスルホン酸ナトリウム０．５重量％、アクリル酸メチル９．５重量％であった。さらに、実施例１における重合体２を得た方法と同様の方法によりアクリロニトリル５０重量％、アクリル酸メチル４０重量％、ＳＡＭ１０重量％の重合体１０を得た。重合体９：重合体１０の重量比が９２：８の比率になるように混合した物を紡糸原液とし、孔径０．１ｍｍ、ホール数１０，０００のノズルを通して、ＤＭＦ／水＝６０／４０、１５℃の凝固浴に紡出し、８５℃の熱水中にて７倍に延伸し、さらに乾燥後、さらに１６５℃にて緩和熱処理を行い、３．３ｄｔｅｘの繊維を得た。さらに実施例１と同様の方法でクリンプ付与、切断を行い短繊維を得た。 (Example 5)
233 parts of dimethylformamide (DMF), 90 parts of acrylonitrile, 9.5 parts of methyl acrylate, and 0.5 part of sodium 2-acrylamido-2-methylpropanesulfonate are charged into a pressure-resistant polymerization reactor having an internal volume of 20 L, and purged with nitrogen did. The internal temperature of the polymerization machine was adjusted to 65 ° C., and 0.5 part of 2,2-azobis (2,4-dimethylvaleronitrile) (AIVN) was added as an initiator to initiate polymerization. In the middle of the polymerization, 1.0 part of AIVN was added and polymerized for 2 hours, then heated to 70 ° C. and polymerized for 10 hours to obtain a polymer 9 corresponding to the polymer (A) of the present invention. The composition of the obtained copolymer was 90% by weight of acrylonitrile, 0.5% by weight of sodium methallylsulfonate, and 9.5% by weight of methyl acrylate. Further, a polymer 10 having 50% by weight of acrylonitrile, 40% by weight of methyl acrylate, and 10% by weight of SAM was obtained by the same method as that for obtaining the polymer 2 in Example 1. A mixture of polymer 9 and polymer 10 in a weight ratio of 92: 8 was used as a spinning stock solution, passed through a nozzle having a hole diameter of 0.1 mm and a hole number of 10,000, and DMF / water = 60/40, The fiber was spun into a 15 ° C. coagulation bath, stretched 7 times in hot water at 85 ° C., further dried, and further subjected to relaxation heat treatment at 165 ° C. to obtain 3.3 dtex fibers. Further, crimping and cutting were performed in the same manner as in Example 1 to obtain short fibers.

（実施例６）
実施例５における重合体９を得た方法と同様の方法により、アクリロニトリル９０重量％、メタリルスルホン酸ナトリウム０．５重量％、酢酸ビニル９．５重量％の重合体１１を得た。さらに、実施例１における重合体２を得た方法と同様の方法によりアクリロニトリル５０重量％、アクリル酸メチル４０重量％、ＳＡＭ１０重量％の重合体１０を得た。重合体１１：重合体１０の重量比が９２：８の比率になるように混合した物を紡糸原液とし、実施例５と同様の方法で短繊維を得た。 (Example 6)
By the same method as that for obtaining the polymer 9 in Example 5, a polymer 11 comprising 90% by weight of acrylonitrile, 0.5% by weight of sodium methallylsulfonate, and 9.5% by weight of vinyl acetate was obtained. Further, a polymer 10 having 50% by weight of acrylonitrile, 40% by weight of methyl acrylate, and 10% by weight of SAM was obtained by the same method as that for obtaining the polymer 2 in Example 1. Short fibers were obtained in the same manner as in Example 5 using a mixture of polymer 11: polymer 10 in a weight ratio of 92: 8 as a spinning dope.

（実施例７）
実施例２と同様に短繊維を得、７０℃で６０分間染色した繊維を用いて（パイル加工法及び風合評価）手順によりポリシャーを６回かけ、パイル作成し、評価を行った。 (Example 7)
A short fiber was obtained in the same manner as in Example 2, and a pile was made by using a fiber dyed at 70 ° C. for 60 minutes (pile processing method and feel evaluation) to create a pile and evaluated.

（比較例１）
実施例４における重合体７（アクリロニトリル４９重量％、スチレンスルホン酸ナトリウム０．５重量％、塩化ビニル５０．５重量％）単独を紡糸原液とし、実施例１と同様の方法で短繊維を得、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに１００℃で６０分間染色した繊維を用いてパイル加工性、風合の評価を行った。 (Comparative Example 1)
A short fiber was obtained in the same manner as in Example 1 except that the polymer 7 in Example 4 (49% by weight of acrylonitrile, 0.5% by weight of sodium styrenesulfonate, 50.5% by weight of vinyl chloride) was used as the spinning dope. Dyeability, dynamic viscoelasticity tan δ, and dischargeability were evaluated in the same manner as in Example 1, and pile workability and texture were evaluated using fibers dyed at 100 ° C. for 60 minutes.

（比較例２）
実施例３における重合体５（アクリロニトリル５２重量％、スチレンスルホン酸ナトリウム１．５重量％、塩化ビニリデン４６．５重量％）単独を紡糸原液とし、実施例１と同様の方法で短繊維を得、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに１００℃で６０分間染色した繊維を用いてパイル加工性、風合の評価を行った。 (Comparative Example 2)
A short fiber was obtained in the same manner as in Example 1 except that the polymer 5 in Example 3 (52% by weight of acrylonitrile, 1.5% by weight of sodium styrenesulfonate, 46.5% by weight of vinylidene chloride) was used as the spinning dope. Dyeability, dynamic viscoelasticity tan δ, and dischargeability were evaluated in the same manner as in Example 1, and pile workability and texture were evaluated using fibers dyed at 100 ° C. for 60 minutes.

（比較例３）
実施例５における重合体９（アクリロニトリル９０重量％、メタリルスルホン酸ナトリウム０．５重量％、アクリル酸メチル９．５重量％）単独を紡糸原液とし、実施例５と同様の方法で短繊維を得、実施例１と同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに１００℃で６０分間染色した繊維を用いてパイル加工性、風合の評価を行った。 (Comparative Example 3)
A short fiber was obtained in the same manner as in Example 5 using only the polymer 9 in Example 5 (acrylonitrile 90% by weight, sodium methallylsulfonate 0.5% by weight, methyl acrylate 9.5% by weight) alone as the spinning dope. The dyeability, dynamic viscoelasticity tan δ, and dischargeability were evaluated in the same manner as in Example 1, and the pile workability and texture were evaluated using fibers dyed at 100 ° C. for 60 minutes.

（比較例４）
比較例１と同様に短繊維を得、同様の方法で染色性、動的粘弾性ｔａｎδ、抜染性を評価し、さらに１００℃で６０分間染色した繊維を用いて（パイル加工法及び風合評価）手順によりポリシャーを８回かけ、パイル作成し、評価を行った。 (Comparative Example 4)
Short fibers were obtained in the same manner as in Comparative Example 1, and dyeing properties, dynamic viscoelasticity tan δ, and discharging properties were evaluated in the same manner, and fibers dyed at 100 ° C. for 60 minutes (pile processing method and texture evaluation). ) According to the procedure, a polisher was applied 8 times to create a pile and evaluated.

以上の実施例１〜７及び比較例１〜４の重合体組成を表１に、また評価結果を表２に示す。 Table 1 shows the polymer compositions of Examples 1 to 7 and Comparative Examples 1 to 4 and Table 2 shows the evaluation results.

表１、表２から明らかなように、比較例のようにスルホン酸基含有モノマーを含むだけでは、染色相対飽和値が低く、低温での染色性は向上しない。従って、染色は１００℃程度の高い温度で行う必要があり、染色時のクリンプセットを抑えることができない。このため、ポリッシャー回数も多くなり、また風合いのよいパイル布帛を得ることは困難である。これに対し、実施例のアクリル系合成繊維は、スルホン酸基含有モノマーの含有量が少ないアクリル系重合体に、スルホン酸基含有モノマーの含有量が多い重合体を混合した重合体組成物を原料とすることで、重合体中のスルホン酸基含有モノマーの総含有量が少なくても染色相対飽和値が高い。したがって、９０℃以下の低温での染色が可能で、染色のためのエネルギー（熱量）を低減できるうえ、染色時のクリンプセットが抑えられる。このため、ポリッシャーの回数が少なくても風合いの優れたパイル布帛を得ることができ、またポリッシャー回数を増やせば、さらに風合いのよいパイル布帛を得ることができる。また、本発明のアクリル系合成繊維は、抜染性にも優れる。

As is apparent from Tables 1 and 2, the dyeing relative saturation value is low and the dyeability at low temperature is not improved only by including the sulfonic acid group-containing monomer as in the comparative example. Therefore, the dyeing needs to be performed at a high temperature of about 100 ° C., and the crimp set during dyeing cannot be suppressed. For this reason, the number of polishers increases and it is difficult to obtain a pile fabric with a good texture. On the other hand, the acrylic synthetic fibers of the examples are made from a polymer composition obtained by mixing a polymer having a high content of sulfonic acid group-containing monomers with an acrylic polymer having a low content of sulfonic acid group-containing monomers. Thus, even if the total content of sulfonic acid group-containing monomers in the polymer is small, the dyeing relative saturation value is high. Therefore, dyeing at a low temperature of 90 ° C. or lower is possible, energy (heat amount) for dyeing can be reduced, and crimp set during dyeing can be suppressed. Therefore, a pile fabric having an excellent texture can be obtained even if the number of polishers is small, and a pile fabric having a better texture can be obtained if the number of polishers is increased. Moreover, the acrylic synthetic fiber of this invention is excellent also in dischargeability.

Claims

アクリロニトリル４０〜９５重量％、スルホン酸基含有モノマー０〜３重量％、その他共重合可能なモノマー５〜６０重量％を合計１００重量％となるように含有する重合体（Ａ）６０〜９９重量％と、アクリロニトリル５〜９０重量％、（メタ）アクリル酸及びそれらの塩類、（メタ）アクリル酸エステル類、（メタ）アクリルアミド、酢酸ビニルから選ばれる１種以上のモノマー９〜９４重量％、スルホン酸基含有モノマー１〜４０重量％を合計１００重量％となるように含有する重合体であって、該重合体中にスルホン酸基含有モノマーを前記重合体（Ａ）よりも多量に含有する重合体（Ｂ）１〜４０重量％を、前記重合体（Ａ）と重合体（Ｂ）との合計が１００重量％となるように混合した重合体組成物を湿式紡糸してなるアクリル系合成繊維。 Polymer (A) 60 to 99% by weight containing 40 to 95% by weight of acrylonitrile, 0 to 3% by weight of sulfonic acid group-containing monomer, and 5 to 60% by weight of other copolymerizable monomers to a total of 100% by weight 5 to 90% by weight of acrylonitrile, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylamide, 9 to 94% by weight of monomer selected from vinyl acetate, sulfonic acid A polymer containing 1 to 40% by weight of group-containing monomers in a total amount of 100% by weight, wherein the polymer contains a larger amount of sulfonic acid group-containing monomers than the polymer (A). (B) Acrylic obtained by wet spinning a polymer composition in which 1 to 40% by weight is mixed so that the total of the polymer (A) and the polymer (B) is 100% by weight. Synthetic fibers.

スルホン酸基含有モノマーを、前記重合体（Ａ）中に０〜１．５重量％、前記重合体（Ｂ）中に３〜３０重量％含有してなる請求項１記載のアクリル系合成繊維。 The acrylic synthetic fiber according to claim 1, wherein the sulfonic acid group-containing monomer is contained in the polymer (A) in an amount of 0 to 1.5 wt% and in the polymer (B) in an amount of 3 to 30 wt%.

重合体組成物中のスルホン酸基含有モノマーの総含有量が０．５〜３重量％である請求項１または２に記載のアクリル系合成繊維。 The acrylic synthetic fiber according to claim 1 or 2, wherein the total content of the sulfonic acid group-containing monomer in the polymer composition is 0.5 to 3% by weight.

８０℃の染色相対飽和値が０．５以上であり、沸水に３０分浸漬した時の収縮率が５％以下である請求項１〜３のいずれかに記載のアクリル系合成繊維。 The acrylic synthetic fiber according to any one of claims 1 to 3, which has a dyeing relative saturation value at 80 ° C of 0.5 or more and a shrinkage ratio of 5% or less when immersed in boiling water for 30 minutes.

先染め繊維を白色抜染した後の白度がＷ値で７０以上となる抜染性を有する請求項１〜４のいずれかに記載のアクリル系合成繊維。 The acrylic synthetic fiber according to any one of claims 1 to 4, wherein the synthetic fiber has a dischargeability such that the whiteness after the white dyeing of the dyed fiber is 70 or more in terms of W value.

請求項１〜５のいずれかに記載のアクリル系合成繊維を、６０〜９０℃の温度で染色してなり、染色前後での、動的粘弾性測定のｔａｎδが最大値を示す温度の変化が７℃以下である請求項１〜５のいずれかに記載のアクリル系合成繊維。 The acrylic synthetic fiber according to any one of claims 1 to 5 is dyed at a temperature of 60 to 90 ° C, and a change in temperature at which tan δ of dynamic viscoelasticity measurement shows a maximum value before and after dyeing. It is 7 degrees C or less, The acrylic synthetic fiber in any one of Claims 1-5.

請求項１〜５のいずれかに記載のアクリル系合成繊維を、紡糸後、クリンプ付与し、これを所定長さに切断して短繊維を得、該短繊維を６０〜９０℃の温度で染色し、該染色後の繊維からパイル布帛を作成し、仕上げ加工してなるパイル布帛。 The acrylic synthetic fiber according to any one of claims 1 to 5 is subjected to crimping after spinning, cut into a predetermined length to obtain a short fiber, and the short fiber is dyed at a temperature of 60 to 90 ° C. And a pile fabric formed by finishing a pile fabric from the dyed fibers.

還元可能なカチオン染料で染色された繊維からパイル布帛を作成した後、抜染してなる請求項７記載のパイル布帛。

The pile fabric according to claim 7, wherein the pile fabric is formed by discharging the fabric after the fiber is dyed with a reducible cationic dye.