JPH10266078A - Simultaneous shrink-resistant and functional processings of structure of animal hair fiber such as wool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a brilliant dyed product excellent in washing durability, shrinkage resistance and sunlight fastness by adhering a polymer reacted with a specific dye to the insides and/or the surfaces of the fibers of a fiber structure containing animal hair fibers such as wool by an interfacial polymerization method. SOLUTION: This method for simultaneously imparting shrink resistance and functionality to the structure of animal hair fibers such as wool comprises immersing a wool woven fabric in an aqueous solution containing a chlorotriazine type reactive dye and/or an amino group-containing acidic dye, a water-soluble diamine such as hexamethylenediamine and an alkali agent such as sodium hydroxide, squeezing the fabric with a mangle, immersing the squeezed fabric in a nonaqueous solution comprising an acid chloride such as sebacoyl chloride and a water-insoluble solvent such as toluene, and subsequently drying or thermally treating the fabric to form a dyed polyamide thin film on the surfaces of the wool fibers by the interfacial polymerization method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and a product for producing an animal hair fiber structure such as wool, characterized in that functional processing such as dyeing, softening, antibacterial processing and water-repellent processing is performed simultaneously with shrinkproofing processing. It is. More specifically, animal hair fibrous structures such as wool are shrink-proof with excellent washing durability, and at the same time, they have high color fastness to sunlight. Rather, it relates to a method of applying and a product thereof.

[0002]

2. Description of the Related Art Animal hair fibers such as wool have a flaky structure (scale) on the fiber surface, and due to this surface structure, entanglement between the fibers occurs during washing, resulting in a remarkable shrink felt. Until now, various methods have been proposed to suppress this disadvantage.

[0003] For example, in oxidizing agent treatment (for example, chlorinating), a method has been proposed in which scale is removed, and as a result, the fiber surface is smoothed. This method has problems such as difficulty in uniform treatment by oxidizing agent treatment, change in color tone due to yellowing, and work environment. On the other hand, a method of coating the scale of the animal hair fiber surface with, for example, a urethane resin or an acrylic resin has also been proposed, but a large amount of resin adhesion is required to obtain satisfactory shrink resistance, and as a result, There is a problem that the texture becomes coarse and hard. A method using these methods in combination has also been proposed, but it is difficult to obtain a sufficient shrinkage-preventing effect, the texture becomes coarse and hard, the fiber yellows and becomes brittle, and the texture inherent in animal hair fibers such as wool is possessed. There are drawbacks such as significant impairment.

For dyeing animal hair fibers such as wool, generally, acid dyes such as leveling dyes and milling dyes and gold-containing dyes such as 1: 1 type dyes, 1: 2 type sulfonamide dyes and 1: 2 type sulfonate dyes are used. A variety of anionic dyes such as acid mordant dyes and reactive dyes are used, and the treatment is performed for about one hour at a temperature at or near boiling. However, this staining method
Damage to animal hair fibers such as wool is large, and the fibers are yellowed and embrittled. Furthermore, except for the reactive dye, the bonds to the fibers are ionic bonds, hydrogen bonds, polar van der Waals bonds, non-polar van der Waals bonds, and the like, and are not sufficiently strong. For this reason, dyeing fastness becomes insufficient, and as a countermeasure, fixing treatment is generally performed after dyeing in many cases. In addition, the reactive dye is often adsorbed on the fiber in a non-reacted state, in addition to the part where the fiber and the dye are completely reacted. When animal hair fibers such as wool are dyed in a clear and pale color, there is a disadvantage that light resistance is poor. This is largely due not only to the degradation of the dye itself by light, but also to the weak light resistance of animal hair fibers such as wool, which is a substrate polymer. Various methods have been proposed to remedy this drawback.

[0005] It has been proposed to dye animal hair fibers such as wool with a disperse dye having relatively high light resistance (Japanese Patent Laid-Open No. 49-7 / 1979).
1277, JP-A-49-71278),
This method not only lacks sharpness due to the disperse dye, but also has insufficient fastness. Further, a method has been proposed in which wool is dyed by a pad method with a reactive dye and then subjected to interfacial polymerization of a polyimine resin or a polyamine resin (Japanese Patent Laid-Open Publication No. Sho.
No. 1-179385, JP-A-61-179386), but also in this case, the dye did not sufficiently react with the fiber, and the fastness was insufficient.

Further, in the field of clothing, beautiful colors such as pink, turquoise blue and emerald green and vivid colors having a very light density are demanded from the viewpoint of fashionability. Dyes with very vivid colors are used, but the light fastness of these dyes themselves is very poor, and products dyed with these dyes have problems as actual products, Urgent improvements and improvements are desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a shrink-resistant material having excellent washing durability without impairing the feel and characteristics of animal hair fiber structures such as wool, which cannot be achieved by the prior art. At the same time, it is an object of the present invention to provide a new coloring method and a product thereof which can obtain a clear and high sunlight fastness.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention is an animal hair fiber structure such as wool to which a polymer in which a water-soluble dye and / or a water-dispersible dye is reacted as one component is provided by an interfacial polymerization method,
Further, it is an animal hair fiber structure such as wool, wherein the water-soluble dye and / or water-dispersible dye is a bifunctional reactive dye and / or an acid dye. Hereinafter, the content of the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The animal hair fibers such as wool in the present invention means natural keratinous fibers obtained from animals such as wool, camels, goats and rabbits. The animal hair fiber structure such as wool means a woven fabric, knitted fabric, nonwoven fabric, or the like obtained by using animal hair fiber such as wool alone or by mixing animal hair fiber such as wool with other fibers. Other fibers mixed and used here include synthetic fibers such as polyester, acrylic, nylon, aramid and vinyl chloride, natural fibers such as silk, cotton and hemp, and regenerated cellulose fibers such as rayon.

[0010] The term "fiber products" as used in the present invention refers to fabrics such as woven, knitted and non-woven fabrics using the above-mentioned animal hair fibers such as wool or mixed fibers, and suits, slacks, jackets and skirts obtained using them. , Shirts and other sewn products.

The water-soluble dye and / or water-dispersible dye used in the present invention is a chlorotriazine, chloropyrimidine, chloroquinoxaline type which can react with a diamine which is one component of a polymer obtained by an interfacial polymerization method. And an acidic dye having an amino group capable of reacting with an acid chloride. These dyes react with the polymer formed during the interfacial polymerization described later or are incorporated into the polymer as a component thereof.

The chlorotriazine type reactive dyes described above include Procion Yellow MX-4G and Procion Red MX-
G, Procion Blue MX-R, etc., and as the acrylolopyrimidine type reactive dye, Drimarene Brilli
ant Yellow K-3GL, DrimareneBrilliant Red K-4BL, D
rimarene Brilliant Blue K-BL, and chloroquinoxaline-type reactive dyes include Levafix
Brilliant Yellow E-3G, Levafix Brilliant Blue E-
B, etc., and other types having a chemical structure include Drimalan Red F-2GLS, Lanasol Red 6G, and the like, but are not particularly limited to these, and the reactive dyes May be used in combination.

The acid dye having an amino group described above includes:
Mitsui Acid Blue Black 10B, Suminol Leveling Blue
AGG, Supranol Fast Red F-2GL and the like,
It is not particularly limited to these, and these acid dyes may be used in combination.

Further, if a functional processing agent containing an amino group and / or a hydroxyl group (for example, a softening agent, an antibacterial agent, a water repellent, etc.) is used in place of or in combination with the above-mentioned dye, the required functions can be obtained. Can be imparted, and by adding various processing agents to the same bath, multi-functionality can be imparted at the same time.

Next, the coloring method of the present invention will be described. The animal wool fiber structure such as wool is refined and bleached by a conventional method, and then immersed in an aqueous solution containing a water-soluble diamine and an alkali agent, the above-mentioned dye, and, if necessary, a penetrant, and mangled for about 8 minutes.
0% (% by weight), and then immersed in a non-aqueous solution containing an acid chloride such as sebacoyl chloride at room temperature for about 80%.
%, And then dried to evaporate the organic solvent. By the dyeing process, a colored polyamide thin film is formed on the outermost layer of the animal hair fiber structure such as wool,
Isocyanates and epoxies that can react with diamines can be used in place of the above acid chlorides. After the dyeing process, if necessary, a steaming treatment and / or a treatment with an acidic aqueous solution such as formic acid may be performed, followed by washing with water and drying.

The water-soluble diamine referred to herein includes ethylenediamine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, piperazine, triethylenediamine, diethylenetriamine, triethylenetetraamine, dihexamethylenetriamine, 1,4
Aliphatic diamines such as -diaminocyclohexane, 1,4-diaminomethylcyclohexane, paraphenylenediamine, metaphenylenediamine, paraxylylenediamine, metaxylylenediamine, 4,4'-diaminobiphenyl, 4,4'-diamino Diphenylmethane, 4,
Examples thereof include aromatic diamines such as 4'-diaminodiphenyl ketone and 4,4'-diaminodiphenyl sulfone, but are not particularly limited thereto. These diamines may be used in combination.

The alkali agent mentioned here may be sodium hydroxide, sodium carbonate, sodium silicate, potassium hydroxide, lithium hydroxide or the like. The amount of diamine used may be about 0.03 to 0.7 mol.
The amount of the alkali agent may be about 0.03 to 0.7 mol. The penetrant may be in an aqueous solution concentration of 0.1 to 2.0%.

The dye mentioned here may be at a required concentration. In particular, in this coloring method, since a high light fastness is obtained in a light color that is difficult to obtain by a normal dyeing method, as a dye,
Particularly preferred is a 0.01 to 0.2% aqueous solution concentration. When the amount of the diamine is less than 0.03 mol, not only uniform coloring is not obtained, but also fastness is insufficient.
When it is 0.7 mol or more, there is a disadvantage that the texture becomes hard. The amount of the alkaline agent depends on the amount of the diamine used, but is not limited to 0.1.
If the amount is less than 03 mol, not only uniform coloring cannot be obtained, but also fastness is insufficient.

The cloth is immersed in the above aqueous solution using a normal padder, and then squeezed with a mangle or the like.
% To 90%. If it is less than 50%, uniform coloring cannot be obtained. If it is 90% or more, there is a disadvantage that the texture becomes hard. Immediately after squeezing with a mangle, it is immersed in a non-aqueous solution of acid chloride.

The acid chlorides used herein include aliphatic dicarboxylic acid chlorides such as succinic acid chloride, adipic acid chloride, pimelic acid chloride, suberic acid chloride, azelaic acid chloride, sebacic acid chloride and cyclohexanedicarboxylic acid chloride, and terephthalic acid chloride. , Isophthalic chloride, orthophthalic chloride, 4,
4'-biphenyldicarboxylic acid chloride, 4,4'-diphenylmethanedicarboxylic acid chloride, 4,4'-diphenylketone dicarboxylic acid chloride, 4,4'-diphenylsulfonedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride And the like. However, the present invention is not particularly limited thereto, and these dicarboxylic acid chlorides may be used in combination. Further, in some cases, tri- or more functional acid chlorides such as trimesic acid chloride, trimellitic acid chloride and pyromellitic acid chloride may be used in combination with dicarboxylic acid chloride.

Examples of the non-aqueous solvent include commercially available organic solvents such as toluene, benzene, chloroform and stoddard solvent, but are not limited thereto.
These non-aqueous solvents may be used as a mixture. After immersion, it is squeezed with a mangle and dried to evaporate the solvent.
In some cases, this is followed by a steaming treatment and / or a treatment with an acidic aqueous solution such as formic acid or acetic acid. The steaming treatment is for completing the reaction of the dye, and the acidic aqueous solution treatment is for neutralizing the residue of the alkaline agent contained in the diamine aqueous solution and partially increasing the color development of the dye.

[0022]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples and is not limited to the following Examples. Any of the modifications is included in the technical scope of the present invention.

(Processing sample) Wool fabric: Plain weave (100% merino wool) Yarn count: 2/60 Weight: 145 g / m ² Weave density: 233 × 213

[0024]

[Table 1]

(Evaluation of shrink resistance)
After washing according to JIS L-0217 103 method,
The area shrinkage was calculated. 1. Sample size: fresh (40cm) x side (40c
m) Scores are printed at intervals of 20 cm in the vertical and horizontal directions. 2. Number of washings: 20 repeated washings Area shrinkage = ((L1−L1 ′) × (L2−L
2 ′) / L1 × L2)) × 100 (%) L1: Length between scores in the vertical direction before washing (cm) L2: Length between scores in the horizontal direction before washing (cm) L1 ′: Length between scores in the vertical direction after washing (cm) L2 ': Length between scores in the horizontal direction after washing (cm)

(Hand Evaluation) The following three-step evaluation was performed by touch. ：: Good texture is shown compared to untreated cloth. ：: Shows the same texture as untreated cloth. Δ: Slightly coarser and harder than the untreated cloth. ×: coarser than untreated cloth, showing a significant reduction in texture.

(Sunlight fastness evaluation) JIS L 0841
According to the above, the fastness to sunlight 20 hours after irradiation with xenon light was evaluated using a fade meter.

(Evaluation of washing fastness) JIS L0844
It evaluated according to the A-1 method.

(Evaluation of antibacterial properties) Textile Sanitary Processing Association SE
The evaluation was performed according to the K standard shake flask method.

(Evaluation of water repellency) JIS L 1092-19
The initial water repellency of the examples and comparative examples was evaluated by a spray test of 92. The evaluation of water repellency was performed based on Table 2.

[Table 2]

Example 1 The above-mentioned wool fabric was immersed in the following processing composition liquid 1, squeezed with a mangle so as to have a pickup rate of 80%, and then immersed in the following processing composition liquid 2 so as to have a pickup rate of 80%. After squeezing with a mangle, a drying treatment was performed at 80 ° C.
Then, it was immersed in a 10% formic acid (85%) aqueous solution at room temperature for 3 minutes, washed with water and dried. (Working fluid composition 1): Hexamethylenediamine 0.05 mol / l Sodium hydroxide 0.05 mol / l Dye (described in Table 1 above) 0.1% soln. Tergitol TMN (manufactured by UNION CARBIDE) 0.1% sol. Water residue (working fluid composition 2): sebacoil chloride 0.05 mol / l toluene residue

Example 2 Working fluid compositions 1 and 2 of Example 1 were changed to working fluid compositions 3 and 4 as described below, and the same treatment was performed on the sample shown in Example 1. (Working fluid composition 3): Hexamethylenediamine 0.5 mol / l Sodium hydroxide 0.5 mol / l Dye (described in Table 1 above) 0.1% soln. Tergitol TMN (manufactured by UNION CARBIDE) 0.1% sol. Water residue (Working fluid composition 4): Sebacoil chloride 0.5 mol / l Toluene residue

Example 3 An amino-modified silicone-based softening agent (Mei-Silicon ASE-, manufactured by Meisei Chemical Co., Ltd.) was used in place of the dye of working fluid composition 3 of Example 2.
20) was carried out in the same manner as in Example 1 except that a 2% solution concentration was added.

Example 4 The procedure of Example 2 was repeated except that a 2% solution concentration of a quaternary ammonium salt cationic antibacterial agent (Nikkanone RB, manufactured by Nikka Chemical Co., Ltd.) was used instead of the dye of the working fluid composition 3 of Example 2. The same processing as in Example 1 was performed.

Example 5 An amino-modified silicone-based softening agent (Mei-Silicon ASE-, manufactured by Meisei Chemical Co., Ltd.) was used in place of the dye having the working fluid composition 3 of Example 2.
20) at a 2% solution concentration, a quaternary ammonium salt cationic antibacterial agent (Nikka Chemical KK, Nicanon RB) at a 2% solution concentration, and a fluorine-based water repellent agent (Asahi Glass LS-6015) ) Was added at a 2% solution concentration, and otherwise the same treatment as in Example 1 was performed.

COMPARATIVE EXAMPLE 1 Working fluid compositions 1 and 2 of Example 1 were changed to working fluid compositions 5 and 6 as described below, and the same treatment was performed on the sample shown in Example 1. (Working liquid composition 5): Hexamethylenediamine 0.01 mol / l Sodium hydroxide 0.01 mol / l Dye (described in Table 1 above) 0.1% soln. Tergitol TMN (manufactured by UNION CARBIDE) 0.1% sol. Water residue (working fluid composition 6): Sebacoil chloride 0.01 mol / l Toluene residue

COMPARATIVE EXAMPLE 2 Working fluid compositions 1 and 2 of Example 1 were changed to working fluid compositions 7 and 8 as described below, and the same treatment was performed on the sample shown in Example 1. (Working fluid composition 7): Hexamethylene diamine 0.8 mol / l Sodium hydroxide 0.8 mol / l Dye (described in Table 1 above) 0.1% soln. Tergitol TMN (manufactured by UNION CARBIDE) 0.1% sol. Water residue (Working fluid composition 8): Sebacoil chloride 0.8 mol / l Toluene residue

Comparative Example 3 The above-mentioned wool fabric was dyed by a conventional method using the dyes shown in Table 1.

As is clear from Table 3 which summarizes the above results, the wool woven fabric obtained in the examples was not treated, and the wool woven fabric obtained in Comparative Examples 1 and 3 did not reduce the texture originally possessed by wool. It can be seen that the shrinkage resistance was significantly improved. Comparative Example 2 has good shrinkage resistance, but the texture is significantly reduced. Further, from Example 3, the texture was improved by using the softener in combination. In addition, it can be seen from Example 4 that antibacterial performance was imparted. And from Example 5, flexibility,
It can be seen that antibacterial properties and water repellency have been imparted, confirming that multifunctional processing has been achieved.

As apparent from Table 4, Examples 1 and 2
Compared to Comparative Example 1 and Comparative Example 3 dyed by a conventional dyeing method, the light fastness is remarkably improved, and the washing fastness has no problem. In Comparative Example 2, the amount of applied resin was large, and as a result, the light fastness was also improved. However, as described above, the texture was significantly reduced and was not practical.

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

According to the present invention, it is possible to obtain excellent shrinkage resistance without significantly impairing the properties of animal hair fibers such as wool, and at the same time, a product which is colored in a bright color with high light fastness and functionality. Can be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI // D06M 101: 10 (72) Inventor Masakatsu Oguchi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Laboratory (72) Invention Person Shigeki Fukuoka 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Laboratory

Claims (2)

[Claims] 1. A polymer in which a water-soluble dye and / or a water-dispersible dye is reacted as one component is applied to the inside or / and the surface of a fiber structure containing animal hair fibers such as wool by an interfacial polymerization method. A method for processing an animal hair fiber structure such as wool, comprising: 2. The water-soluble dye and / or water-dispersible dye is a bifunctional reactive dye and / or an acid dye.
A method for processing a fibrous structure according to the above.