JP4467098B2 - Dyeing assistant, dyeing method and textile product for polyamide / cellulose composite fiber - Google Patents

Description

【００２９】
実施例１〜４で処理されたナイロン布は、耐光堅牢度の低下が非常に少なく、直接染料の汚染防止性に優れていることがわかる。
【００３０】
【発明の効果】
ポリアミド／セルロース複合繊維製品を直接染料で染色する際に、本発明の染色助剤を用いれば、ポリアミド繊維への直接染料の汚染防止性に優れ、かつ、耐光堅牢度の低下が非常に少ない染色物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dyeing aid for polyamide / cellulose composite fibers, a dyeing method using the same, and a polyamide / cellulose composite fiber product dyed thereby. In particular, the present invention relates to a dyeing aid used when dyeing a composite fiber product of polyamide fiber and cellulose fiber with a direct dye alone or with an acid dye and a direct dye, a dyeing method using the same, and a polyamide dyed thereby. / Cellulose composite fiber products.
[0002]
[Prior art]
When dyeing a composite fiber product composed of polyamide fiber and cellulose fiber, when dyeing in the same dyeing bath using an acid dye for dyeing polyamide fiber and a direct dye for dyeing cellulose fiber, In the case where only the cellulose fiber is dyed using only the direct dye, there arises a problem that the polyamide fiber side is contaminated by the direct dye. This is because the sulfonic group of the direct dye tends to form an ionic bond with the amino group present at the end of the polyamide molecule. In order to prevent this contamination, conventionally, a compound obtained by condensing dihydroxydiphenyl sulfone and phenol sulfonate, which is called synthetic tannin, with formaldehyde or a compound obtained by condensing dihydroxydiphenyl sulfone and its sulfate with formaldehyde is used. It is used in combination with a dyeing bath, and the dyeing is advanced after the amino group of the polyamide fiber is blocked with the above synthetic tannin. In this case, due to the difference in affinity (directness) between the synthetic tannin, the acid dye, and the direct dye and the polyamide, the acid dye is attached to the polyamide fiber together with the synthetic tannin, thereby preventing contamination of the direct dye.
[0003]
However, although these synthetic tannins have better light fastness than natural tannic acid, they also have the property of fading easily by sunlight, and even after dyeing the fibers, they can be washed with water or soaped from polyamide fibers. Since it is difficult to fall off, the light fastness of the polyamide fiber portion becomes poor particularly when the dyed product is light-colored or when one piece of cellulose fiber is dyed.
[0004]
[Problems to be solved by the invention]
The present invention relates to a dyeing aid for polyamide / cellulose composite fibers which prevents contamination of polyamide fibers by dyes and does not reduce light fastness when dyeing composite fiber products of polyamide fibers and cellulose fibers, and dyeing using the same It is made for the purpose of providing the method and the textiles obtained by it.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a compound obtained by adding an alkylene oxide to a synthetic tannin as described above as a dyeing assistant, thereby preventing contamination by dyes and light fastness. Based on this finding, the present invention has been completed.
[0006]
That is, the present invention provides the following dyeing assistants (1) and (2).
(1) A condensation reaction product of the following (A), (B) and (D), a condensation reaction product of the following (A), (C) and (D), a condensation reaction product of the following (C) and (D) or Contains a compound in which 50 to 100 equivalent% of an alkylene oxide having 2 to 4 carbon atoms is added to the equivalent of the hydroxyl group of the condensation reaction product of the following (A), (B), (C) and (D) Dyeing aid for polyamide / cellulose composite fibers.
[0007]
(A) 4,4′-dihydroxydiphenylsulfone (B) alkali metal salt of phenolsulfonic acid (C) alkali metal salt of sulfated 4,4′-dihydroxydiphenylsulfone (D) formaldehyde (2) alkylene oxide The dyeing assistant according to (1) above, which is ethylene oxide.
[0008]
The present invention also provides the following staining method (3).
(3) A method for dyeing a polyamide / cellulose composite fiber, comprising dyeing the polyamide / cellulose composite fiber in the presence of the dyeing aid of (1) or (2) above.
Furthermore, the present invention provides the following (4) textile product.
(4) A polyamide / cellulose composite fiber product dyed by the dyeing method of ( 3 ) above.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The compound used for the dyeing aid of the present invention can be obtained by a conventionally known method. For example, a mixture of 4,4′-dihydroxydiphenylsulfone, an alkali metal salt of phenolsulfonic acid and formaldehyde is reacted at 100 to 130 ° C. for 4 to 10 hours using an alkali such as sodium hydroxide as a catalyst in an aqueous solvent. After obtaining the condensation reaction product, ethylene oxide is added to the above condensation reaction product by introducing alkylene oxide, for example, ethylene oxide, into the aqueous solution of the condensation reaction product at pH of 8.0 to 9.0 at 90 to 100 ° C. The resulting compound is obtained.
[0010]
Alternatively, an alkali agent is added to a sulfate of 4,4′-dihydroxydiphenylsulfone obtained by reacting 4,4′-dihydroxydiphenylsulfone and sulfuric acid in acetic anhydride to obtain an alkali metal salt. Next, using an alkali such as sodium hydroxide as a catalyst in an aqueous solvent, a mixture of the above-mentioned sulfate and formaldehyde or a mixture of the above-mentioned sulfate, 4,4′-dihydroxydiphenylsulfone and formaldehyde is used in an amount of 100 to 130. After obtaining a condensation reaction product by reacting at 4 ° C. for 4 to 10 hours, an alkylene oxide such as ethylene oxide is introduced at 90 to 100 ° C. into an aqueous solution of the condensation reaction product at pH 8.0 to 9.0. A compound in which ethylene oxide is added to the condensation reaction product is obtained.
[0011]
(A) 4,4′-dihydroxydiphenylsulfone, (B) alkali metal salt of phenolsulfonic acid, (C) sulfated when synthesizing a condensation reaction product that is an intermediate of the above compound used in the present invention The preferred ratio of the alkali metal salt of 4,4′-dihydroxydiphenylsulfone and (D) formaldehyde is not related to the composition of the raw materials to be condensed and the amount of alkylene oxide added, but cannot be generally described. In the case of the condensation reaction of B) and (D), (B) is 0.2 to 2.0 mol per mol of (A), and (D) is the total mol of (A) and (B). 60 to 120 mol% of the number is preferable, and in the case of the condensation reaction of (A), (C) and (D), (C) 1.0 to 0.8 mol with respect to (A) 0 to 0.8 mol. 2 mol, (D) is 60 of the total number of moles of (A) and (C). Preferably 120 mol%. In the case of the condensation reaction of (A), (B), (C) and (D), the total number of moles of (B) and (C) is 0.2 to 1 per mole of (A). At 0 mol, (D) is preferably 60 to 120 mol% of the total number of moles of (A), (B) and (C).
[0012]
Examples of the alkali metal salt of phenolsulfonic acid and alkali metal salt of 4,4′-dihydroxydiphenylsulfone sulfate include lithium, sodium, potassium, etc., but sodium is economical. preferable.
Furthermore, examples of the alkylene oxide used include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide is preferable because of its good reactivity with hydroxyl groups, but these alkylene oxides can be used alone or in combination. . At this time, the addition amount of alkylene oxide needs to be 50 to 100 mol%, preferably 60 to 90 mol%, based on the hydroxyl group of the condensation reaction product. If the ethylene oxide content is less than 50 mol%, the light fastness cannot be sufficiently prevented from decreasing, and if it exceeds 100 mol%, the effect of preventing the direct dye contamination of the polyamide fiber becomes very weak.
[0013]
When dyeing a polyamide / cellulose composite fiber, the method using the dyeing aid of the present invention may be the same as the method using the conventional dyeing aid. For example, the dyeing aid of the present invention is 0.1 to 5%. 0.0% owf, leveling agent and, if necessary, a dyeing bath in which an acid such as acetic acid or a decomposition acid is dissolved. First, the article to be dyed is immersed at room temperature to 80 ° C for 5 to 20 minutes, and then the dyeing bath. Examples thereof include a method in which an acid dye or a direct dye is charged therein and dyed at 80 to 100 ° C. for 10 to 60 minutes.
[0014]
In the present invention, polyamide / cellulose composite fiber products include aliphatic polyamide fibers such as nylon 66 and nylon 6, polyamide fibers such as xylylenediamine polyamide fibers and other aromatic polyamide fibers, and cotton and hemp. It may be a blended or unwoven product with cellulose fibers, and examples of the form include yarn, woven fabric, knitted fabric, and non-woven fabric.
[0015]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Synthesis example Condensation reaction product A
An autoclave reaction vessel was charged with 2500 g of 4,4′-dihydroxydiphenylsulfone, 980 g of sodium paraphenolsulfonate, 240 g of sodium hydroxide, 1000 g of a 37% formaldehyde aqueous solution, and 2860 g of water, and reacted by heating and stirring at 130 ° C. for 4 hours. An aqueous solution of condensation reaction product A having an active ingredient of 50% and a pH of 8.5 was obtained.
[0016]
Condensation reaction product B
5000 g of 4,4′-dihydroxydiphenylsulfone and 2500 g of acetic anhydride are placed in a flask, dissolved at 120 ° C. in a nitrogen gas atmosphere to be uniform and cooled, and then 1000 g of 98% sulfuric acid is added dropwise at 100 ° C. The reaction was carried out at 6 ° C. for 6 hours. After the reaction, the mixture was cooled to 40 ° C. and diluted with 3120 g of water, 1620 g of 37% formaldehyde aqueous solution was added, and a condensation reaction was performed at 105 ° C. for 10 hours. Thereafter, the resulting solution of the condensation reaction product was decompressed and evaporated to dryness to obtain 6080 g of condensation reaction product B.
[0017]
Example 1
400 g of the aqueous solution of the condensation reaction product A was put in a pressure vessel, and 34.9 g of ethylene oxide (60 mol% based on hydroxyl group) was introduced at 90 to 95 ° C. using an autoclave, and then at 90 to 95 ° C. for 3 hours. The reaction was followed by cooling and dilution with 34.9 g of water to give a 50% aqueous solution of condensation product A ethylene oxide adduct.
[0018]
Example 2
400 g of the aqueous solution of the above condensation reaction product A was placed in a pressure vessel, and 52.7 g of ethylene oxide (90 mol% based on hydroxyl groups) was introduced at 90 to 95 ° C. using an autoclave, and then at 90 to 95 ° C. for 3 hours. The reaction was followed by cooling and dilution with 52.7 g of water to give a 50% aqueous solution of condensation product A ethylene oxide adduct.
[0019]
Example 3
200 g of the above condensation reaction product B and 206 g of water were placed in a pressure vessel and neutralized with 40.0 g of sodium hydroxide to adjust the pH to 8.6. Next, after introducing 34.7 g of ethylene oxide (60 mol% based on hydroxyl group) at 90 to 95 ° C. using an autoclave, the mixture was reacted at 90 to 95 ° C. for 3 hours, then cooled, and 34.7 g of water. To obtain a 50% aqueous solution of the condensation product B ethylene oxide adduct.
[0020]
Example 4
200 g of the above condensation reaction product B and 206 g of water were placed in a pressure vessel and neutralized with 40.0 g of sodium hydroxide to adjust the pH to 8.6. Next, after introducing 52.1 g of ethylene oxide (90 mol% based on hydroxyl group) at 90 to 95 ° C. using an autoclave, the mixture was reacted at 90 to 95 ° C. for 3 hours, then cooled, and 52.1 g of water. To obtain a 50% aqueous solution of the condensation product B ethylene oxide adduct.
[0021]
Comparative Example 1
400 g of the aqueous solution of the condensation reaction product A was put in a pressure vessel, and 17.4 g of ethylene oxide (30 mol% relative to hydroxyl group) was introduced at 90 to 95 ° C. using an autoclave, and then at 90 to 95 ° C. for 3 hours. The reaction was followed by cooling and dilution with 17.4 g of water to give a 50% aqueous solution of condensation product A ethylene oxide adduct.
[0022]
Comparative Example 2
200 g of the above condensation reaction product B and 206 g of water were placed in a pressure vessel and neutralized with 40.0 g of sodium hydroxide to adjust the pH to 8.6. Then, after introducing 69.5 g of ethylene oxide (120 mol% based on hydroxyl group) at 90 to 95 ° C. using an autoclave, the mixture was reacted at 90 to 95 ° C. for 3 hours, then cooled, and 69.5 g of water. To obtain a 50% aqueous solution of the condensation product B ethylene oxide adduct.
[0023]
Comparative Example 3
Aqueous solution of condensation reaction product A (active ingredient 50%)
Comparative Example 4
200 g of the condensation reaction product B was dissolved in 206 g of water, and then neutralized with 40.0 g of sodium hydroxide to obtain an aqueous solution with an active ingredient of 50% and a pH of 8.6.
[0024]
Comparative Example 5
Dyeing aid not used
Process 1
Using Examples 1 to 4 and Comparative Examples 1 to 5 as dyeing assistants, dyeing was performed under the following conditions. After dyeing, the samples were washed with running water for 1 minute, dehydrated, and then dried at 100 ° C. for 3 minutes. .
[0025]
Sample: Nylon taffeta and cotton broad were used at a weight ratio of 90:10.
Leveling agent: Newbon D-100 (manufactured by Nikka Chemical Co., Ltd.) 1.0% owf
Acid: 90% acetic acid 0.2 g / liter anhydrous sodium sulfate: 10 g / liter Dyeing assistant: 3% owf
Bath ratio: 1:20
Dyeing temperature: 98 ° C. × 30 minutes (from 30 ° C. to 2 ° C./minute)
Process 2
Using Examples 1 to 4 and Comparative Examples 1 to 5 as dyeing assistants, dyeing was performed under the following conditions. After dyeing, the samples were washed with running water for 1 minute, dehydrated, and then dried at 100 ° C. for 3 minutes. .
[0026]
Sample: Nylon taffeta and cotton broad were used at a weight ratio of 90:10.
Test dye: C.I. I. Direct Blue 108 0.1% owf
Leveling agent: Newbon D-100 (manufactured by Nikka Chemical Co., Ltd.) 1.0% owf
Acid: 90% acetic acid 0.2 g / liter anhydrous sodium sulfate: 10 g / liter Dyeing assistant: 3% owf
Bath ratio: 1:20
Dyeing temperature: 98 ° C. × 30 minutes (from 30 ° C. to 2 ° C./minute)
Evaluation test Nylon cloth treated with light fastness treatment 1 was irradiated for 40 hours at 63 ° C using a fade-o-meter (manufactured by Suga Test Instruments Co., Ltd.), and the degree of discoloration was used for contamination. The results determined by gray scale (JIS L 0805) are shown in Table 1 (the larger the series, the better the light fastness).
[0027]
The result of determining the degree of contamination of the nylon cloth treated by the contamination prevention treatment 2 by using a contamination gray scale (JIS L 0805) is shown in Table 1 (the larger the series, the better the contamination prevention).
[0028]
[Table 1]

[0029]
It can be seen that the nylon fabrics treated in Examples 1 to 4 have very little reduction in light fastness and are excellent in direct dye contamination prevention.
[0030]
【The invention's effect】
When dyeing polyamide / cellulose composite fiber products with a direct dye, the dyeing aid of the present invention can be used to provide excellent dyeing resistance against direct dyeing of polyamide fibers and very little reduction in light fastness. Things are obtained.

Claims (4)

The following (A), (B) and (D) condensation reaction products, the following (A), (C) and (D) condensation reaction products, the following (C) and (D) condensation reaction products or the following (A) ), (B), (C) and polyamide / cellulose containing a compound in which 50 to 100 equivalent% of an alkylene oxide having 2 to 4 carbon atoms is added to the equivalent of the hydroxyl group of the condensation reaction product of (D) Dyeing aid for composite fibers.
(A) 4,4′-dihydroxydiphenylsulfone (B) alkali metal salt of phenolsulfonic acid (C) sulfated 4,4′-dihydroxydiphenylsulfone alkali metal salt (D) formaldehyde The dyeing assistant according to claim 1, wherein the alkylene oxide is ethylene oxide. A method for dyeing a polyamide / cellulose composite fiber, comprising dyeing the polyamide / cellulose composite fiber in the presence of the dyeing assistant according to claim 1. A polyamide / cellulose composite fiber product dyed by the dyeing method according to claim 3 .