JP4058689B2 - Spun yarn for frost land and dyeing method thereof - Google Patents

Description

  In the present invention, after mixing two kinds of raw fibers, each of which is cationized and modified using two kinds of cationization modifiers, and three unmodified raw fibers, a spun yarn is manufactured, The present invention relates to a melange spun yarn that can be post-dyed and capable of expressing the effect of multi-colored frosting (hereinafter referred to as melange) in a wide range of hues and colors by dyeing the spun yarn with an anionic dye.

For the purpose of creating high-value-added textile products, production systems that apply multi-hue patterns to textiles have been studied.
Even now, the production method that expresses multi-hue patterns using the same material is a so-called “dye-dying” method in which a spun yarn is dyed to a target hue and then combined with a plurality of dyed yarns. It has become mainstream. This method is mainly applied to cellulose fiber products, but it takes a lot of time from design and color determination to completion of the fiber products, and there is a long-term inventory risk of raw materials that are dyed spun yarns. There are drawbacks such as an increase, and improvements have been demanded for a long time. In order to solve this problem, so-called “post-dyeing”, in which textile products knitted and knitted by combining different materials are dyed sequentially or by adding different dyes in the same bath using the difference in dyeability of the materials. A method has been proposed.

  Specifically, dyeing is performed using a combination of cotton fibers and polyester fibers, recycled cellulose fibers and acrylic fibers, cotton fibers, polyester fibers, and nylon fibers as different materials. However, the combination of different types of materials such as synthetic fibers and cellulose-based fibers has a drawback that the characteristics such as natural and soft texture that are characteristic of cellulose materials cannot be realized sufficiently. From such a point of view, a combination of cellulose fibers alone is used, and knitted products using cationized cotton and cationized untreated cotton or their yarns are dyed with post-dyeing, marbling, and producing a gradation effect. It is disclosed that it is possible. (For example, see Non-Patent Document 1.) However, a product obtained by such treatment is characterized by utilizing a difference in dyeability with respect to an anionic dye, and it is impossible to obtain a product expressed in two or more hues. It was. To make it possible to express multiple hues of two or more hues with a single material, further study the dyeing mechanism, obtain new cellulose fibers with excellent dyeing fastness by post-dyeing, and combine them. is required.

The applicant has invented a naphthol dye-modified regenerated cellulose fiber having a difference in dyeability by modifying the fiber itself while being the same cellulose-based material. (See Patent Document 1.) Three types of this naphthol dyeable modified recycled cellulose fiber, cationized modified cellulose fiber and normal cellulose fiber are selected, and these three types of fibers are mixed. After that, it was invented that a spun yarn can be produced and dyed with a specific anionic dye to obtain a two-colored melange yarn, and was filed as Japanese Patent Application No. 2002-147495. However, it was not possible to realize a multi-color dyeable melange yarn using a complete single material (for example, cotton fiber) rather than a large classification of cellulose-based material (similar material).
"View line and its development" (Fukuoka Junichi "Textile Processing" extra printing notebook 24, VOL. 38, 1986, pp. 32-37) JP 2003-3322 A (2nd page, 2nd column)

  An object of the present invention is to provide a spun yarn for melange that can express the effect of melange of multiple hues with a single natural material in a wide range of hues and colors, and a dyeing method thereof.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio, respectively. The raw fibers have a large difference in dyeability, and when they are each dyed with an acid dye, it is found that the fixing rate to both is remarkably different, and these two types of cationized modified raw fibers are unmodified. After adding the original fiber and blending the three, it was made into a spun yarn and dyed with an anionic dye, so that a wide range of hues and colors could be expressed in melange.

  In other words, the spun yarn of the present invention is cationized using a fibrillated cationized modifier using a cationization modifier having a high percentage of hydrophobic groups and a cationization modifier having a low percentage of hydrophobic groups. It is a spun yarn for melange made by blending modified and unmodified raw fibers. As a cationization modifier having a high percentage of hydrophobic groups, the general formula (1)

（但し、Ｒ_１は炭素数が８〜１８のアルキル基、フェニル基又はフェニルメチル基であり、Ｘはハロゲン基である。）で示されるカチオン化改質剤を用い、疎水基の構成率の低いカチオン化改質剤としては、一般式（２）

(Wherein R ₁ is an alkyl group having 8 to 18 carbon atoms, a phenyl group or a phenylmethyl group, and X is a halogen group.) As a low cationization modifier, the general formula (2)

（但し、Ｒ_２は炭素数が1〜３のアルキル基であり、Ｘはハロゲン基である。）あるいは一般式（３）

(Wherein R ₂ is an alkyl group having 1 to 3 carbon atoms, and X is a halogen group.) Or general formula (3)

（但し、Ｘはハロゲン基であり、ｎは２〜１２の整数を表す。)で示されるカチオン化改質剤を用いる。本発明の上記霜降地用紡績糸は、酸性染料と反応染料で染色することにより霜降り状外観を表現するメランジ用紡績糸を得ることが出来、更に、該紡績糸を酸性染料と反応染料と直接染料で染色することにより、より複雑な色相を有する霜降り状外観を表現するメランジ用紡績糸を得ることが出来る。

(However, X is a halogen group and n represents an integer of 2 to 12). The above-mentioned spun yarn for frost landing according to the present invention can obtain a spun yarn for melange that expresses a marbling appearance by dyeing with an acid dye and a reactive dye. Further, the spun yarn is directly combined with an acid dye and a reactive dye. By dyeing with a dye, it is possible to obtain a melange spun yarn expressing a marbling appearance having a more complex hue.

  Since the raw fiber is cation-modified using two types of cationization modifiers, there is a significant difference in the dyeing properties of acid dyes, and multicolor dyeing is possible by mixing unmodified raw fiber As a result, we can dye multi-colored frosty ground in any color tone and use the same material, so we can make multi-colored textile products without damaging the properties of the material. Can be obtained.

  The material of the spun yarn referred to in the present invention is not particularly limited as long as it is a material having a functional group capable of reacting with a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio. Single material selected from plant fibers such as cotton and hemp, animal fibers such as wool and silk, recycled cellulose fibers such as viscose rayon, copper ammonia rayon, solvent-spun cellulose fiber, etc. Can be used. When cotton fibers are used, scoured and bleached cotton fibers that have better drug penetration than untreated cotton fibers are more preferred.

（但し、Ｒ_１は炭素数が８〜１８のアルキル基、フェニル基又はフェニルメチル基であり、Ｘはハロゲン基である。）で示され、例えば、３−クロロ−２−ヒドロキシジメチルドデシルアンモニウムクロライドが挙げられ、商品名としてＣＤＤＡ［四日市合成（株）製）、ＨＬＡ（阪本薬品工業（株）製］があり、これらを用いることができる。 The cationization modifier having a high constitutional ratio of hydrophobic groups referred to in the present invention is represented by the general formula (1).

Where R ₁ is an alkyl group having 8 to 18 carbon atoms, a phenyl group or a phenylmethyl group, and X is a halogen group. For example, 3-chloro-2-hydroxydimethyldodecyl ammonium chloride There are CDDA (manufactured by Yokkaichi Gosei Co., Ltd.) and HLA (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) as trade names, and these can be used.

  In the treatment method, a mixed aqueous solution of a cationization modifier and a reaction catalyst having a high percentage of hydrophobic groups is adjusted to pH 10 to 13.5, and the raw fiber to be treated is bath ratio 1: 5 to 1:30, temperature. After treatment at 50 to 80 ° C. for 60 minutes, washing, neutralization, washing, and oil agent treatment may be performed followed by dehydration and drying. The treatment concentration of the cationization modifier having a high percentage of hydrophobic groups is not particularly limited, but it depends on the contrast with other modified fibers that are dyed in shades or different hues from unmodified fibers. In the range of 1.0 g / l to 20.0 g / l. When the treatment concentration is less than 1.0 g / l, since the introduction of cationic groups is reduced, the difference in shade of the same hue with the unmodified raw fiber is undesirably small, and the concentration exceeds 20.0 g / l. In contrast, the reaction amount of the cationization modifier in the portion that is dyed darkly is saturated, whereas the reaction amount of the cationization modifier in the portion that is dyed lightly increases, resulting in a small difference in shade of the same hue. This is not preferable.

（但し、Ｒ_２は炭素数が１〜３のアルキル基であり、Ｘはハロゲン基である。）、あるいは一般式（３） In the present invention, the cationization modifier having a low composition ratio of the hydrophobic group is represented by the general formula (2).

(Wherein R ₂ is an alkyl group having 1 to 3 carbon atoms, and X is a halogen group), or general formula (3)

（但し、Ｘはハロゲン基であり、ｎは２〜１２の整数を表す。)で示され、一般式（２）の化合物としては、例えば、３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロライドが挙げられ、商品名としてカチオンマスターＣ［四日市合成（株）製］、ＣＯＰＡ−６０［三菱ガス化学（株）製］、ワイステックスＮ−５０［ナガセケムテックス（株）製]があり、これらを用いることができる。また、一般式（３）の化合物としては、例えば、１，６ビス−（３−クロロ−２−ヒドロキシジメチルアンモニウム）ヘキサンジクロライドが挙げられ、商品名としてカチオノンＵＫ［一方社油脂工業（株）製］があり、これを用いることができる。その処理方法は、一般式（２）あるいは一般式（３）のカチオン化改質剤と反応触媒の混合水溶液をｐH１０から１３．５に調整し、処理対象の原繊を浴比１：５〜１：３０、温度５０〜８０℃で６０分間処理した後、洗浄、中和、洗浄、油剤処理を行った後脱水・乾燥を行う方法を採ればよい。

(However, X is a halogen group, n represents the integer of 2-12.) As a compound of General formula (2), 3-chloro- 2-hydroxypropyl trimethyl ammonium chloride is mentioned, for example. There are Cation Master C [manufactured by Yokkaichi Gosei Co., Ltd.], COPA-60 [manufactured by Mitsubishi Gas Chemical Co., Ltd.], WISTEX N-50 [manufactured by Nagase ChemteX Corporation] as trade names, and these are used. be able to. Moreover, as a compound of General formula (3), 1, 6 bis- (3-chloro- 2-hydroxydimethyl ammonium) hexane dichloride is mentioned, for example, Cationone UK [one company oil and fat industry Co., Ltd. product is mentioned as a brand name. ], Which can be used. The treatment method is to adjust the mixed aqueous solution of the cationization modifier of the general formula (2) or the general formula (3) and the reaction catalyst to a pH of 10 to 13.5, and the raw fiber to be treated has a bath ratio of 1: 5 to 5. After treatment at 1:30 and a temperature of 50 to 80 ° C. for 60 minutes, after washing, neutralization, washing and oil agent treatment, dehydration and drying may be employed.

  The treatment concentration of the cationization modifier having a low composition ratio of the hydrophobic group is not particularly limited, but it depends on the contrast with the other modified fibers dyed in a shade difference or a different hue from the unmodified fibers. In the case of the cationization modifier of the general formula (2), 0.3 g / l to 8.0 g / l, and in the case of the cationization modifier of the general formula (3), 1.0 g / l to 20 g. It can be appropriately set within a range of 0 g / l. When the treatment concentration is lower than 0.3 g / l or less than 1.0 g / l, the introduction of cationic groups is reduced, so the difference in shade of the same hue with the unmodified raw fiber is reduced, which is not preferable. When the treatment concentration exceeds the upper limit of 8.0 g / l or 20.0 g / l, the reaction amount of the cationization modifier in the portion that is darkly dyed is saturated, whereas the cation in the portion that is lightly dyed As a result of increasing the reaction amount of the chemical modifier, it is not preferable because the difference in shade of the same hue becomes small.

  As a reaction catalyst for the cationization modifier, an alkali metal compound such as lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, or an alkaline earth metal compound such as calcium hydroxide or magnesium hydroxide is used. Although it can be used, it is preferable to use an aqueous alkali metal compound solution which is easy to handle and the aqueous solution is alkaline.

  The reason for selecting two kinds of cationizing agents, a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio, used in the present invention is the dyeing solution containing an acid dye. In this case, when these cationized modified fibrils are treated in the same bath, the fibrils modified with a cationized modifier with a high percentage of hydrophobic groups are selectively dyed with acid dyes. To do. The dyeing difference is proportional to the difference in carbon number of the hydrophobic group in the chemical formulas represented by the general formulas (1) to (3), and when the difference in carbon number of the hydrophobic group is in the range exceeding 5, the dyeing difference. Becomes obvious.

  The spun yarn for melange of the present invention is a cationized modified fiber using a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio. A post-work yarn is obtained by mixing the modified raw fiber and the unmodified raw fiber, and a conventional method can be used for the method of mixing and spinning.

  As a result of the test, the mixing ratio (% by weight) of these three fibrils was determined as follows: [(Fabric cation-modified using a cationization modifier having a high hydrophobic group composition ratio) + (Composition of hydrophobic groups) Raw fiber cationized and modified using a low rate cationization modifier)]: (Unmodified raw fiber) = [(3 + 3)]: (94)-[(3-77) + (77- 3)]: It has been found that a good frosting yarn can be obtained when it is configured to fall within the range of (20). That is, it is necessary that unmodified raw fiber is contained at least 20% of the entire spun yarn. The spun yarn mixed at such a ratio is dyed into a multi-colored dye using a subsequent anionic dye, and then a cationized modified fiber using a cationized modifier having a high composition ratio of the dyed hydrophobic group. And the difference in hue between the three fibers of the original fiber cationized and modified using a cationization modifier having a low hydrophobic group composition and the unmodified raw fiber, and each dyed or undyed fiber By the balance of the amount, the effect of a melange whose appearance is marbling can be exhibited.

  The dyeing process of the melange yarn after cationization modification according to the present invention and the effect of the dyeing will be described below. The form of the dyed material to be dyed may be in the form of a seed or cocoon, a knitted fabric, or a sewn textile product, and can be used as appropriate according to the purpose. The anionic dye used in the present invention is an acid dye, a reactive dye and a direct dye. When an unmodified raw fiber is made off-white by dyeing a cationized modified raw fiber, an acidic dye and a reactive dye are used. Use acid dyes, reactive dyes and direct dyes when dyeing all of the three original fibers.

  As the acid dye, those satisfying the dyeing fastness required in the market are desirable, and examples thereof include half-milling type, milling type, and metal complex type acid dyes. Examples of half milling types include acid dyes such as Sumiol First, Kayanol, Sandran MF, etc., and examples of milling types include Sumino Milling, Kayano Luminating, sand orchid N, etc. are mentioned, and as the metal complex salt type, the name of the dye of the product is Ranil W, Kayalux, or Isolan S, which can be appropriately selected.

  Examples of the reactive dye include reactive dyes having a trade name of Procion P, Kayashion P, Shivacron P, Mikashion, Kayashion E, Prosilon M, or Rebafix E, and can be appropriately selected from these. Examples of the direct dye include direct dyes such as Kayaras, Sirius, Shivafix, Indozol, Solar, etc., which can be appropriately selected from these.

  The dyeing method of dyeing raw fibers modified with different cationization modifiers of the present invention in multiple colors and making unmodified raw fibers off-white uses acid dyes and reactive dyes such as sodium hydroxide. A method of dyeing at a bath ratio of 1:10 to 1:30 at a temperature of 50 to 100 ° C. for 20 to 60 minutes using only a strongly basic catalyst as a dyeing assistant, or only a leveling agent using an acid dye and a reactive dye. As a dyeing assistant, any of methods for dyeing at a bath ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. for 20 to 60 minutes can be selected. Moreover, a positively charged sequestering agent can be used as appropriate in order to sequester the dyed seat where the cationized modified raw fiber remains. For the dyeing using an acid dye and a reactive dye, either a one-step dyeing method using two kinds of dyes at the same time or a two-step dyeing method for dyeing with each dye can be selected.

  When the two-stage dyeing method is used, the acid dye is a dye only with a bath ratio of 1:10 to 1:30, a method of dyeing at a temperature of 80 to 100 ° C. for 20 to 60 minutes, or a bath with an acid dye and a leveling agent. A ratio of 1:10 to 1:30 is dyed at a temperature of 80 to 100 ° C. for 20 to 60 minutes. The reactive dye is a dye and a basic catalyst in a bath ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. A method of dyeing for 20 to 60 minutes or a method of dyeing with a reactive dye and a leveling agent at a bath ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. for 20 to 60 minutes may be used in combination. Further, a fixing agent can be used according to the required dyeing fastness. The spun yarn dyed by this method has a cationization modification with a high cationization modifier with a high hydrophobic group composition, and the cationized fiber portion has a hue dyed with an acid dye. The fiber portion cationized and modified using a modifier exhibits a hue dyed with a reactive dye, and the unmodified fiber portion becomes a spun yarn for marbling areas having an off-white hue.

  In the present invention, the method of dyeing all three kinds of raw fibers is a method in which an object to be dyed is put into a dyeing solution prepared by using three kinds of dyes of acid dyes, reactive dyes and direct dyes and a leveling agent as a dyeing assistant. After neutralizing, neutral salt such as mirabilite is added and dyeing is performed at a temperature of 50 to 100 ° C. for 20 to 60 minutes. Moreover, a positively charged sequestering agent can be used as appropriate in order to sequester the dyed seat where the cationized modified raw fiber remains. The dyeing procedure is a one-step dyeing method using three types of dyes at the same time, but after following the above-mentioned method of dyeing raw fibers that have been cation-modified from unmodified raw fibers to off-white using acid dyes and reactive dyes. , A method of dyeing a neutral salt such as a direct dye and mirabilite as a dyeing assistant, or a method of dyeing using a neutral dye such as a reactive dye and mirabilite and a basic catalyst such as soda ash The two-stage dyeing method or the three-stage dyeing method can be selected. Further, a fixing agent can be used according to the required dyeing fastness.

The spun yarn dyed by the method of dyeing all three kinds of raw fibers is directly applied to the hue dyed with an acid dye on the fiber part cationized and modified with a cationization modifier having a high composition ratio of hydrophobic groups. A dye or reactive dye is directly applied to a hue dyed with a reactive dye on a fiber part that has been cationized and modified using a cationization modifier with a low hydrophobic group composition ratio, and the hue dyed with a dye or reactive dye is superimposed. The hues dyed in (1) and (2) exhibit a hue that overlaps, and the unmodified portion exhibits a hue that is directly dyed with a dye or a reactive dye. For example, when red acid dyes, blue reactive dyes and yellow direct dyes or yellow reactive dyes are used at equal dye concentrations, a portion that has been cationized using a cationization modifier with a high percentage of hydrophobic groups Exhibits an orange phase in which the red phase of the acid dye is directly overlapped with the yellow phase of the reactive dye or the reactive dye, and the portion cationized with a cationization modifier having a low hydrophobic group composition is the blue phase of the reactive dye. The yellow phase of the direct dye or the reactive dye overlaps with the yellow phase, and the unmodified part exhibits the yellow phase of the direct dye or the reactive dye. Further, when a marbling area is knitted using this yarn, a three-color melange knitted fabric of an orange hue, a scarlet hue, and a yellow hue is obtained. Also, a three-color melange knitted fabric can be obtained by mixing the three types of raw fibers and then dyeing them in the same manner.
The article to be dyed after the dyeing process is transferred to processes such as soaping, resin processing, finishing oil treatment, and the like, but these processes are not particularly limited and can be performed by generally used methods.

・染色堅牢度の測定方法
耐光堅牢度：ＪＩＳ Ｌ ０８４３：９８ キセノンア−ク灯光に対する染色堅牢度試験方法に準拠し測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this range. In addition, the determination method and dyeing fastness of the melange effect in this example were measured based on the following methods.
-Method for judging the effect of melange The degree of appearance of the stained sample by the sensory inspection by five inspectors was judged according to the following criteria.

-Measuring method of dyeing fastness Light fastness: JIS L 0843: 98 It measured based on the dyeing fastness test method with respect to a xenon arc lamp light.

Example 1
US cotton fiber 35% hydrogen peroxide aqueous solution 5g / l, hydrogen peroxide stabilizer [trade name: IP Kyreate D-40, manufactured by Yushi Co., Ltd.] 2g / l, 48% hydroxylated Scouring for 40 minutes at a bath ratio of 1:15 and a temperature of 95 ° C. with a treatment solution containing 4 g / l of an aqueous sodium solution and 0.5 g / l of a penetrant for scouring [trade name: Espirol BSconc, manufactured by Sun Chemical Co., Ltd.] After bleaching, it was washed with water, neutralized with a treatment bath containing 1 g / l of acetic acid [trade name: reagent acetic anhydride, manufactured by Kanto Chemical Co., Ltd.] at a bath ratio of 1:15 at a temperature of 50 ° C. and then washed with water. Thereafter, 3-chloro-2-hydroxydimethyldodecylammonium chloride (trade name: CDDA, manufactured by Yokkaichi Gosei Co., Ltd.) 5 g / l, which is a cationization modifier having a high composition ratio of hydrophobic groups, reaction catalyst [trade name: Reagent sodium hydroxide, manufactured by Kanto Chemical Co., Ltd.] 10 g / l, wet penetrant [trade name: Clean N-15, manufactured by Otsuka Kogyo Co., Ltd.] 2 g / l, bath ratio 1:15, after reacting at a temperature of 60 ° C. for 60 minutes, thoroughly washed with water, and a treatment bath containing 1 g / l of acetic acid [trade name: reagent acetic anhydride, manufactured by Kanto Chemical Co., Ltd.], bath ratio 1:15 , Neutralized at 50 ° C. for 15 minutes, washed with water, then soft and smooth finish [trade name: Zontes TA-460-15, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.] 8 g / l, spinning oil [trade name: Teron LE, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.] containing 2 g / l In a bath ratio 1:15 after treatment at a temperature 50 ° C. 20 min, spun dry, cationized was scoured, bleached and dried at 80 ° C. hot air reforming cotton fibers (A1) was about 1000g produced.

US cotton fiber 35% hydrogen peroxide aqueous solution 5 g / l, hydrogen peroxide stabilizer 2 g / l as described above, 48% sodium hydroxide aqueous solution 4 g / l, scouring penetrant 0.5 g as described above Scouring and bleaching with a treatment liquid containing 1 / l bath at a temperature of 1:15 and a temperature of 95 ° C. for 40 minutes, followed by washing with water and a treatment bath containing 1 g / l of acetic acid as described above, a bath ratio of 1:15 and a temperature of 50 ° C. 1,6 bis- (3-chloro-2-hydroxydimethylammonium) hexane dichloride which is a cationization modifier having a low composition ratio of a hydrophobic group having an active ingredient of 40% after neutralizing with water for 15 minutes [Trade name: Cationone UK, manufactured by Otsuka Oil Co., Ltd.] 20 g / l, a treatment bath containing 10 g / l of the same reaction catalyst as described above, and 2 g / l of the same wet penetrant as described above, with a bath ratio of 1: 15. After reacting at a temperature of 60 ° C. for 60 minutes, In a treatment bath containing 1 g / l of acetic acid as described above, neutralize at a bath ratio of 1:15 and a temperature of 50 ° C. for 15 minutes, then washed with water, and then 8 g of a soft and smooth finish similar to that described above. / L, a treatment bath containing 2 g / l of a spinning oil similar to the above, treated at a bath ratio of 1:15 and a temperature of 50 ° C. for 20 minutes, centrifuged and dehydrated, dried with warm air at 80 ° C., and scoured and bleached About 1000 g of the cationized modified cotton fiber (B1) was produced.
US cotton fiber 35% hydrogen peroxide aqueous solution 5 g / l, hydrogen peroxide stabilizer 2 g / l as described above, 48% sodium hydroxide aqueous solution 4 g / l, scouring penetrant 0.5 g as described above Scouring and bleaching with a treatment liquid containing 1 / l bath at a temperature of 1:15 and a temperature of 95 ° C. for 40 minutes, followed by washing with water and a treatment bath containing 1 g / l of acetic acid as described above, a bath ratio of 1:15 and a temperature of 50 ° C. And then washed with water and treated in a treatment bath containing 8 g / l of a soft and smooth finish similar to that described above and 2 g / l of a spinning oil similar to that described above at a bath ratio of 1:15 and a temperature of 50 ° C. for 20 minutes. Then, about 1000 g of unmodified cotton fiber (C1), which was centrifugally dehydrated, dried with hot air at 80 ° C., scoured and bleached, was produced.

  Next, a cotton fiber (A1) cationized and modified using a cationization modifier having a high composition ratio of hydrophobic groups obtained as described above, and a cationization modifier having a low composition ratio of hydrophobic groups is used. After blending at the mixing ratio shown in Table 1 using three types of cotton fibers: cationized modified cotton fiber (B1) and scoured and bleached unmodified US cotton fiber (C1) , Manufactured a spun yarn of 19.68 tex using a quick spin system (model: QSS-R20, manufactured by SDL International LTD) 1-No. 9 and comparative yarn no. 1-No. 3 and using these socks knitting machines, a sock knitted fabric having a length of about 30 cm is knitted. 1-No. 9 and comparative fabric No. 1-No. It was set to 3.

The obtained knitted fabric No. 1-No. 9 and comparative fabric No. 1-No. 3 is red acidic dye [trade name Sandlan Red MF-TNS, manufactured by Clariant Japan Co., Ltd.] 1.5% owf, blue reactive dye [Kayacion Blue P-3R, manufactured by Nippon Kayaku Co., Ltd.] 1.5% owf In a dye bath containing 1:20 at room temperature and 10 minutes at room temperature, then heated to 90 ° C. and 10 minutes later, a basic reaction catalyst [trade name: Espolon A-609; [Production] 4 g / l was added, treated at 90 ° C. for 20 minutes, and then cooled to 80 ° C. Next, after washing with water, a positively charged sequestering agent (trade name: 5MA-51, manufactured by Yushi Kogyo Co., Ltd.) with a treatment solution containing 2 g / l, a bath ratio of 1:20, and a temperature of 80 ° C. for 20 minutes. After the blocking treatment, in a treatment liquid containing 3.0 g / l of a surfactant [trade name: Bisnor RK, manufactured by Yushi Kogyo Co., Ltd.], a bath ratio of 1:20 at a temperature of 80 ° C. is 15 After soaping for a minute, the sample was washed with water and then dried with warm air at 120 ° C. 1-No. 9 and comparative sample no. 1-No. 3 was obtained.
As a result, a comparative sample No. 1 containing only fibers cationized and modified using a cationization modifier having a high composition ratio of hydrophobic groups was used. No. 1 was dyed in dark red, and comparative sample No. 2 consisting only of fibers cationized and modified using a cationization modifier having a low percentage of hydrophobic groups was dyed in dark blue.

  The obtained sample No. 1-No. 9 and comparative sample no. 1-No. Table 2 shows the observation results of hue 3 and the determination results of the melange effect.

  As apparent from Table 2, the sample No. 1-No. 9 and comparative sample no. 1-No. The dyed product of cotton fiber (A1) cationized and modified using a cationization modifier having a high composition ratio of 3 hydrophobic groups is dyed dark red under the condition of a red acidic dye concentration of 1.5% owf. The dyed product of cotton fiber (B1) cation-modified with a cationization modifier having a low group composition was dyed dark blue under the condition of a blue reactive dye concentration of 1.5% owf. The scoured and bleached unmodified cotton fiber (C1) had a slightly contaminated off-white hue. Sample No. 2 in which the amount of dyed sample was 2% and the amount of scoured and bleached unmodified cotton fiber (C1) exhibiting an off-white hue was 98%. No. 1 is a sample No. 1 in which the amount of the stained sample is small and the effect of melange is not clearly recognized, and the amount of the stained sample is 90% and the amount of the off-white sample is 10%. Since the amount of off-white of 9 was small, the effect of melange was not clearly recognized. Sample No. with a dyed sample amount of 20% to 50% and an off-white sample amount of 50% to 80%. 4, Sample No. 5, Sample No. No. 6 was a good marbling area where the effect of melange in two hues of dark red and dark blue was clearly recognized. In addition, the sample No. 1 in which the amount of the stained sample is 6% of the whole, the ratio of dark blue to dark red is almost equal, and the amount of off-white is 94%. Sample No. 3 in which the effect of melange was recognized, the amount of the stained sample was 80% of the whole, the ratio of dark blue to dark red was 19: 1, and the amount of off-white was 20%. 7 also showed the effect of melange of two hues. However, sample No. 1 was 6% of the total dyed sample, of which the ratio of dark blue to dark red was 5: 1 and the amount of off-white sample was 94%. 2 shows that the effect of melange of two hues is not clearly observed, the amount of the stained sample is 80% of the whole, and the ratio of dark blue to red is 79: 1, and the off-white sample Sample No. having an amount of 20%. Since the effect of melange with two hues is not clearly observed in Fig. 8, it is clear that the balance between the hue and the amount of the stained sample and the amount of the off-white sample is related to the expression of the melange effect. It was.

[Example 2]
3-chloro-2-hydroxypropyltrimethylammonium chloride (trade name: Cation Master-C, manufactured by Yokkaichi Synthesis Co., Ltd.), 20 g / l, which is a cationization modifier having a low hydrophobic group composition rate from US cotton fiber In a treatment bath containing 10 g / l of the same reaction catalyst as in Example 1 and 2 g / l of the same wet penetrant as in Example 1, the mixture was reacted at a bath ratio of 1:15 and a temperature of 60 ° C. for 60 minutes, and then thoroughly washed with water. Then, the same treatment bath containing 1 g / l of acetic acid as in Example 1 was neutralized at a bath ratio of 1:15 and a temperature of 50 ° C. for 15 minutes, followed by washing with water, and then 8 g of the same soft and smooth finish as in Example 1. / L, a treatment bath containing 2 g / l of the same spinning oil as in Example 1, treated at a bath ratio of 1:15 and a temperature of 50 ° C. for 20 minutes, then spin-dehydrated and dried with hot air at 80 ° C. About 1000 g of modified cotton fiber (B2) was produced.
About 1000 g of US cotton fibers were prepared and used as unmodified cotton fibers (C2).
15% by weight of the cotton fiber (A1) cation-modified using the cationization modifier having a high hydrophobic group composition ratio in Example 1 and the cation using the cationization modifier having a low hydrophobic group composition ratio. After blending 15% by weight of the modified cotton fiber (B2) and 70% by weight of the unmodified cotton fiber (C2), a spun yarn of 19.68 tex was manufactured using a quick spin system. , The test yarn No. It was set to 10. Test thread No. 10 is used to knit a sock knitted fabric having a length of about 30 m using a sock knitting machine. It was set to 10.

Knitted fabric No. 10 is the same 35% hydrogen peroxide aqueous solution 5g / l as in Example 1, the same hydrogen peroxide stabilizer 2g / l as in Example 1, 48% sodium hydroxide aqueous solution 4g / l, the same as in Example 1. In a treatment bath containing 0.5 g / l of a scouring penetrant, scouring and bleaching at a bath ratio of 1:15 and a temperature of 95 ° C. for 40 minutes, followed by washing with water and the same treatment bath containing 1 g / l of acetic acid as in Example 1, Bath ratio 1:15, neutralized at 50 ° C. for 15 minutes, washed with water, blue acidic dye [trade name: Kayacryl Sky Blue R, manufactured by Nippon Kayaku Co., Ltd.] 0.4% owf, red reactive dye [trade name : Kayacion Red P-4BN, manufactured by Nippon Kayaku Co., Ltd.] 0.4% owf, yellow direct dye [trade name: Kyarus Supra Yellow GLS, manufactured by Nippon Kayaku Co., Ltd.] 0.4% owf, leveling agent [Product name: UDA-104K, one company oil industry ( )] In a dye bath containing 1:20 at room temperature for 10 minutes, heated to 90 ° C., added with 10 g / l of sodium sulfate, treated at 90 ° C. for 30 minutes, and then treated at 80 ° C. The temperature was lowered. Next, after washing with water, soap (Sunmol 120, manufactured by Nikka Chemical Co., Ltd.) with a treatment solution containing 2 g / l was soaked at a bath ratio of 1:20 at a temperature of 80 ° C. for 15 minutes, and then washed with water. Next, the sample No. 1 was stained with warm air of 120 ° C. and stained. 10 was obtained.
The obtained sample No. Table 3 shows the observation results of ten hues, the determination results of the melange effect, and the measurement results of the fastness to dyeing with respect to xenon arc lamp light.

  Sample No. No. 10 was finished in a high quality knitted fabric with a marbling appearance in which dark blue and dark orange were mixed in light yellow. Cotton fiber A1, which has been cationized and modified with a cationization modifier having a high percentage of hydrophobic groups, is dyed blue with a blue acid dye and simultaneously dyed yellow with a yellow direct dye, so the two hues overlap. Cotton fiber B2 dyed dark blue and cationized with a cationization modifier with a low hydrophobic group composition rate is dyed red with a red reactive dye and simultaneously dyed yellow with a yellow direct dye. Therefore, the unmodified cotton fiber C2 dyed in a deep orange color with two hues overlapped and scoured and bleached was dyed pale yellow with a yellow direct dye. Sample No. 70% of the unmodified cotton fiber, which was 70%, was dyed after scouring and bleaching, but there was no problem in appearance quality. Cationized and modified cotton fibers occupying 30% of 10 were not affected by the scouring and bleaching performed after the modification, and there was no problem in appearance quality.

  By using the spun yarn for frost ground according to the present invention, it is possible to dye a multi-colored frost ground in an arbitrary color by dyeing in one step, so that the time required for manufacturing a textile product is shortened, and it is suitable for small-quantity multi-product production Yes. Moreover, since the spun yarn of the present invention uses the same material, it is a spun yarn for melange that can be made into a fiber product excellent in hygroscopicity and touch without impairing the properties of the material.

Claims (6)

  Original fiber cation-modified with a cationization modifier with a high percentage of hydrophobic groups, and original fiber cation-modified with a cationization modifier with a low percentage of hydrophobic groups A spun yarn for frosty ground, which is made by blending high-quality raw fibers into spun yarn. A cationization modifier having a high percentage of hydrophobic groups is represented by the general formula (1).

(Wherein R ₁ is an alkyl group having 8 to 18 carbon atoms, a phenyl group or a phenylmethyl group, and X is a halogen group.)
A cationization modifier having a low percentage of hydrophobic groups is represented by the general formula (2).

The spun yarn for frost landing according to claim 1, wherein R ₂ is a cationization modifier represented by R ₂ is an alkyl group having 1 to 3 carbon atoms and X is a halogen group. A cationization modifier having a high percentage of hydrophobic groups is represented by the general formula (1).

(Wherein R ₁ is an alkyl group having 8 to 18 carbon atoms, a phenyl group or a phenylmethyl group, and X is a halogen group.)
A cationization modifier having a low composition ratio of a hydrophobic group is represented by the general formula (3).

The spun yarn for frost landing according to claim 1, which is a cationization modifier represented by the formula (where X is a halogen group and n is an integer of 2 to 12).   The spun yarn for frost landing according to any one of claims 1 to 3, wherein the unmodified raw fiber contains at least 20% by weight of the entire spun yarn.   Original fiber cation-modified with a cationization modifier with a high percentage of hydrophobic groups, and original fiber cation-modified with a cationization modifier with a low percentage of hydrophobic groups A method for dyeing spun yarn for frost ground, characterized by dyeing a spun yarn made of quality raw fiber with an acid dye and a reactive dye.   Original fiber cation-modified with a cationization modifier with a high percentage of hydrophobic groups, and original fiber cation-modified with a cationization modifier with a low percentage of hydrophobic groups A method for dyeing spun yarn for frost ground, characterized by dyeing a spun yarn made of quality raw fiber with an acid dye, a reactive dye and a direct dye.