JP2005060874A - Heterogeneously cationization-modified fabric and method for dyeing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a three-hue heterodyed fabric excellent in fashionability, and to provide a dyeing method for the fabric. <P>SOLUTION: A heterogeneously cationization-modified fabric is provided. This fabric is obtained by using two kinds of cationization modifiers, i.e. a cationization modifier of high hydrophobic group constitution ratio and a cationization modifier of low hydrophobic group constitution ratio. The three-hue heterodyed fabric is obtained by dyeing the above fabric with an acid dye and a reactive dye to effect heterodyeing with gentle gradient in a heterohue fashion and further, as necessary, by dyeing the whole fabric with a direct dye or a reactive dye. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fabric that is non-uniformly cationized and modified using two types of cationization modifiers: a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio. The present invention also relates to a dyeing method in which the fabric is spotted with an anionic dye into a different color having a gentle gradient.

In general, textile products are usually made into products by coloring them with dyes or pigments from the viewpoint of consumer needs and fashionability. The dyeing methods are roughly divided into dyeing and printing. When dyeing a knitted fabric that uses a single material, dye it in a single hue, or dye a cross fabric made of warps and wefts of different materials. In some cases, dyeing warp and weft into different hues is an important indicator for determining commercial value.
On the other hand, in recent years, for the purpose of diversifying consumer needs and improving fashionability, artificially generating stained spots and development of new products with high sensibility have been carried out. As methods for artificially producing stain spots, there are a method using a physical dyeing agent such as wax and a chemical dyeing agent such as an organic acid, and a method using a discharging agent that decomposes dye molecules with an oxidizing agent or a reducing agent. Are known. In order to obtain a high-quality product using these methods, it is necessary to pay close attention to process management such as the concentration of chemicals used and processing temperature, and a simple new method has been demanded.

As one of such methods, a polyhalogenopolyazine compound or a sulfatoethylsulfone compound is covalently bonded to a part of the functional group of the fiber product, and then dyed to share the functional group of the compound with the fiber product. It is composed of a bonded non-dyed portion and a dyed portion that does not react with the functional group of the compound and the textile product, and is dyed afterwards, or there is no non-dyed portion or the density of the non-dyed portion is low and dyed at a high density, It is disclosed that the density of the non-dyed portion is dyed at a low density, whereby the shade of the color can express natural spotting. (Refer to Patent Document 1) However, even though this method can deal with the light and shade dyeing of the same hue, it cannot deal with the dyeing of two different hues, and the non-dyed part is generated, so that there are many unfixed dyes, As a result, there is a disadvantage that the environmental load becomes large.
As another method, the cellulose fiber structure is allowed to pass through a treatment liquid containing a quaternary ammonium base-containing compound capable of reacting covalently with the cellulose fiber in the presence of an alkali. A method of causing the treatment liquid to migrate rapidly by drying and then raising and dyeing, and after raising the cellulose fiber structure, the same treatment is carried out to raise the raised fiber Has disclosed a method for producing a cellulose fiber nap product having different dyeing concentrations at the tip and the root. (See Patent Document 2.)

The applicant has applied naphthol dye-modified modified cellulose fiber, cationized modified cellulose fiber and ordinary cellulose having different dyeability by modification while being the same cellulose-based material. -Three types of fiber were obtained, and it was invented that these fibers can be used to express multicolors of three or more hues with a specific anionic dye, and filed as Japanese Patent Application No. 2002-147495. However, this dyeing method cannot be used to spot-dye textile products. In addition, the applicant dyes the cationized modified part and the cationized modified part, but dyes the cationized modified part and the non-cationized modified part, but the cationized modified part. An undyed portion is dyed using a dye that is not dyed, and a method of dyeing so as to have a portion dyed in two colors and a portion dyed with a gentle density gradient is invented. Filed as 328192. However, it is not possible to spot the fabric in three colors by this method.
JP 11-81131 A (page 3, column 3, lines 5-13) JP-A-5-5279 (page 4, column 5, lines 5 to 13)

  An object of the present invention is to provide a three-color spot-dyed fabric excellent in sensitivity and fashionability and a method for dyeing the same.

  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. When the dyed fabric is dyed with an anionic dye, attention is paid to the fact that the fixation rate to the both is remarkably different. The present inventors have found that it is possible to produce a patch-dyed fabric having the present invention.

That is, the first invention of the present invention uses two types of cationization modifiers, a cationization modifier having a high percentage of hydrophobic groups and a cationization modifier having a low percentage of hydrophobic groups. It is a fabric that is non-uniformly cationized with a modifier.
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。

(However, X is a halogen group and n represents an integer of 2 to 12).

  The above-mentioned non-uniformly cation-modified fabric is a non-uniformly cation-modified portion of the non-uniformly cation-modified fabric that is non-uniformly cation-modified using a cationization modifier having a high percentage of hydrophobic groups. Is dyed with an acid dye, and a non-uniformly cationized modified part is dyed with a reactive dye using a cationization modifier with a low hydrophobic group composition ratio, and each of them is used for spotting with a gentle gradient in different colors. Stain. Furthermore, the whole fabric dyed and dyed is dyed directly with a dye, or the whole fabric is dyed with a reactive dye.

  Since fabrics that have been cationized using two types of cationization modifiers have a significant difference in dyeing properties with acid dyes, fabrics that have been non-uniformly cationized and modified have different colors. It is dyed and dyed with a gentle gradient. The whole dyed and dyed fabric is further directly dyed or dyed with a reactive dye, thereby enabling three-color spotted dyeing.

The fabric of the present invention is a woven fabric or a knit and a sewn product obtained by sewing them. The material 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 percentage of hydrophobic groups and a cationization modifier having a low percentage of hydrophobic groups, such as cotton and hemp. Regenerated cellulose fibers such as vegetable fibers, animal fibers such as wool and silk, viscose rayon, copper ammonia rayon, solvent-spun cellulose fiber and the like can be used. Also, a composite material obtained by blending these materials and synthetic fibers such as polyester fiber, polyamide fiber, and acrylic fiber and knitting and knitting can be used.
The cationization modifier having a high constitutional ratio of hydrophobic groups referred to in the present invention is represented by 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、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。

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.

The treatment concentration of the cationization modifier having a high composition ratio of the hydrophobic group is not particularly limited, but is appropriately set in the range of 1.0 g / l to 20.0 g / l depending on the intended difference in density or contrast of different colors. can do. When the treatment concentration is less than 1.0 g / l, the introduction of cationic groups is reduced, so that the difference in density is not preferred, and when the treatment concentration exceeds 20.0 g / l, the cationization modifier of the portion that is darkly dyed is not preferred. Although the reaction amount is saturated, the reaction amount of the cationization modifier in the portion that is lightly dyed increases, and as a result, the difference in density becomes small.
In the present invention, the cationization modifier having a low composition ratio of the hydrophobic group is represented by 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、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。
疎水基の構成率の低いカチオン化改質剤の処理濃度は特に限定されないが、目的とする濃淡差または異色相のコントラストに応じて一般式（２）のカチオン化改質剤の場合は０．３ｇ／ｌ〜８．０ｇ／ｌ、一般式（３）のカチオン化改質剤の場合は１．０ｇ／ｌ〜２０．０ｇ／ｌの範囲で適宜設定することができる。処理濃度が下限の０．３ｇ／ｌあるいは１．０ｇ／ｌ未満の場合はカチオン基の導入が少なくなるので濃淡の差が小さくなり好ましくなく、処理濃度が上限の８．０ｇ／ｌあるいは２０．０ｇ／ｌを超える場合は濃く染色される部分のカチオン化改質剤の反応量が飽和されるのに対して、淡く染色される部分のカチオン化改質剤の反応量が多くなる結果、濃淡差が小さくなるので好ましくない。

(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 concentration of the cationization modifier having a low composition ratio of the hydrophobic group is not particularly limited. However, in the case of the cationization modifier of the general formula (2), it is 0. In the case of the cationization modifier of 3 g / l to 8.0 g / l and general formula (3), it can be appropriately set within the range of 1.0 g / l to 20.0 g / l. When the treatment concentration is less than the lower limit of 0.3 g / l or 1.0 g / l, the introduction of cationic groups is reduced, so the difference between the shades is less preferred, and the treatment concentration is at the upper limit of 8.0 g / l or 20. When the amount exceeds 0 g / l, the reaction amount of the cationization modifier in the portion that is darkly dyed is saturated, whereas the reaction amount of the cationization modifier in the portion that is lightly dyed increases. This is not preferable because the difference is small.

Examples of the reaction catalyst for the cationization modifier used in the present invention include alkali metal compounds such as lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, or calcium hydroxide and magnesium hydroxide. Although an alkaline earth metal compound can be used, it is preferable to use an aqueous alkali metal compound solution that is easy to handle and the aqueous solution is alkaline. The concentration of the reaction catalyst aqueous solution may be an amount that can adjust the pH of the mixed aqueous solution to 10 to 13.5.
In the present invention, the mixed aqueous solution of the cationization modifier and the reaction catalyst is uniformly impregnated into the fabric. The temperature of the mixed aqueous solution is preferably 5 to 25 ° C. in order to suppress hydrolysis of the cationization modifier. As the impregnation method, the impregnation rate is preferably 50 to 100% by a commonly used dip dyeing method or padding method.

  Next, wrinkles are imparted to the impregnated fabric. For example, there are known methods such as a method of folding into an irregular shape, a method of folding after forming a loop shape, a method of filling an irregular shape in a loose carrier, etc. The method can be used as appropriate. The fabric is dried in a wrinkled state, but is preferably dried by spraying hot air on the fabric at a temperature of 80 to 120 ° C., and the cationization modification reaction is completed while the drying is completed. In this drying process, the cationization modifier moves along with the movement of moisture due to drying. As a result, the cationization modifier is concentrated in the fast-drying part. Conversely, in the slow-drying part, the cationization modifier moves to the fast-drying part. Since the reaction with the fabric is completed in a state where the concentration becomes light and the concentration change continues, as a result, the fabric has both a portion with a large and non-uniform cationization modification degree and a portion with a small cationization modification degree. Is obtained. The portion having a large degree of cationization modification and non-uniform modification is a fabric having a gentle gradient, with the degree of modification being reduced slightly from a portion having a high drying rate to a portion having a low drying rate. Since the unreacted product derived from the cationization modifier and the alkali reaction catalyst remain in the dried fabric, the cationization can be performed by washing and drying after a normal neutralization treatment as a post-treatment. A fabric having a high degree of modification and a nonuniformly modified part and a part having a small degree of cationization modification is obtained.

In the present invention, the fabric is treated using two kinds of cationization modifiers. However, the fabric may be treated in the same bath or in two steps. In order to make the appearance and fashionability more conspicuous, it is more preferable to treat the different-colored spot-dyed fabric obtained by the method of the present invention in two steps. In the treatment method, after treatment with a mixed aqueous solution of one kind of cationization modifier and reaction catalyst, wrinkles are applied, dried, neutralized, and then washed and dried. In the treatment of the cationization modifier twice, the order of which of the cationization modifier with a high hydrophobic group composition rate and the cationization modifier with a low hydrophobic group composition rate is performed first is appropriate. You can choose. Parts that have been cationized and modified by the respective cationization modifiers and have been modified non-uniformly with a large degree of non-uniform modification, overlapping parts, and parts with a small degree of cationization modification. A cationized modified fabric consisting of four parts is obtained.
In the present invention, when these non-uniformly cationized and modified fabrics are treated in a dyeing solution containing an acid dye which is an anionic dye, the non-uniformly modified cationization modifier having a high hydrophobic group composition rate is used. The dyeing portion is selectively dyed with an acid dye, but the dyeing difference is the difference in the carbon number of the hydrophobic group in the chemical formulas represented by the general formulas (1) to (3). It becomes obvious when the difference is in the range exceeding 5.

  Next, using the difference in dyeing, the anion dye is used to dye the non-uniformly cationized modified portion in different colors. The anionic dye used is an acid dye and a reactive dye, and the composition ratio of hydrophobic groups The non-uniformly cationized modified part with a high cationization modifier is an acidic dye, and the non-uniformly cationized modified part with a low hydrophobic group constituent rate reacts. Dye different colors with dyes. Furthermore, since the entire fabric can be dyed by using a direct dye or reactive dye, it is possible to separate the three colors even though it is a single material, which is impossible with the conventional method. In other words, the cationization modification part that is non-uniformly cationized using a cationization modifier with a high percentage of hydrophobic groups will result in cationization with a low percentage of hydrophobic groups in the overlapping hues of acid dyes and direct or reactive dyes. Portions that have been non-uniformly cationized with a modifier can be dyed into overlapping hues of reactive dyes and direct or reactive dyes.

  As the acid dye used in the present invention, 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 whose trade names are 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 used in the present invention include direct dyes such as Kayaras, Sirius, Shivafix, Indozol, Solar, etc., whose dye names are trade names, and can be appropriately selected from these. .

  The composition of the hydrophobic group is formed by dyeing the non-uniformly cationized modified portion with an acidic dye using a cationization modifier having a high composition ratio of the hydrophobic group constituting the non-uniformly cationized modified fabric of the present invention. The method of dyeing the non-uniformly cation-modified part with a low-rate cationization modifier with a reactive dye, and then dyeing the spots with a gentle gradient in each hue uses an acid dye and a reactive dye. Using a method in which only a strongly basic catalyst such as sodium hydroxide is used as a dyeing auxiliary, and a bath ratio of 1:10 to 1:30, a temperature of 50 to 100 ° C. for 20 to 60 minutes, or an acid dye and a reactive dye are used. Any one of the methods of dyeing at a bath ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. for 20 to 60 minutes using only the leveling agent as a dyeing assistant can be selected. In addition, a positively charged blocking agent can be appropriately used in order to block the dyed seat where the non-uniformly cationized modified portion 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. In the case of using the one-stage dyeing method, 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 ratio of an acid dye and a leveling agent. A method of dyeing at a temperature of 1:10 to 1:30 and a temperature of 80 to 100 ° C. for 20 to 60 minutes is employed. 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 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 employed. Further, a fixing agent can be used according to the required dyeing fastness.

  The composition of the hydrophobic group is formed by dyeing the non-uniformly cationized modified portion with an acidic dye using a cationization modifier having a high composition ratio of the hydrophobic group constituting the non-uniformly cationized modified fabric of the present invention. A non-uniformly cationized modified portion is dyed with reactive dyes using a low-rate cationization modifier, and then the whole fabric is dyed with direct dyes. The method consists of charging the dyed product into a dyeing solution prepared using three types of dyes, acid dyes, reactive dyes, and direct dyes, and a leveling agent as a dyeing assistant, raising the temperature to a predetermined temperature, and then neutral salt such as mirabilite. And a method of dyeing at a temperature of 50 to 100 ° C. for 20 to 60 minutes may be employed. In addition, a positively charged blocking agent can be appropriately used in order to block the dyed seat where the non-uniformly cationized modified portion remains. The dyeing procedure may be one-step dyeing using three types of dyes at the same time, or after following the above-mentioned method of dyeing non-uniformly cationized fabric with acid dyes and reactive dyes. Either a two-stage dyeing method or a three-stage dyeing method of dyeing with a natural salt as a dyeing assistant can be selected. Further, a fixing agent can be used according to the required dyeing fastness.

  The composition of the hydrophobic group is formed by dyeing the non-uniformly cationized modified portion with an acidic dye using a cationization modifier having a high composition ratio of the hydrophobic group constituting the non-uniformly cationized modified fabric of the present invention. A non-uniformly cationized modified portion is dyed with a reactive dye using a low-rate cationization modifier, and then the entire fabric is dyed with a reactive dye. The method is a method of dyeing for 20 to 60 minutes at a bath ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. using only an acid dye and a reactive dye as a dyeing assistant for a strong basic catalyst such as sodium hydroxide, Alternatively, after dyeing by using any of a dyeing method using an acid dye and a reactive dye as a dyeing auxiliary agent, a dye ratio of 1:10 to 1:30 and a temperature of 50 to 100 ° C. for 20 to 60 minutes, Such as reactive dyes, neutral salts such as mirabilite and soda ash In Irosuke agent, bath ratio 1:10 to 1:30, Taking a method for dyeing 20-60 minutes at a temperature 50 to 100 ° C.. In addition, a positively charged blocking agent can be appropriately used in order to block the dyed seat where the non-uniformly cationized modified portion remains. Further, a fixing agent can be used according to the required dyeing fastness.

The dyed material dyed by these methods was dyed directly or with a reactive dye on the hue that was non-uniformly cationized and modified with an acid dye using a cationization modifier with a high hydrophobic group composition rate. The hue dyed directly with the reactive dye or the hue dyed with the reactive dye on the part that was non-uniformly cationized and modified using a cationization modifier with a low composition ratio of the hydrophobic group. This is a fabric dyed and dyed with a gentle gradient in different hues, in which overlapping hues and portions with a low degree of cationization modification exhibit hues directly dyed with a dye or reactive dye. For example, when red acid dyes, blue reactive dyes, yellow direct dyes or yellow reactive dyes are used at equal dye concentrations, cationization modification is performed unevenly using a cationization modifier with a high percentage of hydrophobic groups. The part that has been subjected to an acid dye red phase directly overlaps the yellow phase of the reactive dye or reactive dye, and is a non-uniformly cation-modified part using a cationization modifier with a low hydrophobic group composition. Has a faint hue in which the direct dye or the yellow phase of the reactive dye overlaps the blue phase of the reactive dye, and the portion with a low degree of cationization modification exhibits the yellow phase of the direct dye or reactive dye, each with a gentle gradient in three hues. A fabric dyed and dyed. In addition, the color of the article to be dyed by the three dyes obtained by this method is slightly contaminated by the remaining two dyes, but the appearance quality is not affected.
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.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this range. In addition, the dyeing fastness in a present Example was measured based on the following method.
-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
1,6 bis- (3-chloro-2-hydroxydimethylammonium) hexane dichloride which is a cationization modifier with a low composition ratio of a hydrophobic group having an active ingredient of 40% [trade name: Cationone UK, on the other hand, Yushi Co., Ltd. (Manufactured by Co., Ltd.) 40 g and reaction catalyst (trade name: reagent sodium hydroxide, manufactured by Kanto Chemical Co., Ltd.) 3 g were dissolved in 20 ° C. water to make 1 liter, and a treatment liquid 1 having a pH of 12.5 was prepared.
Size of 25cm x 100cm 100% cotton plain fabric (14.75tex x 14.75tex / 90 pieces / inch x 100 pieces / inch) that has been baked, scoured, scoured, bleached and martised under normal conditions 4 are cut out and impregnated with a treatment solution 1 which is a mixed aqueous solution of a cationization modifier and a reaction catalyst having a low composition ratio of hydrophobic groups at a drawing ratio of 80% by a padding method, and then formed into a loop shape and an irregular shape. Folding wrinkles were applied to the sample and dried for 5 minutes in a hot air dryer at 100 ° C. Next, after washing with water, neutralization treatment with 1 g / l aqueous solution of acetic acid (trade name: reagent acetic acid, manufactured by Kanto Chemical Co., Ltd.), water washing, centrifugal dehydration, and drying for 5 minutes with a 100 ° C. hot air dryer. Four test fabrics were prepared that were both non-uniformly cationized and modified with a portion having a high degree of cationization modification and a portion having a low degree of cationization modification. These were designated as Sample A, Sample B, Sample C, and Sample D, respectively.

Separately, 5.0 g of 3-chloro-2-hydroxydimethyldodecylammonium chloride (trade name: CDDA, manufactured by Yokkaichi Gosei Co., Ltd.), which is a cationization modifier having a high percentage of hydrophobic groups, and a reaction catalyst (trade name: 3 g of reagent sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was dissolved in 20 ° C. water to make 1 liter, and a treatment liquid 2 having a pH of 12.5 was prepared.
Sample C and sample D are impregnated into a loop shape after impregnating treatment solution 2 which is a mixed aqueous solution of a cationization modifier and a reaction catalyst having a high hydrophobic group constituent ratio with a padding method at a drawing ratio of 80%. Folding wrinkles were applied to the standard shape and dried for 5 minutes in a hot air dryer at 100 ° C. Next, after washing with water, neutralization treatment with 1 g / l aqueous solution of acetic acid (trade name: reagent acetic acid, manufactured by Kanto Chemical Co., Ltd.), water washing, centrifugal dehydration, and drying for 5 minutes with a 100 ° C. hot air dryer. Sample C1 and sample D1 having both a portion having a high degree of cationization modification and a portion having a low degree of cationization modification were prepared.

  Sample B, Sample C1 and Sample D1 were bathed in a staining solution containing 1.0% owf of red acidic dye (trade name: Sandlan Red MF-TNS, manufactured by Clearant Japan Co., Ltd.) at a bath ratio of 1:20. After 10 minutes of treatment at room temperature, the temperature was raised to 95 ° C., treated for 20 minutes, and then lowered to 80 ° C. Next, after washing with water, a processing solution containing 2 g / l of a surfactant (trade name: Adecanol TS-800, manufactured by Asahi Denka Kogyo Co., Ltd.), a bath ratio of 1:20, and a temperature of 80 ° C. for 15 minutes. -After pinging, washing with water, centrifugal dehydration, drying with warm air at 100 ° C and spotting red, sample B1, sample C2 and sample D2 were obtained.

Next, two samples of sample C2 and sample D2 spotted in red are dyed in a staining solution containing 0.4% owf of a blue reactive dye (trade name: Kayacion Blue P-3R, manufactured by Nippon Kayaku Co., Ltd.). After a bath ratio of 1:20 and treatment at room temperature for 10 minutes, the temperature was raised to 95 ° C., and 10 minutes later, a basic reaction catalyst [trade name: Espolon A-609, manufactured by Otsuka Industries Co., Ltd.] 4 g / l was added. After treatment at a bath ratio of 1:20 and a temperature of 95 ° C. for 20 minutes, the temperature was lowered to 80 ° C. and then washed with water. Subsequently, the dyeing seat was sealed for 20 minutes at a bath ratio of 1:20 and a temperature of 80 ° C. with a treatment liquid containing 2 g / l of a positively charged blocking agent [trade name: 5MA-51, manufactured by Yushi Kogyo Co., Ltd.] And then washed with water. Subsequently, two samples of sample C3 and sample D3, which were spotted in two colors of red and blue, were obtained by washing with water, soaping, washing with water, centrifugal dehydration, and hot air drying under the same conditions as described above.
Next, the sample D3 was treated for 10 minutes at a bath ratio of 1:20 and a temperature of 70 ° C. in a staining solution containing 0.5% owf of a yellow reactive dye (trade name: Sumifix Supra Yellow 3GF, manufactured by Sumitomo Chemical Co., Ltd.). Then, after adding 20 g / l of mirabilite, after 15 minutes, 10 g / l of soda ash was further added and fixed for 40 minutes, followed by washing, soaping, washing, centrifugal dehydration under the same conditions as described above. The sample D4 dye | stained by orange, green, and yellow was obtained by drying with warm air.
Table 1 shows the results of measuring the hue of each part and the fastness to staining with a xenon arc lamp using Sample A as Comparative Sample 1, Sample B1 as Comparative Sample 2, Sample C3 as Sample 1, and Sample D4 as Sample 2.

Each sample is heterogeneously modified using a cationization modifier with a high percentage of hydrophobic groups and heterogeneous with a cationization modifier with a low percentage of hydrophobic groups. The comparative sample 1 before dyeing has an off-white hue, but the comparative sample 2 is dyed with a red acid dye. As shown in the figure, the portion with a high degree of modification, which was modified non-uniformly using a cationization modifier with a high percentage of hydrophobic groups, was spotted with a gentle concentration gradient from dark red to light pink, and the rest The part of was kept off-white hue. When this sample is further dyed with a blue reactive dye, as shown in Sample 1, a portion having a high degree of modification, which is non-uniformly modified using a cationization modifier having a high hydrophobic group constituent ratio, is dark red to light pink. The part with a high degree of modification changed from dark blue to light sky blue by using a cationization modifier with a low hydrophobic group composition ratio, which remains dyed with a gentle concentration gradient. Spotted with a gentle density gradient, and the portion with a small degree of cationization modification maintained an off-white hue. When this sample is further dyed with a yellow reactive dye, as shown in Sample 2, the portion having a large degree of modification, which is non-uniformly modified using a cationization modifier having a high hydrophobic group constituent ratio, is dark red to light pink. The degree of modification is unevenly modified with a cationization modifier that has a low density of hydrophobic groups and is dyed from dark orange to light orange because it is spotted with a gentle gradient and overlaps yellow. The part with a large density was dyed with a gentle density gradient from dark blue to light blue, and yellow was superimposed, so it was stained dark green to light green, and the part with a low degree of cationization modification was stained yellow .
The obtained dyed product is partially modified with a cationization modifier having a high hydrophobic group composition ratio and a non-uniformly modified portion with a high degree of modification and a cationization modifier with a low hydrophobic group composition ratio. There were parts where the parts with high degree of modification, which were modified unevenly using, overlapped, but the hues were mixed gently, there was no sense of incongruity, excellent appearance quality, dyeing fastness was also required for commercial use Satisfy the standards.

[Example 2]
A treatment liquid 2 which is a mixed aqueous solution of a cationization modifier having a high hydrophobic group composition ratio and a reaction catalyst adjusted to the same pH of 12.5 as in Example 1 was prepared. The same reaction as Example 1 with 10 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride [trade name: Cation Master-C, manufactured by Yokkaichi Synthesis], which is a cationization modifier having a low hydrophobic group composition 3 g of the catalyst was dissolved in 20 ° C. water to make 1 liter, and a treatment liquid 3 having a pH of 12.5 was prepared. Size of 25 cm x 50 cm 100% cotton plain fabric (11.81 tex x 11.81 tex / 132 pcs / inch x 80 pcs / inch) that has been baked, defatted, scoured, bleached and martised under normal conditions Then, after impregnating the treatment liquid 2 with a drawing method at a drawing rate of 80%, it was made into a loop shape, folded in an irregular shape, wrinkled, and dried in a hot air dryer at 100 ° C. for 5 minutes. Next, after washing with water, neutralizing with 1 g / l aqueous solution of acetic acid as in Example 1, washing with water, centrifugal dehydration, and drying for 5 minutes in a 100 ° C. hot air dryer, non-uniform cationization modification One test fabric having a portion with a high degree of modification and a portion with a low degree of modification was prepared.

After impregnating the obtained test fabric with the treatment liquid 3 which is a mixed aqueous solution of a cationization modifier having a high hydrophobic group composition ratio and a reaction catalyst adjusted to pH 12.5 at a drawing ratio of 80% by a padding method, It was made into a loop shape, folded in an irregular shape, wrinkled, and dried in a hot air dryer at 100 ° C. for 5 minutes. Next, after washing with water, neutralizing with 1 g / l aqueous solution of acetic acid as in Example 1, washing with water, centrifugal dehydration, and drying for 5 minutes in a 100 ° C. hot air dryer, non-uniform cationization modification One test fabric having both a portion with a high degree of modification and a portion with a low degree of modification was prepared and used as Sample E.
Sample E was then treated with a blue acid dye [trade name: Kayacryl Sky Blue R, manufactured by Nippon Kayaku Co., Ltd.] 0.4% owf, a red reactive dye [trade name: Kayacion Red P-4BN, 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 [trade name: UDA-104K; After a treatment at a bath ratio of 1:20 at room temperature for 10 minutes, the temperature was raised to 90 ° C., 10 g / l of sodium sulfate was added, and the mixture was treated at a temperature of 90 ° C. for 30 minutes, then 80 The temperature was lowered to ° C. 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. Subsequently, the sample 3 was dried by warm air of 120 ° C. to obtain a dyed sample 3.
Table 2 shows the observation result of the hue of each part of the obtained sample 3 and the measurement result of the color fastness to xenon arc lamp light.

The highly modified portion of the sample 3 that was non-uniformly modified using a cationization modifier having a high percentage of hydrophobic groups was dyed blue with an acid dye and simultaneously dyed yellow with a direct dye. As a result, the degree of modification is unevenly modified using a cationization modifier with a low concentration ratio of hydrophobic groups. The large part was dyed red with a reactive dye and simultaneously dyed yellow with a direct dye, so it was spotted with a gentle gradient from dark orange to pale orange with two hues overlapping, and cationization modification The small portions were directly dyed in the yellow phase of the dye, resulting in mottled and dyed fabrics each having a gentle gradient in three hues.
The resulting dyed product was partially modified with a cationization modifier having a high hydrophobic group composition ratio and a non-uniformly modified portion with a high degree of modification and a cationization modifier with a low hydrophobic group composition ratio. There were parts where the parts with high degree of modification that were modified non-uniformly overlapped, but the hues were mixed gently, there was no sense of incongruity, excellent appearance quality, and dyeing fastness was also required for commercial use Satisfy the standards.

  According to the method of dyeing a non-uniformly cation-modified fabric of the present invention, the non-uniform cationization modification is performed twice using two types of cationization modifiers, and dyed with a specific anionic dye. As a result, it is possible to obtain a fabric that has three colors and is dyed in natural shades and that has an unprecedented high sensitivity and fashionability. The fabric dyed in the three hues of the present invention is a new material that cannot be obtained by the conventional dyeing technique, and has the effect of greatly contributing to the development of new products in the fashion industry.

Claims (6)

  A fabric that is non-uniformly cationized and modified using two types of cationization modifiers: a cationization modifier having a high hydrophobic group composition ratio and a cationization modifier having a low hydrophobic group composition ratio. 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 fabric according to claim 1, wherein 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).

(However, X is a halogen group and n represents the integer of 2-12.) The fabric of Claim 1 which is a cationization modifier shown.   The non-uniformly cationized modified fabric according to claim 1 is dyed with an acidic dye at a portion of the non-uniformly cationized modified fabric using a cationized modifier having a high percentage of hydrophobic groups. Non-uniformly characterized by dyeing the non-uniformly cationized modified portion with a reactive dye using a cationization modifier with a low composition ratio, and dyeing with a dying dye having a gentle gradient in each hue A method for dyeing a cationized fabric.   A method for dyeing a non-uniformly cation-modified fabric, characterized in that the fabric dyed by the dyeing method according to claim 4 is further dyed on the whole fabric with a direct dye. A method for dyeing a non-uniformly cation-modified fabric, characterized in that the fabric dyed by the dyeing method according to claim 4 is further dyed with a reactive dye.