JPH0813361A - Dark color dyeing method for animal protein fibers or textile products - Google Patents

Abstract

PURPOSE:To dye an animal protein fiber or a fiber product into dark color using various dyes such as synthetic dyes and natural dyes by carrying out simple pretreatment without using specific dyeing processing facility and a processing machine. CONSTITUTION:An animal protein fiber or a fiber product is subjected to pre- treatment with an alkali water solution having such low alkali concentration as not to substantially damage the fiber or the fiber product, and then, the fiber or the fiber product is subjected to dyeing treatment.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for deep color dyeing of animal protein fibers or fiber products.

[0002]

2. Description of the Related Art Among modern practical fiber materials, silk protein fibers derived from insects are natural materials which are rich in sensitivity among clothing materials, and have excellent moisture absorption and dyeing properties, and excellent touch and feel.
Animal protein fibers contain a large number of basic groups, acidic groups, hydroxyl groups, and nonpolar groups, which serve as adsorption sites for dyes, so that vivid and deep dyeing is possible. There are many types of dyes such as direct dyes, acid dyes, vat dyes, and reactive dyes, and any dye can be applied to animal protein fibers. Many kinds of natural and synthetic dyes are known as dyes, but most of industrially important dyes are synthetic dyes. Such synthetic dyes are dyes having a single structure in chemical composition, and are produced inexpensively and in large quantities.
Further, in the dyeing using a synthetic dye, as long as the dyeing conditions are the same, it is possible to dye the same color tone every time, and it is possible to easily develop a primary color or a fluffy and highly saturated color tone depending on the preference.

[0003] In recent years, the nature orientation has become popular, and in the field of dyeing and processing, the tendency of nature orientation and regression to nature has been remarkable, and plant dyeing with natural dyes has caused a secret boom among women. Plant dyeing is a method of dyeing with dyes obtained from natural plants. With the "skin-friendly and safe" function as a weapon, technological development of plant dyeing is underway to expand new demand, and its application is spreading to towels, baby products, socks, etc. Dyeing protein fiber products with these dye plants can produce deep, soothing and astringent natural colors that can never be obtained with synthetic dyes. Also, the colors obtained from vegetable dyes never give an unpleasant hue, no matter what color is combined. However, dyeing with a natural dye has a problem in that it is less vivid than a color dyed with a synthetic dye. In addition, although the color tone varies depending on the type of plant, even if it is the same plant, the color tone varies depending on the roots, stems, leaves and flowers of the plants, and the location where the plants are collected, the season, the extraction method, etc. Since it changes subtly, it is difficult to get exactly the color you want. Further, in the case of using natural dyes, the color tone changes subtly only when the material to be dyed is different from silk or wool, and the color tone greatly differs depending on the type of the metal salt in the mordant treatment for color fixing. Although these are fats because they are naturally extracted pigments, the biggest problem with natural dyes in practice is that it is difficult to dye natural animal protein fibers in dark colors.

In general, in order to increase the surface dyeing density of textiles, a complicated and complicated dyeing technique which requires labor such as increasing the dye density of a dye bath and repeating the dyeing operation several to several tens of times is required. I have. There has been a demand for the development of a processing technique for easily dyeing dark colors without uneven dyeing. Silk can be dyed in vivid colors, but it is difficult to dye silk with black dye in deep colors. In deep-color dyeing, many dyes must be adsorbed in the fiber, but silkworm silk has a small number of basic amino acid residues that can serve as dyeing seats, so the amount of dye adsorbed in the fiber is small, resulting in a dark black color Dyeing becomes difficult. If black dyeing becomes possible on silk fabrics, it is expected to be a breakthrough in developing demand for formal men's clothing and casual products.

[0005] For dyeing protein fiber products, usually, a dyeing bath is prepared in a weakly acidic bath using a dyeing assistant such as acetic acid, ammonium acetate, ammonium sulfate or the like, and is heated from room temperature to 80 to 95 ° C.
Temperature for 30 to 45 minutes until the temperature rises to 30 to 60 minutes.
The method of dyeing while maintaining for a minute is a general dyeing method.
As described above, at the time of dyeing, the temperature of the dyeing bath must be increased, and heat energy is required for that. At low temperatures,
It is expected that the dark color dyeing technology that can be done in a short time will be an ideal dyeing processing method in terms of energy saving and efficiency improvement. In order to dye protein fiber products in dark colors, it was necessary to increase the dye concentration, reduce the bath ratio, or lower the pH. Alternatively, it is necessary to take measures for the dyeing process such as increasing the concentration of the dyeing aid. If the bath ratio is reduced and the pH of the dyeing bath is lowered in order to achieve deep color dyeing, there is a risk of uneven dyeing. If the dyeing is too rapid, uneven dyeing is likely to occur, while if it is too slow, there is a problem that the dyeing does not easily reach the desired desired density. For this reason, there has been a demand for a technique capable of performing a deep-color dyeing process in a dyeing process by performing processing by a simple method.

As a conventional dyeing technique for deep color dyeing, there is a dyeing method in which silica is added to a dyeing bath (Japanese Patent No. 1757485). By adding fine silica gel to the dye liquor and performing the neutral bath dyeing method, the dye anions are concentrated on the surface of the object to be dyed based on the interfacial electrochemical action of the silica gel, and as a result, the dye molecules are easily adsorbed in the fibers. It is considered that deep color dyeing can be realized. In this silica dyeing method, it is possible to perform deep dyeing by adding fine-particle silica gel to an ordinary dyeing bath without specially treating an object to be dyed. However, the particle size of silica gel greatly affects the deep-dyeing effect, and the effect of deep-dyeing is extremely weakened if the particle size is too large or too small. Also,
It has been found that the amount of silica gel added affects the staining effect. In general, the fastness to washing, rubbing, and abrasion, which are important practical properties of the dyed product dyed with silica, is lowered, and development of a dark color dyeing technique other than silica dyeing is desired. In order to solve these problems of the conventional dark-color dyeing technology, it is practical to pre-treat the material to be dyed by a simple method prior to the dyeing process, and to dye by a conventional general method. It is considered to be a color dyeing process, and development of the dyeing technology has been desired.

[0007]

The present invention is directed to synthetic dyes,
Solving the above problems that occur when dyeing animal protein fiber products with all kinds of dyes such as natural dyes, and without using special dyeing processing equipment or processing machines, the protein fiber products can be processed prior to dyeing processing. An object of the present invention is to provide a dyeing method capable of performing deep color dyeing with a wide range of dyes such as synthetic dyes and natural dyes by performing a simple pretreatment.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that animal protein fibers such as silk and wool or fiber products are first treated prior to the dyeing step of the dyed object. The inventors have found that the amount of the dye adhering to the fiber or the fiber product can be remarkably increased by pretreatment with a dilute alkaline solution, briefly drying, and then dyeing, and completed the present invention.

That is, according to the present invention, the animal protein fiber or fiber product is pretreated with an alkaline aqueous solution of a low concentration that does not substantially damage the fiber or fiber product, and then the dyeing process is performed. Provided is a method for deep color dyeing of a characteristic animal protein fiber product.

The dyeing material used in the present invention is an animal protein fiber or a fiber product. Examples of such a material include silk protein fibers derived from silkworms and wild silkworms, and fiber products thereof, wool keratin fibers, fiber products thereof, and the like. In the present invention, in order to dye such animal protein fibers or fiber products in a deep color, a pretreatment with an aqueous alkaline solution is performed prior to the dyeing step. The alkaline solution used for the alkaline treatment may be any alkaline agent in a concentrated range that does not impair the physical properties and microstructure of the protein fiber itself. As the alkaline chemical for treatment, an alkaline compound showing water solubility such as an alkali metal hydroxide or an alkaline earth metal hydroxide is used. In the present invention, it is particularly preferable to use sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium silicate. Among these agents, sodium hydroxide is particularly desirable as a pretreatment agent for deep color dyeing.

The alkali concentration in the alkaline aqueous solution used in the present invention may be any concentration which does not substantially damage the fiber or fiber product to be dyed, and is generally 12 g / L.
(Liter) or less, preferably 10 g / L or less. In the case of silkworm silk fibers or fiber products, the alkali concentration is preferably in the range of 1 to 4 g / L, and is 2 to 3 g.
/ L, especially 2.5 g / L concentration is most preferred. Since wild silk silk fibers or fiber products have excellent alkali resistance, in this case, an alkali concentration of 2 to 15 g / L gives a good result, and in particular, an alkali concentration of 8 to 12 g / L gives an excellent effect. . In the case of wool that is susceptible to structural changes due to alkali, 0.2-2 g / L, preferably 0.4-
An alkali concentration of 0.6 g / L is good. As described above, it is desirable to adjust the concentration of the alkaline aqueous solution in accordance with the alkali resistance properties of the fiber or fiber product to be dyed.

To carry out the alkali treatment of animal protein fiber or fiber product, the fiber or fiber product is immersed in a predetermined alkaline aqueous solution for about 5 to 45 minutes and then pulled up. In this case, the excess alkali aqueous solution is removed, and the dewatering rate (pickup rate) for the fiber or textile product is set to 80.
It is good to adjust to about 150% by weight, preferably 90 to 110% by weight, particularly about 100% by weight. Next, the fiber or fiber product containing the aqueous alkali solution is heated at 20 to 45 ° C., preferably 30 to 35 ° C., for 10 to 30 minutes, preferably 20 to 45 ° C.
Hold for 25 minutes. Thereby, effects such as microscopic loosening of the microstructure of the fiber can be obtained without damaging the mechanical properties of the animal protein fiber or the fiber product. Next, the alkali-treated fiber or fiber product thus obtained is dried. As a drying method, a temperature of 25 to 100 ° C.
In addition to the heating and drying method described above, a conventionally known method such as a method of contacting with heated air at 80 to 110 ° C. and a vacuum drying method can be employed. In this way, animal protein fibers or fiber products having excellent dyeability and fastness properties can be obtained.

Other methods for alkali treating animal protein fibers or fiber products include Pad / Batch.
Can show the law. This method is a method in which a fiber or a fiber product absorbing an alkaline aqueous solution is sealed in a plastic bag and kept for a predetermined time. In order to carry out this method, the fibers or textiles are treated with the fibers or textiles 10.
1000 parts by weight or more, preferably 1 part by weight with respect to 0 parts by weight
Put in 500 to 2000 parts by weight of alkaline aqueous solution
After leaving it for 0 to 45 minutes, preferably about 15 to 25 minutes, it is dehydrated with roll mangle to obtain a liquid removal rate of 80 to 150.
%, Preferably 90 to 110% by weight, especially about 100%
A fiber or fiber product is obtained that has absorbed a weight percent alkaline aqueous solution. Next, the fiber or fiber product wet with the alkaline aqueous solution is put in a plastic bag such as polyethylene, and the opening is heat-sealed or sealed with cellophane tape, and in this state, at a temperature of 25 to 35 ° C. After leaving it for 20 to 30 hours, preferably about 24 hours, the bag is opened, the contents are taken out, thoroughly washed with running water, and dried.

As described above, the fiber or the fiber product which has been subjected to the alkali treatment has a very good dyeing property.
Even if this is dyed by an ordinary dyeing method, it is possible to obtain a high-concentration dyed product having excellent fastness, which cannot be achieved with alkali-untreated fibers or fiber products. The dye for dyeing the alkali-treated fibers or textile products is not limited at all, and various types of conventionally known natural and synthetic dyes can be used. Such dyes include
Examples thereof include acid dyes, disperse dyes, direct dyes, and other synthetic dyes and natural dyes. In particular, acid dyes and a wide range of natural dye extractable dyes show good dyeing properties on the alkali-treated fibers or textiles according to the invention.

As a method for dyeing the alkali-treated fiber or fiber product according to the present invention, a conventionally known method is adopted. The dyeing liquor used at that time is not restricted at all, and a dyeing liquor having a component composition generally used conventionally can be used as it is. Fibers or fiber products obtained by dyeing after alkali treatment in advance according to the present invention are dyed much deeper than those obtained by dyeing without conventional alkali treatment. In the conventional deep-color dyeing method using silica gel, the dye does not penetrate and diffuse into the interior of the fiber, and is mainly localized on the fiber surface. Therefore, when the dyed material is washed or soaked in water, the dye on the surface falls off. Therefore, there is a problem that the fastness to friction is low. On the contrary,
In the present invention, since the distribution of the dye occurs uniformly in the fiber, the dyeing product obtained by the present invention is a conventional dark dyeing technique (Patent No. 1757485) in which fine particle silica gel is added to the dyeing solution.
Weathering resistance and fastness to rubbing are remarkably improved as compared with the dyed product obtained in No. 1), and it is effective as a dark color dyeing method for compensating for the drawbacks of the conventional techniques.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to Examples. The invention is not limited by these examples. In addition,% shown below is weight%.

Example 1 A 14-broom household silkworm silk feather dub (manufactured by Japan Standards Association) manufactured for JIS dye fastness test according to JIS L 0803 was used as a sample cloth. A sample cloth was washed with a sodium hydroxide solution (2 g / L, 4 g
/ L) for 20 minutes, followed by dewatering with a roll mangle to a dewatering rate of 100%. The sample cloth was put in a transparent bag made of polyethylene, the opening was folded back a few times and sealed with cellophane tape. This was placed in a constant temperature oven at 30 ° C. and kept for 24 hours to carry out an alkali treatment. After a predetermined time, the sample cloth was taken out of the polyethylene bag, and the fibers were washed with running water to completely remove the alkali components contained in the fibers, and then dried for 1 hour in a dryer at 105 ° C. Next, the alkali-treated sample cloth thus obtained was dipped in the safflower extract (yellow) obtained as described below, and dyed at 70 to 80 ° C. for 30 minutes. In order to fix the dyeing, it is placed in a 2 g / L tin solution (stannic chloride as a tin compound, SnCl ₂ dissolved in water), mordanted at 25 ° C. for 20 minutes, and washed with water.

(Preparation of Safflower Extract) A plant dye safflower (dried state) was weighed 4 times the weight of the sample cloth, placed in a gauze bag, and immersed in water 60 times the weight of the sample cloth for 1 day. An extract containing a yellow color of safflower was obtained.

Next, 2 mL of the remaining solution after the above-mentioned staining was
After diluting with L of distilled water, the absorbance of the residual dye solution was measured as follows. The value of the absorbance of the safflower yellow pigment at a main wavelength of 402 nm was measured using a Shimadzu self-recording spectrophotometer (UV-31).
00S) and the reflectance R (%) near 402 nm at which the absorbance of the yellow dye molecule is maximized, and then the dye concentration (K / S) on the fiber surface is determined by Kubelka.
It was calculated and evaluated according to the following formula proposed by Munch. K / S = (1−R) ² / 2R where R is the reflectance (%) at the maximum absorption wavelength of the dye molecule, K / S is the surface dyeing density, and L is the lightness (light).
Ness), a, and b are hue indices, and the physical quantities of these Ravies are all computer programs (UV-2100 / 31) installed in the spectrophotometer.
00). Table 1 shows the dyeability data such as the absorbance of the residual dye solution, the reflectance (R) of the material to be dyed, and the surface dyeing concentration (K / S).

[0020]

[Table 1] Dyeing results with plant dye (yellow pigment of safflower)吸 光 Absorbance of residual dye R% K / S Lab ──────────────────────────────────── Control group (conventional method) 86.19 37.0 0.54 65.42 0.87 35.51 Invention product (I) (2 g / L) * 86.70 36.5 0.55 65.23 1.02 35.20 Invention product (II) (4 g / L) * 85.68 35.0 0.60 64.04 1.30 34.72 ── ────────────────────────────────── * Indicates the alkali concentration in the alkali treatment.

In the dyeing of the sample cloth treated with the alkali according to the present invention, the absorbance of the residual dyeing solution is slightly lower than that of the control group. The decrease in the dye concentration in the residual dye solution means that the dye has penetrated the silk thread of the sample cloth and has been dyed in a deep color. In addition, according to the surface dyeing concentration (K / S) measurement of the material to be dyed, which is different from the method using the residual dye solution, the K / S value of the dyed material of the alkali-treated sample cloth slightly increased. It corresponds well with the measurement result of the method using the residual liquid.

Example 2 As shown in Example 1, a yellow pigment can be first extracted from safflower. After the yellow pigment is extracted, the red pigment (including the main component, carthamin) can be further extracted from the extracted safflower. In Example 2, it was decided to dye the silkworm domestic silk with a red pigment. The safflower after the extraction of the yellow pigment used in Example 1 was put into a gauze bag, put in a 2 g / L aqueous solution of sodium carbonate, and left at 25 ° C. for 24 hours to extract the red pigment. Put silk cloth as a sample cloth in the red dye solution of safflower,
Treat at 40 ° C for 30 minutes and stain. To fix the dye, it was immersed in a 0.5% citric acid aqueous solution at room temperature for 30 minutes to perform mordant treatment. Since the spectral curve of the residual liquid stained with the safflower red pigment became flat as a whole, the absorbance value at a wavelength of 400 nm at which absorption was relatively large was measured. Also, as described in Example 1, its absorbance,
The reflectance (R)% and the surface dyeing concentration (K / S) of the material to be dyed were measured. The obtained results are shown in Table 2.

[0023]

[Table 2] Dyeing results with plant dyes (red color of safflower)吸 光 Absorbance R% K / S Lab 対 照 Control (conventional Method) 9.23 23.94 1.21 59.07 25.34 -3.62 Inventive product (I) (2 g / L) * 9.11 21.71 1.41 57.18 26.68 -3.81 Inventive product (II) (4 g / L) * 8.97 18.58 1.74 53.69 27.35 -2.07 ─── ─────────────────────────────────

The absorbance of the residual dye solution upon dyeing the alkali-treated sample cloth according to the present invention was slightly lower than that of the control, and the same results as in Example 1 were obtained. According to the measurement of the surface dyeing density (K / S) of the article to be dyed, an increase in the K / S value of the dyed article of the alkali-treated sample cloth is more effective in deep-color dyeing than the safflower yellow pigment (Example 1). It is remarkable, and the deep dyeing effect is clear by the alkali treatment.

Example 3 Acid dye (Suminol FAST Red B conc; manufactured by Sumitomo Chemical Co., Ltd.)
Was used to carry out a dyeing experiment on wool. The dye concentration is 1% os. Per fiber weight. w. f. Acetic acid as a dyeing aid,
The ammonium acetate concentration was 3% o. w. f. , 2
% O. w. f. Adjusted to. The temperature of the dye bath was raised to 80 ° C. over 40 minutes from 40 ° C., and the dyeing was completed by treating at 80 ° C. for 30 minutes. During the temperature rising process, when the temperature of the dyeing bath was gradually increased to 53.3 ° C, 66.6 ° C, and 79.9 ° C, after the temperature of the dyeing bath reached 80 ° C,
After a lapse of 15 minutes and 30 minutes, the material to be dyed was taken out of the dyeing bath. The dyeing residual bath was diluted 5-fold, and the absorbance at a wavelength of 505 nm was measured using a Shimadzu self-recording spectrophotometer (UV-3100S).
I asked for. Separately from this, a standard curve was prepared by obtaining the absorbance of a dyeing stock solution having a predetermined concentration with different concentrations. The values of the absorbance at 505 nm of the various residual stains were applied to a calibration curve, and the respective staining concentrations were determined. The absorbance, dye concentration, dyeing rate and pH of the residual dye solution during the dyeing process were measured. Table 3 shows the obtained results. The dilution ratio was 1: 5. The unit of the concentration of the residual staining solution is 10 ⁻⁵ g / mL. The dyeing ratio was calculated from the dye bath dye concentrations before and after dyeing according to the following formula. Dyeing rate = (Dye bath concentration before dyeing−Dye residual solution concentration) / (Dye bath concentration before dyeing) The reflectance of the material to be dyed and the surface dyeing concentration were measured. The results obtained are shown in Table 4.

[0026]

[Table 3] Wool dyeing characteristics (absorbance, dye concentration, dyeing ratio, pH) ─────────────────────────────── ────── Absorbance of residual dyeing solution Dye concentration Dye ratio (%) pH ────────────────────────────── ────── Wool control 1) 53 ℃ 1.2 15.8 21 4.50 2) 67 ℃ 0.74 9.7 52 4.53 3) 80 ℃ 0.17 2.2 89 4.62 4) 80 ℃, 15 minutes 0.37 1.0 95 4.59 5) 80 ℃, 30 Min 0.23 0.6 97 4.60 Invented method Wool 2g / L NaOH solution treatment 1) 53.3 ℃ 0.23 3.0 85 4.99 2) 66.6 ℃ 0.4 1.0 95 4.98 3) 79.9 ℃--95-4) 80 ℃, 15 minutes 0.33 0.9 96 5.04 5) 80 ° C, 30 minutes 0.33 0.9 96 4.99 ─────────────────────────────────────

[0027]

[Table 4] Dyeing characteristics of wool (reflectance, surface dyeing concentration, etc.) ──── R% K / S Lab 対 照 Control 1) 53.3 ° C 13.0 2.91 52.56 42.57 13.36 2) 66.6 ° C 5.5 8.12 42.74 51.81 16.15 3) 79.9 ° C 2.5 19.0 37.11 56.40 17.88 Inventive method (wool 2g / L) 1) 53.3 ° C 2.5 19.0 36.40 52.42 16.67 2) 66.6 ° C 2.5 19.0 36.72 55.08 17.83 3) 79.9 ℃ 2.5 19.0 36.79 55.40 18.03 ──────────────────────────────────── However The dye concentration before dyeing is 20 × 10 ⁻⁵ g dye / mL and the pH of the dye bath before dyeing is 4.53.

Example 4 In the same manner as in Example 3, an experiment for dyeing tussah silk was performed. Table 5 shows the measurement results of the dyeing characteristics (absorbance of dyeing residual liquid, dye concentration, dyeing ratio, pH) of the mulberry silk thread by Suminol FAST Red B conc.

[0029]

[Table 5] Dyeing characteristics of tussah silk (absorbance, dye concentration, pH) ─────────────────────────────────吸 光 Absorbance of residual dye solution Dye concentration Dyeing ratio (%) pH ───────────────────────────────── ─── Tussah silk control 1) 53 ° C 1.29 3.4 83 5.37 2) 67 ° C 0.93 2.5 88 5.31 3) 80 ° C 1.05 2.8 86 5.29 4) 80 ° C, 15 minutes 0.98 2.6 87 5.29 5) 80 ° C, 30 minutes 1.1 2.9 86 2g / L NaOH solution treatment method of the present invention 1) 53.3 ° C 1.65 4.3 79 5.02 2) 66.6 ° C 0.89 2.3 89 4.95 3) 79.9 ° C 0.78 2.1 90 4.96 4) 80 ° C, 15 minutes 0.75 2.0 90 5.02 5) 80 ℃, 30 minutes 0.70 1.8 91 5.00 ────────────────────────────────────

Example 5 In the same manner as in Example 3, an experiment for dyeing silkworm silk was performed. Table 6 shows the results of measurement of the dyeing properties (absorbance of the residual dye, dye concentration, dyeing rate, pH) of silkworm silk using Suminol FAST RedB conc.

[Table 6] Stainability of silkworm domestic silk (absorbance, dye concentration, pH) ────────────────────────────────── ─── Absorbance of dye residual solution Dye concentration Dyeing rate (%) pH ────────────────────────────────── ─── Silkworm silk control 1) 53 ℃ 0.81 2.1 90 2) 67 ℃ 0.61 1.6 92 4.76 3) 80 ℃ 0.75 2.0 90 4.85 4) 80 ℃, 15 minutes 0.76 2.0 90 4.75 5) 80 ℃, 30 minutes 0.73 1.9 91 4.75 Inventive method Silkworm 2g / L NaOH solution treatment group 1) 53.3 ℃ 1.08 2.8 86 4.99 2) 66.6 ℃ 0.65 1.7 92 4.99 3) 79.9 ℃ 0.82 2.2 89 5.00 4) 80 ℃, 15 minutes 0.89 2.3 89 5.00 5) 80 ° C, 30 minutes 0.84 2.2 89 5.08 ─────────────────────────────────────

Example 6 The mechanical properties of alkali-treated silk were evaluated in order to clarify the change in the physicochemical properties of protein fibers caused by alkali treatment with sodium hydroxide as a pretreatment for dyeing. In the measurement of the mechanical properties, the values of the strength and elongation of the silk thread at the time of cutting are shown. The measurement conditions were a sample length of 50 mm, a pulling speed of 10 mm / min, and a chart scale of 250 g, which were determined by Instron manufactured by Shimadzu (Autograph AGS-5D). The results obtained are shown in Table 7. However, the cutting strength of the sample fiber and the strength (g / d) mean the cutting strength per denier. The values of the degree of crystallinity and the degree of crystallinity of the optical properties, which are directly related to the mechanical properties of the samples, were evaluated by measuring the refractive index. The refractive index was measured using a polarizing microscope manufactured by Olympus, and the refractive index (n) in the fiber direction was measured by the Becke method.
I) and the refractive index (nII) in the direction perpendicular to the fiber axis were measured. Table 8 below shows the results obtained by taking the difference between the two refractive indexes as the birefringence (Δn) of the sample and the value determined by (nI + 2nII) / 3 as the average refractive index (niso). Note that the value obtained by (nI-nII) is △ n
And

[0032]

[Table 7] ──────────────────────────────────── Moisture absorption rate (%) Strength (g / d ) Elongation (%) ──────────────────────────────────── Control Ward Silkworm Silk 8.2 4.6 20.2 2.5 g / L NaOH-treated domestic silkworm silk thread 8.2 4.1 22.4 Control mulberry silkworm silk fiber 9.4 2.8 27.1 2.5 g / L NaOH treated mulberry silk thread 2.9 29.5 4.0 g / L NaOH-treated mulberry silk thread 10.9 2.6 26.8 8.0 g / L NaOH treated mulberry silk thread 11.2 2.9 28.2 ─ ───────────────────────────────────

The refractive index characteristics of the silkworm silk and wild silkworm silk pretreated with an aqueous sodium hydroxide solution and the acid dye (Suminol
FAST Red B conc.), The absorbance, dye concentration, and pH of the residual dye solution are shown below. The absorbance of the residual solution is a value at the maximum absorption wavelength of the dye at 505 nm.

[0034]

[Table 8] ────────────────────────────────────Δn niso Absorbance Dye concentration pH ───家 Control silkworm silk 0.0495 1.555 0.52 1.25 4.47 2.5g / L NaOH-treated silkworm silk 0.050 1.555 0.58 1.27 4.69 Tussah silk of control group 0.034 1.542 0.32 0.82 4.66 4.0 g / L NaOH-treated tussah silk 0.033 1.548 0.75 2.00 4.77 12 g / L NaOH-treated tussah silk 0.032 1.549 0.85 2.18 5.04 ──────────単 位 Unit: Dye concentration × 10 ⁻⁵ g dye / mL As can be seen from the above results, the silkworm silk has 2 0.5g /
The mechanical properties of the tussah silk yarn hardly change even when pretreated with an L sodium hydroxide solution or with an 8 g / L sodium hydroxide aqueous solution. The moisture absorption of the silkworm silk did not change before and after the pretreatment, but the tussah silk showed a tendency to gradually increase. No change in the optical refractive index measurement after the pretreatment was observed for both samples. Thus, it is clear that the alkali treatment of the present invention does not substantially damage the mechanical properties of the material to be dyed.

Example 7 Pad using 2 g / L aqueous sodium hydroxide solution
A hydrochloric acid adsorption experiment was carried out on a sample prepared by pretreatment of domestic silkworm, tussah silkworm and wool fiber by the / Batch method as follows. First,
Hydrochloric acid was added to pure water from which carbon dioxide was removed by boiling to adjust the pH to 4. The concentration of hydrochloric acid before and after the immersion was determined by titration at room temperature with sodium hydroxide having a concentration almost equivalent to that of hydrochloric acid using a recording type automatic titrator ART-2 type manufactured by Hirama Seisakusho. Table 9 shows the measurement results of the obtained hydrochloric acid adsorption amounts.

[0036]

[Table 9] ──────────────────────────────────── Hydrochloric acid adsorption amount Moisture absorption amount (%) ── ────────────────────────────────── Domestic silkworm silk yarn control area 18.56 8.6 Domestic silkworm silk yarn 2.0g / L treated area 19.52 8.5 Yuzu silk silk control area 38.40 8.8 Kisel silk thread 2.0 g / L treatment area 40.32 9.2 Wool yarn control area 39.36 10.7 Wool thread treatment area 44.60 12.1 ───────────────────── ─────────────── Hydrochloric acid adsorption unit: × 10 ^-5 mol / g

As is clear from the results shown in the above table,
The amount of hydrochloric acid adsorption of the silkworm and tussah silk is slightly increased after the alkali treatment, but the amount of hydrochloric acid adsorption of the wool fiber is
It was confirmed that the increase was about 10% after the alkali treatment. Perhaps because the scale of the wool fiber surface was weakened by the alkali treatment and loosened structurally, slight hydrolysis occurred and acidic amino acids and bases such as glutamic acid, aspartic acid, lysine, arginine, and histidine contained in the wool in large amounts This is because the amount of carboxyl groups and amino groups that can react with alkali in the side chain portion of the acidic amino acid and become an adsorption site for hydrochloric acid is increased.

[0038]

According to the present invention, by pretreating a protein fiber product with a dilute alkaline aqueous solution, the dyeing speed of synthetic dyes and vegetable dyes can be increased, and dyeing at a low temperature and in a short time becomes possible.
The functional and hand properties of the animal protein fibers or fiber products pre-treated with alkali are not different from those of the unprocessed ones, and no adverse effects appear by the alkali treatment. The most remarkable effect of pretreatment with alkali was wool. After a simple pretreatment such as immersing in an alkaline solution and loosening the fine structure of the fibers microscopically, the animal protein fibers or fiber products can be dyed in a dark color by dyeing by a conventional method.

Claims (2)

[Claims] 1. An animal protein fiber characterized by being subjected to a dyeing treatment after pretreatment of the animal protein fiber or fiber product with an alkaline aqueous solution of a low concentration that does not substantially damage the fiber or fiber product. Or a method of deep-color dyeing of textiles. 2. The alkaline aqueous solution is sodium hydroxide,
The method according to claim 1, which is an aqueous solution containing at least one compound selected from potassium hydroxide, calcium hydroxide, sodium carbonate and sodium silicate. [0001]