JPH05311582A - Production of textile product dyed with safflower - Google Patents

Abstract

PURPOSE:To obtain a method for industrially producing an elegant textile product, dyed with a safflower, good in dyeability and having high color fastness and further antimicrobial activity and pharmacodynamic effects. CONSTITUTION:A textile product such as cotton, hemp or silk is brought into contact with a pretreating liquid containing tannic acid, subjected to treatment with the tannic acid and then, as necessary, fixing treatment with tartar emetic. The resultant product is subsequently brought into contact with a mordant liquid containing a mordant such as ashes made from burned plants to carry out the fixing of the tannic acid and mordanting. The mordanted textile product is then brought into contact with a dye liquor containing an extract of a safflower and subjected to the dyeing reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a safflower dyed fiber product having good dyeability, high dyeing fastness, grace, and antibacterial properties.

[0002]

2. Description of the Related Art Although natural dyes have been destroyed by synthetic dyes for a long time, plant dyeing has unique astringency, calmness, luster, and texture that synthetic dyes cannot produce, so today's natural orientation is increasing. It is being reassessed.

Among the plant dyes, safflower dye is one of the most beautiful plant dyes and has a long history.

The following documents give a detailed explanation of the history and technique of safflower dyeing. -Staining α, 1983, No. 24, March issue, 2-1
Page 0 "Yamagata Prefecture Flower Cultivation and dyeing of safflower" ・ Dyeing α, 1983, No. 24, March issue, 54-
Page 57 "Enjoyable Dyeing Class 14 Add safflower dye to your sex appeal UP" ・ Dyeing α, 1990, No. 109, April issue, 68
~ P. 71 "Safflower dyeing this and that" -Dyeing α, 1990, No. 113, August issue, 18
Pp.23 "" Romantic Romance "Kahokucho <Yamagata> Moto safflower” ・ Dyeing α, 1990, No. 113, August issue, 24
Pp.33 "In search of a clear and vivid color, the technique of cold dyeing, which is used for safflower dyeing"

According to these articles, safflower dyeing is typically performed by the following procedure. (A) Pick the yellow flowers that are about to turn red on the third day of flowering,
After fermenting, it is solidified and made into Hanamochi. (B) The safflower rice cake is put in a cotton bag and immersed in water to elute and remove the yellow pigment. (C) The safflower rice cake from which the yellow pigment has been removed is taken out of the bag, dipped in an alkaline aqueous solution to extract the safflower pigment, then put in the bag again and squeezed to obtain a dyeing solution. (D) Immerse a material to be dyed in water in this dyeing solution. (E) After pulling up the article to be dyed, acid is added stepwise, and the article to be dyed is dipped again.

[0006] In Japanese Patent Laid-Open No. 59-36873, the petals of safflower around 3 days of flowering are picked, wrapped in a cloth or the like and well fermented, and then fermented. Soak this safflower rice cake in water to remove the yellow pigment, then soak it in an alkaline solution to extract the red pigment, add an acidic solution and add p.
A safflower dyeing method for cotton, in which cotton is dyed by neutralizing it at H8-9 positions, is shown. This method appears to be essentially no different from the typical safflower dyeing described above, except for cotton. This publication describes that cotton dyed by such safflower dyeing method has an antibacterial effect when used for daily use cotton products such as handkerchiefs, towels, underwear, and sheets, and prevents and recovers sores and rashes. It is described that it is effective as a wearable product for people with weak skin, infants, and the like.

Japanese Examined Patent Publication No. 62-46670
0-126388), a step of producing a dyeing stock solution by extracting a pigment from a natural dye such as purple root and safflower with an organic solvent containing a lower alcohol as a main component, and an object to be dyed is an aluminate and a silicate. A step of squeezing hard after immersing in a mordant solution containing, and scouring the dyed object by continuously performing this several times,
After immersing the scoured object to be dyed in the dyeing stock solution, immersing the object to be dyed in an aqueous solution of gallic acid, and then repeating the immersion of the object to be dyed in the dyeing stock solution and the mordant solution alternately. A method of dyeing a natural dye with an organic solvent, which comprises a step of dyeing an object to be dyed, is disclosed. This method is characterized in that it is dyed using an organic solvent, and that dyeing is carried out by the procedure of mordant treatment → dyeing treatment → gallic acid (containing tannic acid at a high concentration) aqueous solution. However, the example of this publication only gives an example of purple root dyeing.

Japanese Examined Patent Publication No. 62-53637
No. 1-225384), a cation group is introduced into silk in advance, and then, this is dyed with a safflower dyeing solution extracted from safflower, and the dyed product is partially decolorized to give a red color to the silk. The method of dyeing silk by safflower, which makes two colors, yellow and yellow, appear is shown. This method is characterized by the introduction of cationic groups and the partial decolorization.

Japanese Unexamined Patent Publication (Kokai) No. 62-64866 discloses a method of dyeing red with safflower yellow dye by dyeing safflower yellow dye on a fiber product and coloring the dyed fiber product with hydrogen peroxide. There is.

[0010]

[Problems to be Solved by the Invention] "Dyeing α" described above
Although the traditional safflower dyeing method as described in 1) is a method that is traditionally performed, it is not always easy to dye a dark color, lack of fastness to light, and especially the initial fading There are problems such as being large.

The method of dyeing safflower on cotton in JP-A-59-36883 also has the same disadvantages as described above in terms of dyeing property and dyeing fastness.

The dyeing method disclosed in Japanese Examined Patent Publication No. 62-46670 is carried out in the following procedure: dyeing using an organic solvent, mordant treatment → dyeing treatment → gallic acid (containing tannic acid in high concentration) aqueous solution. Although it is characterized in that the use of an organic solvent (a mixed solvent of methanol and acetone of 4: 1 in the example) is not preferable in the working environment and the waste liquid treatment, and it is dyeable when applied to safflower. There is still room for improvement in terms of dyeing fastness.

The method of dyeing silk disclosed in Japanese Patent Publication No. 62-53637 has a problem in that the step of introducing a cation group into the silk to be dyed is complicated and is industrially disadvantageous.

According to the safflower dyeing method disclosed in Japanese Patent Laid-Open No. 62-64866, dyeing is performed using a water-soluble yellow dye which has been conventionally discarded, but there is a drawback in terms of beauty of dyed products. ..

As described above, the safflower dyeing method that has been conventionally adopted or proposed has problems in dyeing property, dyeing fastness, grace of dyed product, industrial property and the like, and its solution is strongly desired. There is.

Under such a background, the present invention provides a method for industrially producing a safflower dyed fiber product which has good dyeability, high dyeing fastness, grace, and further has antibacterial and medicinal properties. It is intended to be provided.

[0017]

Means for Solving the Problems The dyed fiber product of the present invention is treated with tannic acid by contacting the fiber product with a pretreatment liquid containing tannic acid, and then, if necessary, fixed with tartar stone, Then, the tannic acid is fixed and mordanted by contacting it with a mordanting solution containing a mordanting agent, and then the textile product after mordanting is contacted with a dyeing solution containing safflower extract to cause a dyeing reaction. is there.

The present invention will be described in detail below.

The fiber products in the present invention include fibrils, threads, piles, cotton-like materials, woven fabrics, knitted fabrics, non-woven fabrics, and flocked fabrics. In addition, paper products, wood products, etc. are also included in the textile products referred to in the present invention.

The materials of these textile products are cotton, linen,
Natural fibers such as silk and wool, or mixed spinning products of these natural fibers and chemical fibers, mixed woven products, knitted products, and even fiber products made of rayon are optional, but especially dyed by the conventional safflower dyeing method. One of the features of the present invention is that it can be applied to cotton and linen, which have poor properties and low fastness.

In the present invention, desizing, scouring, bleaching, etc. are carried out if necessary, and then the fiber product is first subjected to a tannic acid treatment by contacting with a pretreatment liquid containing tannic acid.

As the tannic acid, a purified one can be used, but it is also preferable to use an extract of a natural plant having a high tannic acid content such as quintile, gallic or the like, or a semi-purified product thereof as it is. The quintile contains about 60-75% tannic acid and the gallate contains about 55-65% tannic acid. Purified tannic acid is also obtained by crushing quintet or gallic and extracting with a mixture of ether and ethanol, adding water to the leachate to transfer tannic acid to water, and further purifying it if necessary. Therefore, it can be said that it is a natural product.

The bath ratio during the tannic acid treatment is about 10 to 100 times (particularly about 20 to 60 times) the weight of the fiber product,
The bath temperature is about 50 to 95 ° C (especially about 60 to 90 ° C), the treatment time is about 10 minutes to 2 hours (especially about 20 minutes to 1.5 hours), and the tannic acid concentration is 5 to the weight of the textile product. 20
Although it is often about 10% by weight, it is not necessarily limited to this range.

After the tannic acid treatment, 0.2 to 1 of tartarite (antimony potassium tartrate) is used to fix the tannic acid.
It is preferable to bring the solution into contact with a solution of about 0% by weight (based on the weight of the textile product), but since the fixing of tannic acid can be achieved by a mordant step which is the next step, the fixing step of tannic acid with tartar is It can be omitted.

After the tannic acid treatment, tannic acid is fixed and mordanted by contacting with a mordant solution containing a mordant. This step is important, and if this step is not performed, the dyeing property and dyeing fastness in the next dyeing step will be insufficient.

Here, as the mordant, it is preferable to use plant ash (wood ash or straw ash) such as camellia ash, sawathagi ash, hisakaki ash, kunugi ash, azalea ash, and swede ash. In addition to aluminum ions, these plant ashes contain other metal ions and alkaline substances useful for dyeing.

With or in place of these plant ash, aluminum acetate, aluminum sulfate,
Aluminum salts such as aluminum chloride, alum, burnt alum and potassium alum, and alumina mordants such as commercially available aluminum liquids can also be used. In this case, an alkali such as calcium carbonate, sodium carbonate, calcium hydroxide or sodium hydroxide may be used together.

In addition to or in place of the above-mentioned plant ash, an iron mordant (iron salt of iron acetate, ferrous sulfate, iron nitrate, ferrous acetate, iron acetate, etc.), copper mordant (copper sulfate) , Copper salts such as copper acetate), tin mordants (tin salts such as stannous chloride, sodium stannate, and stannic chloride), chromium mordants (chromium salts such as chromium acetate and chromium alum), and the like.

The bath ratio at the time of mordant is 10 with respect to the weight of the textile product.
˜100 times (particularly about 20 to 60 times), the bath temperature is room temperature to boiling temperature, and the treatment time is usually about 10 minutes to 1 hour, but it is not necessarily limited to this range.

After the tannic acid treatment and the mordant treatment, the textile is dyed by contacting it with a dyeing liquor containing an extract of safflower.

As a dye liquor containing an extract of safflower, as in the conventional method, yellow pigment is extracted and removed from safflower (random flower (dry flower) or safflower rice cake), and then an alkaline aqueous solution (a lye, sodium carbonate solution, carbonic acid) is added. After the red pigment is extracted with an aqueous potassium solution, etc., the pH is adjusted with an acid (acetic acid, citric acid, ume, etc.).

The bath ratio during the dyeing reaction treatment is about 10 to 100 times (particularly about 20 to 60 times) the weight of the fiber product, the bath temperature is about 35 to 50 ° C. (particularly about 40 ° C.), and the treating time. Is often about 15 minutes to 2 hours (especially about 20 minutes to 1 hour), but is not necessarily limited to this range. The dye concentration can be selected from a wide range depending on the purpose.

After completion of the dyeing step, after-treatment such as soaping and washing with water is appropriately performed, and then natural drying or hot air drying is performed.

By carrying out the above-mentioned steps, a beautiful and elegant dyed textile product of red color which has been treated with tannic acid and dyed with an extract of safflower can be obtained.

[0035]

[Function] When a tannic acid treatment reaction and a mordant (especially mordant with plant ash) are carried out prior to the dyeing reaction, the dyeing reaction with the safflower extract is facilitated and the active ingredient in the extract and the fiber product are combined. Bonding between them is surely performed, deep reddish dyeing is possible, dyeing fastness is also high, and the best results are obtained in terms of color tone and texture.

[Tannic acid treatment → mordanting treatment → dying treatment]
The order of is important, and changing this order gives relatively poor results in terms of dyeability, dye fastness, grace, and the like.

Since the active ingredient is fixed by dyeing with the safflower extract, the medicinal effects unique to safflower, such as the warming effect, are maximized. It also has a UV blocking effect.

In addition, the safflower-dyed textile product was found to have excellent antibacterial properties. This is due to the antibacterial action of tannic acid fixed to the textile product. It should be noted that, in general plant dyeing, the antibacterial action often does not appear even if pretreated with tannic acid and then dyed, so the dyeing reaction with the safflower extract has the effect of eliciting the antibacterial property of tannic acid. It is considered to have. Since this antibacterial action is a bacteriostatic action that does not affect the human body's ecosystem, it can also be used medicinally for a human body having a skin disease or itch.

Therefore, the safflower dyed textile product of the present invention is used in contact with the skin, for example, underwear, pantyhose, bras, shirts, nightwear, sheets, gloves, hats, sports supporters, swimwear, bandages, sick people. It is particularly useful for clothing, masks, interior or surface materials of footwear, watch bands, socks and the like. Further, because it has fashionability, it does not matter even if it is used for a kimono or the like that does not come into direct contact with the skin.

[0040]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, "%" is% by weight. Note that "% owf
The term "" means a percentage based on the weight of the textile product to be dyed.

Example 1 (Safflower dyed cotton cloth ) Pretreatment of cotton cloth 100 g of cotton cloth was mixed with 3000 ml of water (bath ratio 1:30, acetic acid).
(Including 0.3 ml), heated to 80 ° C. with stirring, heated at this temperature for about 30 minutes, washed with water and dehydrated.

Tannic acid- tartarine treatment 18 g of tannic acid (18% owf) was dissolved in 4000 ml of water (bath ratio 1:40) to prepare a treatment liquid. The acetic acid-treated cotton fabric was put into this treatment solution, heated to about 85 ° C., stirred for about 1 hour, then naturally cooled and left overnight. Add 8 g of tartar to the solution after leaving it at a temperature of 8
The mixture was stirred at 5 ° C. for about 1 hour, washed with water and dehydrated.

Ash treatment 50 g of safflower ash was suspended in 4000 ml of water (bath ratio 1:40), and the cotton fabric treated as described above was added to this suspension.
After heating to about 85 ° C., stirring treatment for about 20 minutes, washing with water twice, and further dehydration.

Preparation of safflower extract 500 g safflower was added to 10 liters of water (bath ratio 1:20) and left overnight, and the yellow liquid extracted the next day was discarded. The same operation was repeated 3 times to remove the yellow component.

500 g of safflower treated as described above was added to 10 liters of water (bath ratio 1:20), 150 g of soda ash (30% to safflower) was added, and the mixture was thoroughly stirred. After standing for 3 hours, suction filtration was performed to obtain an extract with soda ash.

375 ml of acetic acid (250% to soda ash) was added to this soda ash extract, and the mixture was sufficiently stirred until the bubbles disappeared, and immediately used as safflower dye solution.

Dyeing reaction The safflower dye solution obtained above was charged with the above-mentioned ash-treated cotton fabric, heated to a temperature of 40 ° C. with stirring, and heated at this temperature for about 30 minutes to cause a dyeing reaction. After dyeing reaction, wash with water,
It was dehydrated and dried. As a result, a safflower-dyed cotton cloth dyed in a unique natural tone (red) was obtained. This dyed cotton cloth was beautiful and elegant, and the texture and feel were also favorable.

Example 2 (Safflower-dyed cotton fabric) As for the pretreatment of cotton fabric, the tannic acid-tartar treatment, and the ash treatment, Example 1 was repeated as it was.

Preparation of safflower extract 500 g safflower was added to 10 liters of water (bath ratio 1:20) and allowed to stand overnight, and the yellow solution extracted the next day was discarded. The same operation was repeated 3 times to remove the yellow component.

500 g of safflower treated as described above was added to 10 liters of water (bath ratio 1:20), 150 g of soda ash (30% to safflower) and 25 g of wood ash (5% to safflower) and sufficiently stirred. After standing for 3 hours, suction filtration was performed to obtain an extract with soda ash.

375 ml of acetic acid (250% to soda ash) was added to this soda ash extract, and the mixture was sufficiently stirred until the bubbles disappeared, and immediately used as safflower dye solution.

Dyeing reaction The above-mentioned ash-treated cotton fabric was added to the safflower dyeing solution obtained above, heated to a temperature of 40 ° C. with stirring, and heated at this temperature for about 30 minutes to cause a dyeing reaction. After dyeing reaction, wash with water,
It was dehydrated and dried. As a result, a safflower-dyed cotton cloth dyed in a unique natural tone (red) was obtained. This dyed cotton cloth was beautiful and elegant, and the texture and feel were also favorable.

Antibacterial Test Sections of safflower-dyed cotton cloth obtained in Examples 1 and 2 (2 cm
New evaluation method for antibacterial activity (x2 cm) (antibacterial and antifungal, 16 ,
2, 49-57 (1988)), the antibacterial activity test was carried out (medium: nutrient broth, nutrient agar medium, test bacterium: Escherichia coli ATCC 2
5922, Staphylococcus aureus ATCC 25923), and the following antibacterial properties were observed against these test strains.・ E. coli ATCC 25922 Initial bacterial count: 2.78 × 10 ⁵ cells / g (cloth) Viable bacterial count: 6.28 × 10 ⁷ cells / g (cloth)… Example 1 2.78 × 10 ⁷ cells / g (cloth)… Implementation Example 2 Control is 5.35 × 10 ⁸ cells / g (cloth) Active CA (bacteriostatic): 88.3%… Example 1 94.9%… Example 2 ・ S. aureus ATCC 25923 Initial number of bacteria: 1.85 × 10 ⁶ cells / g (cloth) Viable cell count: 0 cells / g (cloth)… Example 1 0 cells / g (cloth)… Example 2 Control is 1.05 × 10 ⁸ cells / g (cloth) Active CA (sterilization): 100%… Example 1 100% ... Example 2

Dyeing fastness test The safflower dyed cotton fabrics obtained in Examples 1 and 2 were also tested .
The following robustness tests were conducted. Light resistance test (inspection of the effects of sunlight, ultraviolet rays from fluorescent lamps, infrared rays, etc.) Washing test (how much discoloration is caused by normal selection,
Also, it is necessary to pay particular attention to the test whether the color shifts when washed with a white cloth, because plant dyeing often causes discoloration with a weak alkaline detergent. ) Sweat test (test to see if the color changes due to human sweat (acidic, alkaline))

The results were as follows: Dyeing fastness Example 1 Example 2 ・ Light resistance (JISL-04842 3/4 grade) 3-4 grade 3-4 grade ・ Washing (JISL-0844A-2) Discoloration 4 grade 4 grade Contamination 5 grade 5 grade Sweat (JISL-0848A method) Acid discoloration and discoloration 4th class 4th class pollution 4-5 class 4-5 class Alkali discoloration 4th class 4th class pollution 4-5 class 4-5 class

From these results, it was objectively proved that the safflower-dyed cotton cloth has a quality as a plant dyeing which has never been obtained.

Example 3 (Safflower-dyed cotton fabric) Example 1 was repeated except that the quintuple extract was used in place of tannic acid, and the same color tone and texture as in Example 1 were obtained.
A safflower-dyed cotton cloth having a feel, antibacterial property, and dyeing fastness was obtained.

Example 4 (Safflower dyed linen fabric) When Example 1 was repeated except that hemp fabric was used in place of the cotton fabric, the same color tone, texture, feel, antibacterial properties and dye fastness as Example 1 were obtained. A safflower-dyed linen fabric having a certain degree was obtained.

Example 5 (Safflower dyed silk fabric) Example 3 was repeated except that silk fabric was used in place of the cotton fabric. As a result, the color tone, texture, feel, antibacterial property and dye fastness higher than those of Example 3 were obtained. A safflower-dyed silk fabric having the same was obtained.

[0060]

EFFECTS OF THE INVENTION According to the present invention, not only silk and wool, which are relatively easy to dye, but also cotton and hemp, which are conventionally difficult to dye safflower, can be dyed with good dyeability. It is possible to obtain dyed fiber products that are beautiful and elegant and have high dyeing fastness.

Moreover, the safflower dyed fiber product obtained has excellent antibacterial properties and also has a warming effect when worn,
It also has the functional features of being gentle to the skin and also having UV blocking properties.

Therefore, the safflower dyed textile product of the present invention can fully meet the natural and health consciousness of consumers.

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[Procedure amendment]

[Submission date] June 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

Claims (2)

[Claims] 1. A tannic acid is prepared by bringing a textile product into contact with a pretreatment liquid containing tannic acid to perform tannic acid treatment, and then fixing treatment with tartar if necessary, and then contacting it with a mordant liquid containing a mordant. A method for producing a safflower dyed fiber product, comprising the steps of: fixing and mordant, and then contacting the mordant fiber product with a dye liquor containing a safflower extract to cause a dyeing reaction. 2. The method according to claim 2, wherein the mordant is grass ash.