JPH0347355B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for improving the color fastness of dyed textile products, and in particular a method for improving the color fastness of textile products made of natural fibers such as cellulose fibers, silk, and wool, or synthetic polyamide fibers such as nylon. Regarding. [Technical Background] It is desired that dyed products have various fastness properties. Among these, fastness to friction (fastness to friction) is particularly important. However, reactive dyes, direct dyes, acid dyes, etc., which are generally used for dyeing natural fibers such as cellulose fibers, silk, and wool, or synthetic polyamides such as nylon, are difficult to produce strong dyed products. This is because these dyes are hydrophilic and have a large molecular structure, so they are not easily absorbed by fibers, and their bond with fibers is not very strong. Therefore, it is difficult to obtain various types of textile products with excellent fastness. [Prior Art and its Problems] Therefore, various methods have been tried in the past in order to improve these fastnesses. One of them is so-called fixing treatment. This can be done by dyeing, for example with dicyandiamide.
This method attempts to firmly fix the dye onto the fiber by treating it with a polycation such as a formalin condensate or a fixing agent such as tannic acid-tartarite. According to this method, certain types of fastness can be dramatically improved. However, other fastness properties may be adversely affected, and there is almost no effect on fastness to rubbing, particularly fastness to wet rubbing. In addition, attempts have also been made to improve the fastness of dyed products by treating them with an emulsion of dimethyl silicone oil, for example, as a finishing treatment. However, none of them is fully satisfactory, and in particular, there is little effect on wet rubbing fastness. [Objective] The object of the present invention is to improve various fastness properties of natural fibers such as cellulose fibers, silk, and wool, or synthetic polyamide fiber products such as nylon.
In addition, the present invention not only improves water fastness, sweat fastness, light fastness, washing fastness, etc., but also dramatically improves abrasion fastness, which has been considered the most difficult, especially wet abrasion fastness. The purpose is to provide a method for improving robustness. [Structure] In order to achieve these objectives, the present inventor conducted intensive research and found that when textile products are treated with a solution consisting of a polysiloxane compound and a compound having a phenolic hydroxyl group, various fastness properties, especially friction fastness, are dramatically improved. The present invention has been completed by discovering that the present invention can be improved. The present invention will be explained in detail below. The polysiloxane used in the present invention is
It is commonly called silicone oil, and various types are commercially available from various companies. Typical examples include dimethyl silicone, amino-modified silicone, epoxy-modified silicone, hydrogen-modified silicone, carboxy-modified silicone, hydroxy-modified silicone, etc., and these can be used alone or in combination. Furthermore, further modified versions of the above silicones may also be used. Among the silicones mentioned above, amino-modified silicones and hydrogen-modified silicones are particularly effective, but similar effects can be seen with other silicones. However, the effects of these silicones alone are insufficient, and the object of the present invention can be achieved by using these silicones together with a compound having a phenolic hydroxyl group. The compound having a phenolic hydroxyl group used in the present invention is represented by the following general formula []. A [O(-C ₂ H ₄ O) n-(-C ₃ H ₆ O) mH]p
...[] However, in the formula [], A is a benzene nucleus, a naphthalene nucleus; benzene substituted with one or more halogen atoms, alkyl groups, aryl groups, aryloxy groups, aralkyl groups, alkaryl groups, cycloalkyl groups Nucleus or naphthalene nucleus; represents a formaldehyde condensate of substituted or unsubstituted benzene nucleus or naphthalene nucleus, or acetaldehyde condensate, n is 0 or an integer of 1 to 10, m is 0 or an integer of 1 to 20 , p each represent an integer from 1 to 3. The compound having a phenolic hydroxyl group may be one in which ethylene oxide or propylene oxide is added to the hydroxyl group. However, the number of moles of ethylene oxide added is 1 to 10 moles, and is selected so that the compound having a phenol hydroxyl group has as little water solubility as possible. Silicone oils and compounds with phenolic hydroxyl groups do not dissolve in water, so they are emulsified or dissolved in a common solvent before application. However, since emulsifiers generally tend to reduce fastness, it is more preferable to use a solvent. Any solvent can be used as long as it simultaneously dissolves silicone oils and compounds with phenolic hydroxyl groups, but trichlorethylene, perchlorethylene, 1.1.1-trichloroethane and the like are preferably used. As a treatment method, any method such as a dipping method, a pad method, a spray method, etc. can be adopted. Processing conditions vary somewhat depending on the processing method, but heating within a range that can remove the used solvent is sufficient. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts in the examples are parts by weight. Also,
The numerical values in Tables 1 to 11 represent the measurement results in gray.
It is evaluated in five stages on a scale, and the higher the value, the better it is. Example 1 (a) Dyeing Refined broad cotton cloth was dyed with Diamira Brilliant Red 2B (manufactured by Mitsubishi Chemical Corporation: reactive dye) 4% (OWF), anhydrous sodium sulfate 80 g/
and 20 g/soda ash, dyeing was carried out at 50° C. for 60 minutes. After washing with water, FWA−
437 (manufactured by Ipposha Yushi Kogyo Co., Ltd.: Soaping agent) 1
After soaping at 80° C. for 20 minutes with an aqueous solution containing g/g, the cloth was washed again with water and dried to obtain a dyed cloth. (b) Fastness improvement treatment The above dyed fabric was pad treated using the following treatment solution (squeezing ratio 120%) and dried at 80°C for 3 minutes to obtain a treated fabric. ●Amino-modified silicone X-22-3810C (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts ●Tristyrenated phenol 2 parts ●Trichlorethylene 90 parts (c) Measurement Measurement of the abrasion fastness in dry and wet conditions of the obtained treated fabric (JIS L-0849). The results are shown in Table 1. In Table 1, untreated dyed fabric was measured as it was, and Comparative Example 1 was a dyed fabric treated with amino-modified silicone alone at the same concentration as in Example 1.

[Table] Example 2 Amino-modified silicone X-22-3801C (manufactured by Shin-Etsu Chemical Co., Ltd.) used in the fastness improvement treatment of Example 1
A mixture of 8 parts of tristyrenated phenol and 2 parts of tristyrenated phenol was emulsified with a 10 mole adduct of nonylphenol and ethylene oxide, and the mixture was adjusted to have the same concentration as in Example 1 with pure silicone and treated to improve fastness. I did it. Staining and measurement were performed in the same manner as in Example 1. The results are shown in Table-2. In Comparative Example 2, amino-modified silicone was emulsified with 10 moles of ethylene oxide adduct of nonylphenol and treated with a liquid adjusted to have the same concentration of pure silicone as Comparative Example 1.

[Table] Example 3 (a) Dyeing Refined nylon jersey white cloth was dyed with Suminol Milling Red 3BNconc (manufactured by Sumitomo Chemical Co., Ltd.: acid dye) 4% (OWF), acetic acid (90%) 1% (OWF). ) for 60 minutes at 98°C. The dyed cloth was then washed with water and dried to obtain a dyed cloth. (b) Fastness improvement treatment Next, immerse in the following treatment solution (20 minutes at room temperature)
After removing the solution, it was dried at 80°C for 3 minutes. ●Amino-modified silicone X-22-3680 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts ●Ortho-phenylphenol 2 parts ●1.1.1-Trichloroethane 93 parts (c) Measurement The rubbing fastness (JIS L) of the obtained treated cloth was
-0849) was measured. The results are shown in Table-3. In Table 3, untreated fabrics are the dyed fabrics as they are, and Comparative Example 3 is the dyed fabrics treated with amino-modified silicone alone at the same concentration as in Example 3.

[Table] Example 4 (a) Dyeing Refined white silk cloth was dyed with Kayanol Milling Black VLG (manufactured by Nippon Kayaku Co., Ltd., acid dye) 10%.
(OWF), acetic acid (90%) 1% (OWF), and ammonium sulfate 1% (OWF) were stained at 95° C. for 90 minutes. Next, it was washed with water and dried to obtain a dyed cloth. (b) Fastness improvement treatment The following treatment solution was applied uniformly to the dyed cloth by spraying, and then left overnight to dry. ●Hydrogen-modified silicone Siloxane H (manufactured by Hoechst) 5 parts ●Cyclohexylphenol 2 parts ●Trichlorethylene 93 parts (c) Measurement The resulting treated fabric was evaluated for rubbing fastness (JIS
L-0849) was measured. The results are shown in Table 4. In Table 4, untreated fabrics are the dyed fabrics as they are, and Comparative Example 4 is the dyed fabrics treated with hydrogen-modified silicone alone at the same concentration as in Example 4.

[Table] Example 5 A refined white wool cloth was dyed in the same manner as in Example 3, subjected to the same fastness improvement treatment, and measured in the same manner. The results are shown in Table-5. Note that Comparative Example 5 is the same as Comparative Example 3.

[Table] Example 6 (a) Dyeing Refined broad cotton cloth was dyed with 10% Direct Deep Black EXconc (manufactured by Nippon Montageson Co., Ltd.: direct dye) (OWF) and 20% anhydrous sodium sulfate.
The sample was stained with an aqueous solution consisting of 100 g/g for 60 minutes at 95°C. The dyed cloth was then washed with water and dried to obtain a dyed cloth. (b) Fastness improvement treatment Next, the above dyed fabric was patch treated with the following treatment solution (squeezing ratio: 120%) and dried at 80°C for 3 minutes. ●Hydrogen-modified silicone KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts ●Hydrogen-modified silicone KF-851 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts ●β-Naphthol 2 parts ●1.1.1-Trichloroethane 93 parts (c) Measurement For the treated fabric obtained, the abrasion fastness (JIS
L-0849) was measured. The results are shown in Table-6. In Table 6, untreated fabric is the dyed fabric as it is, and Comparative Example 6 is the dyed fabric treated with silicone alone at the same concentration as in Example 6.

[Table] Example 7 (a) Dyeing Refined white silk cloth was dyed with Kayaras Black G Conch (manufactured by Nippon Kayaku Co., Ltd.: direct dye) 15% (ow
f.) and 20 g of anhydrous sodium sulfate at 95° C. for 60 minutes. The dyed cloth was then washed with water and dried to obtain a dyed cloth. (b) Fastness improvement treatment Next, patch treatment with the following treatment solution (squeezing rate
120%) and dried at 50°C for 3 minutes. ●Amino-modified silicone X-22-380 (trust

[Table] Equivalent acylation of Etsu Kagaku Kogyo Co., Ltd.) with acetic anhydride 5 parts Formaldehyde condensate of nonylphenol
3 parts ●Trichlororetylene 62 parts ●Xylene 30 parts (c) Measurement The water fastness (JIS L
-0846), sweat fastness (JIS L-0848), light fastness (JIS L-0842), rub fastness (JIS L-
0849) was measured. The results are shown in Table-7.
In Table 7, untreated fabrics are the dyed fabrics as they are, and Comparative Example 7 is the dyed fabrics treated with silicone alone at the same concentration as in Example 7. Example 8 (a) Fixing treatment A cotton cloth dyed in the same manner as in Example 1 was treated with an aqueous solution of 4% (OWF) Pan Fixtures HF-1 (Fixing agent manufactured by Ipposha Yushi Kogyo Co., Ltd.) at 60°C for 20 minutes. Then, after washing with water, it was dried. (b) Fastness improvement treatment Next, after the following treatment, it was subjected to patch treatment (squeezing ratio 120%) and dried at 80°C for 3 minutes. ●Amino-modified silicone KF861 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts ●Epoxy-modified silicone KF-103 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts ●Styrenated hydroquinone 3 parts ●1.1.1-Trichloroethane 92 parts (c) Measurement Obtained Rubbing fastness (JIS
L-0849) was measured. The results are shown in Table-8. In addition, in Table 8, untreated dyed fabric is used as it is, and comparative example 8 is dyed fabric treated with fixes.
These are the results of measuring samples treated with silicone alone at the same concentration.

[Table] Example 9 (a) Fixture treatment A nylon cloth dyed in the same manner as in Example 3 was treated with 3% tannic acid (OWF) and 1% acetic acid (90%) (o.
After treatment at 80°C for 20 minutes with an aqueous solution consisting of wf), it was treated at 70°C for 20 minutes with an aqueous solution consisting of 2% tartarite (OWF), washed with water, and then dried. (b) Fastness improvement treatment Next, after the following treatment, it was subjected to patch treatment (squeezing ratio 120%) and dried at 80°C for 3 minutes. ●Amino-modified silicone KF-864 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts ●5 moles of ethylene oxide adduct of tristyrenated phenol 3 parts ●Perchlorethylene 89 parts (c) Measurement degree (JIS
L-0849) was measured. The results are shown in Table-9. In addition, in Table 9, the untreated dyed fabric is used as it is, and Comparative Example 9 is the dyed fabric that has been fixed treated in Example 9.
This is the result of measuring a sample treated with silicone alone at the same concentration.

[Table] Example 10 (a) Fixing treatment A nylon cloth dyed in the same manner as in Example 3 was treated with an aqueous solution of 4% (OWF) Nylox 1500 (Fixing agent manufactured by Ippo Sha Yushi Kogyo Co., Ltd.).
It was treated at 80°C for 20 minutes, washed with water, and then dried. (b) Fastness improvement treatment Next, it was subjected to patch treatment with the following treatment solution (squeezing ratio: 100%) and dried at 80°C for 3 minutes. ●Hydrogen-modified silicone KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts ●Adduct of nonylphenol with 2 moles of ethylene oxide and 6 moles of propylene oxide 3 parts ●1.1.1-Trichloroethane 92 parts (c) Measurement Obtained treatment For cloth, rub fastness (JIS
L-0849) was measured. The results are shown in Table-10. In addition, in Table 10, the untreated dyed fabric is used as it is, and Comparative Example 10 is the dyed fabric that has been fixed treated.
This is the result of measuring a sample treated with silicone alone at the same concentration.

[Table] Example 11 (b) Fastness improvement treatment Silk cloth dyed in the same manner as in Example 7 was subjected to patch treatment (squeezing rate 100%) using the following treatment solution.
It was left to dry overnight. ●Amino-modified silicone X-22-3801 (manufactured by Shin-Etsu Chemical Co., Ltd.) neutralized in an equivalent amount with acetic acid (90%) 5 parts ●Dimethyl silicone KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts ●Chlorphenol 3 ●Perchlorethylene 89 parts (c) Measurement The abrasion fastness (JIS
L-0849) was measured. The results are shown in Table 11. In Table 11, untreated fabric is treated as it is, comparative example 11 is dyed fabric treated with silicone alone at the same concentration as in example 6, and comparative example 12 is dyed fabric treated with silicone alone at the same concentration as in example 11. These are the results of measuring samples treated with phenol alone.

〔effect〕

As is clear from the above results, improvements in various fastnesses (particularly fastness to dry rub) are observed even when silicones are used alone. However, when treated according to the fastness improvement method of the present invention, not only the dry rub fastness but also the wet rub fastness was significantly improved, making it possible to improve the wet rub fastness, which had been considered difficult in the past. .

Claims (1)

[Scope of Claims] 1. A method for improving color fastness, which comprises treating a dyed textile product with a solution containing a polysiloxane compound and a compound having a phenolic hydroxyl group. 2. The dyeing according to claim 1, wherein the polysiloxane compound is dimethylpolysiloxane, amino-modified polysiloxane, hydrogen-modified polysiloxane, epoxy-modified polysiloxane, carboxy-modified polysiloxane, hydroxy-modified polysiloxane, or a mixture thereof. How to improve robustness. 3. The method for improving color fastness according to claim 1, wherein the compound having a phenolic hydroxyl group is represented by the following general formula []. A [O(-C ₂ H ₄ O) n-(-C ₃ H ₆ O) mH]p
...[] (In the general formula [], A is a benzene nucleus, a naphthalene nucleus; substituted with one or more halogen atoms, alkyl groups, aryl groups, aryloxy groups, aralkyl groups, alkaryl groups, cycloalkyl groups) Benzene nucleus or naphthalene nucleus; represents a formaldehyde condensate of substituted or unsubstituted benzene nucleus or naphthalene nucleus, or acetaldehyde condensate; n is 0 or an integer of 1 to 10; m is 0 or an integer of 1 to 20; (Integer, p represents an integer from 1 to 3.)