JPH08269879A - Production of polyamide dyed product - Google Patents

Abstract

PURPOSE: To obtain a polyamide dyed product having high color fastness by dyeing a polyamide molded material with a disperse dye, reduction washing and fix-treating by using a nylon acidic dye fixing agent. CONSTITUTION: A fastener in which, for a fastener element, a polyamide molded material of 6-nylon is used and for a fastener tape and sewing yarn, polyethylene glycol-copolymerized polyethylene terephthalate is used, is dyed with a disperse dye at 110 deg.C for 60min. Resultant dyed fastener is reduction-washed in caustic soda, hydrosulfite and a detergent, and subjected to fixing treatment by using 1-6wt.% tannin and 0.5-4wt.% tartar emetic, or 1-8wt.% synthetic tannin at 60 deg.C for 30min.

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 polyamide-dyed product which gives a polyamide-dyed product excellent in dyeing fastness even when dyeing with a disperse dye.

[0002]

2. Description of the Related Art In manufacturing a polyamide dyed product by dyeing a polyamide resin molded product or a polyamide molded product such as a polyamide fiber, when the polyamide molded product is dyed with a disperse dye, the obtained polyamide dyed product is dyed. It has poor fastness and could generally only be applied to light color dyeing.

Therefore, in the past, in producing a polyamide dyed product obtained by dyeing the above polyamide molded product, an acid dye is generally used to dye the polyamide molded product.

In the past, there have been blended fabrics of polyamide and other synthetic resins such as polyesters, mixed woven fabrics, and composites. Thus, polyamides and other synthetic resins such as polyesters are combined. It was also practiced to dye a dyed product to produce a polyamide dyed product.

When dyeing a product obtained by combining polyamide and other synthetic resin such as polyester in this way, when dyeing is carried out only with a disperse dye, dyeing of the polyamide dyed product obtained as described above Because the robustness becomes worse,
Conventionally, after first dyeing with a disperse dye, the disperse dye in the polyamide is decolorized, then
The polyamide molding was again dyed with an acid dye.

However, in such a case, there is a problem that it is necessary to perform the dyeing twice, which is very troublesome and costly. Therefore, only the disperse dye is used and the dyeing fastness is high. It has been desired to make it possible to easily produce an excellent polyamide dyeing product.

Further, in recent years, JP-A-5-295 has been proposed.
As disclosed in Japanese Patent No. 676, after dyeing a polyamide fiber with a neutral type gold-containing dye and / or a disperse dye, this is fixed with tannin and a metal salt, and then,
It was proposed to reduce and wash this to improve the dyeing fastness in the polyamide fiber, but even in this case, it is still difficult to obtain a polyamide dyed product having sufficient dyeing fastness. there were.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems in dyeing a molded polyamide product. In the present invention, a disperse dye is used to dye fast. It is an object of the present invention to provide a method for producing a polyamide dyed product, which can easily obtain a highly polyamide dyed product.

[0009]

In the method for producing a polyamide dyed product according to the present invention, in order to solve the above problems, a polyamide molded product is dyed with a disperse dye, which is then reduced and washed. The fixing treatment was carried out using a fixing agent for nylon acid dyes.

Here, as the above-mentioned polyamide, 6-
Nylon, 6,6-nylon, 12-nylon 12,
6,10-nylon or the like can be used, and the molded product may be in any state such as a fiber structure or a resin molded product, but for resin molded products which are generally difficult to dye. Also, by the above, a polyamide dyed product with high dyeing fastness can be obtained.

As the disperse dye used in the present invention, known disperse dyes can be used.
Disperse dyes such as anthraquinone type, azo type, nitrodiphenylamine type, methine type, aminokitone type, ketoimine type can be used, and particularly those which are easy to disperse in water and have a high affinity for polyamide moldings are used. It is preferable.

When dyeing a polyamide molded article with such a disperse dye, a known dip dyeing method or the like can be used.

When the polyamide molded product dyed with the disperse dye as described above is subjected to a reduction treatment, an alkali such as caustic soda or sodium carbonate is used in combination with a reducing agent such as hydrosulfite or thiourea dioxide. Thus, a detergent for washing is usually used together. However, when an acid such as acetic acid or formic acid is combined with sodium sulfoxylate formaldehyde, the dye is decolorized by this reduction washing, which is not preferable.

Here, in the case where the reduction cleaning is performed using the alkali and the reducing agent as described above, the amount of the alkali and the reducing agent used is 0.
5 to 2 g / l, 1 to 4 g / l when using sodium carbonate
1 to 4 g / l when hydrosulfite is used as the reducing agent, and 0.2 to 0.5 g / l when thiourea dioxide is used as the reducing agent, Further, the processing temperature in the reduction cleaning is 60 to 9
The temperature is set to 0 ° C. and the treatment time is set to about 15 to 60 minutes.

Further, when the polyamide molded product which has been reduced and washed as described above is fixed with a fixing agent for nylon acid dyes, the fixing agent for nylon acid dyes is not particularly limited, but tannin such as quintuple tannin is used. It is preferable to use a combination of an acid and tartarite (potassium antimonyl tartrate) or a synthetic tannin.

Here, as the above synthetic tannin, a phenol sulfonic acid derivative, an aromatic sulfonic acid condensate,
An aromatic polymer derivative, an oxysulfonate condensate, a polyhydric phenol derivative, a condensate of allyl sulfonate and formaldehyde, a polymer aromatic sulfonic acid and the like can be used.

In addition, when fixing the polyamide molded product dyed with the above-mentioned nylon acid dye fixing agent, tannic acid and tartar are used in combination with the polyamide molded product. In that case, as the solid content, tannic acid is used in the range of 1 to 6% by weight, and tartar is used in the range of 0.5 to 4% by weight. When synthetic tannin is used, the solid content is used. As 1
It is preferable to use it in the range of 8% by weight, and to carry out the fixing treatment at a pH of 3.5 to 4, a treatment temperature of 50 to 80 ° C., and a treatment time of 15 to 30 minutes.

[0018]

In the method for producing a polyamide dyed product according to the present invention, after the polyamide molded product is dyed with a disperse dye as described above, it is reduced and washed, and further fixed with a fixing agent for nylon acid dye. As a result, the disperse dye is prevented from falling off from the polyamide molded product, and the dyeing fastness of the obtained polyamide dyed product is improved.

[0019]

[Examples] A method for producing a polyamide dyed product according to an example of the present invention will be specifically described below, and a comparative example will be given. According to the method of this example, a polyamide dyed product having high dyeing fastness can be obtained. Make clear.

(Example 1 and Comparative Example 1) In Example 1 and Comparative Example 1, the fastener element 6-
A polyamide molded product made of nylon was used, and a fastener made of polyethylene terephthalate obtained by copolymerizing 4.8% by weight of polyethylene glycol # 600 on the fastener tape and sewing thread was dyed.

Here, in Example 1, as the disperse dye, Miketon Polyester Red 3B- was used.
SF (manufactured by Mitsui Toatsu Dyestuff Co., Ltd.) was used, and
Using owf, dyeing was performed at a dyeing temperature of 110 ° C. for 60 minutes.

Then, 2 g each of caustic soda, hydrosulfite, and a cleaning agent (Daiichi Kogyo Seiyaku Co., Ltd .: amylazine D) were applied to the fastener dyed in this way.
/ L was used for reduction washing.

After that, in carrying out the fixing treatment to this fastener, an aromatic sulfonic acid derivative which is a synthetic tannin (manufactured by Nylox 1500 manufactured by One Company) was used as a fixing agent for the nylon acid dye. Using 8% owf of a fixing agent, a fixing process was performed at a processing temperature of 60 ° C. for 30 minutes.

On the other hand, in Comparative Example 1, the above Example 1 was used.
Dyeing and reduction washing were carried out in the same manner as, but fixing treatment was not carried out.

Next, in order to examine the state of color transfer in each dyed product of Example 1 and Comparative Example 1 obtained as described above, each dyed product of Example 1 and Comparative Example 1 was put together with a vinyl chloride sheet. And put it between the polyester cloth and 1 more
It was sandwiched between 2 × 5 cm plastic plates and a load of 4.5 kg was applied, and the product was placed in a desiccator filled with water in this state, and the desiccator was placed in a high temperature dryer at 40 ° C. and treated for 48 hours. The color transfer to the vinyl chloride sheet or polyester cloth in the element of each fastener of Example 1 and Comparative Example 1 dyed as described above was judged on a gray scale, and the results are shown in Table 1 below.

[0026]

[Table 1]

As is clear from these results, in Example 1, the color transfer to the vinyl chloride sheet or polyester cloth in the element portion composed of polyamide is considerably less than in Comparative Example 1. The dyeing fastness of polyamide was improved.

(Example 2 and Comparative Example 2) In this Example 2 and Comparative Example 2, the fastener element was 6,
A polyamide molded product made of 6-nylon was used, and a fastener tape and a sewing thread using polyethylene terephthalate were dyed.

Here, in Example 2, Dianix Red KBN-SE (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) was used as the disperse dye, and 4% owf of this disperse dye was used at a dyeing temperature of 130 ° C. for 60 minutes. Was done.

With respect to the fastener dyed in this way, 2 g / l of caustic soda, 0.7 g / l of thiourea dioxide (Tokai Denka Co., Ltd .: Techlite), and a cleaning agent (Daiichi Kogyo Seiyaku Co., Ltd .: Reduction reduction was performed using 2 g / l of amylazine D).

After that, in performing the fixing treatment on this fastener, a synthetic tannin oxysulfonate condensate (manufactured by Shichifuku Kagaku Co., Ltd .: Nylon sticker KB soft) was used as a fixing agent for the nylon acid dye. On the other hand, 8% owf of this fixing agent was used, and fixing treatment was performed at a treatment temperature of 60 ° C. for 30 minutes.

On the other hand, in Comparative Example 2, the above Example 2 was used.
Dyeing and reduction washing were carried out in the same manner as, but fixing treatment was not carried out.

Next, the state of color transfer in the elements of the respective fasteners of Example 2 and Comparative Example 2 obtained as described above is judged by gray scale in the same manner as in Example 1 and Comparative Example 1 above. The results are shown in Table 2 below.

[0034]

[Table 2]

As is clear from these results, in the second embodiment, as in the case of the first embodiment, the transfer of color to the vinyl chloride sheet or the polyester cloth in the element portion composed of polyamide is a comparative example. It was considerably less than that of No. 2, and the dyeing fastness in polyamide was improved.

(Example 3 and Comparative Example 3) In Example 3 and Comparative Example 3, the fastener element 6-
A polyamide molded product made of nylon was used, and a fastener made of polyethylene terephthalate obtained by copolymerizing 4.8% by weight of polyethylene glycol # 600 on the fastener tape and sewing thread was dyed.

Here, in Example 3, as the disperse dye, Miketon Polyester Red 3B- was used.
SF (manufactured by Mitsui Toatsu Dyestuff Co., Ltd.) was used, and
Using owf, dyeing was performed at a dyeing temperature of 110 ° C. for 60 minutes.

2 g of caustic soda, hydrosulfite, and a cleaning agent (Daiichi Kogyo Seiyaku Co., Ltd .: amylazine D) were each added to the fastener dyed in this manner.
/ L was used for reduction washing.

After that, when performing the fixing treatment on this fastener, tannic acid and tartar are used in combination as a fixing agent for nylon acid dye, and first, an aqueous solution containing 8% owf of tannic acid is adjusted to pH 4 with acetic acid. The above fastener is used at a processing temperature of 60 ° C for 3
After the treatment for 0 minutes, the above fastener was treated at a treatment temperature of 60 ° C. for 20 minutes by using an aqueous solution containing tartarite of 1.8% owf adjusted to pH 4 with acetic acid to perform the fixing treatment.

On the other hand, in Comparative Example 3, the above Example 3 was used.
Dyeing and reduction washing were carried out in the same manner as, but fixing treatment was not carried out.

Next, the state of color transfer in the elements of the respective fasteners of Example 3 and Comparative Example 3 obtained as described above is judged by gray scale in the same manner as in Example 1 and Comparative Example 1 above. The results are shown in Table 3 below.

[0042]

[Table 3]

As is clear from this result, in the third embodiment, as in the case of the first embodiment, the transfer of color to the vinyl chloride sheet or the polyester cloth in the element portion composed of polyamide is a comparative example. It was considerably less than that of No. 3, and the dyeing fastness in polyamide was improved.

Example 4 and Comparative Example 4 In this Example 4 and Comparative Example 4, 25% of 6-nylon and 75% of polyethylene terephthalate copolymerized with 4.8% by weight of polyethylene glycol # 600 were used. The composite yarn woven fabric containing the finished polyamide was dyed.

Here, in Example 4, as the disperse dye, Miketon Polyester Red 3B- was used.
SF (manufactured by Mitsui Toatsu Dyestuff Co., Ltd.) was used, and
Using owf, dyeing was performed at a dyeing temperature of 110 ° C. for 60 minutes.

Then, 1 g each of sodium carbonate, hydrosulfite, and a detergent (Amylazine D manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added to the thus-dyed composite yarn fabric.
/ L was used for reduction washing.

Thereafter, when the composite yarn fabric is fixed, an aromatic sulfonic acid derivative which is a synthetic tannin (manufactured by Nylox 700) is used as a fixing agent for the nylon acid dye, and the fixing agent is 8%. The aqueous solution containing owf was adjusted to pH 4 with acetic acid, and the composite yarn woven fabric was fixed with this aqueous solution for 30 minutes at a treatment temperature of 60 ° C.

On the other hand, in Comparative Example 4, the above-mentioned Example 4 was used.
Dyeing and reduction washing were carried out in the same manner as, but fixing treatment was not carried out.

Next, in order to examine the state of color transfer in each of the dyed products of Example 4 and Comparative Example 4 obtained as described above, these dyed products were sandwiched together with a polyester cloth and a nylon cloth. Then, sandwich it between 12 x 5 cm plastic plates and apply a load of 4.5 kg, put it in a desiccator filled with water in this state, put this desiccator in a high temperature dryer at 40 ° C and process for 48 hours. After that, the color transfer with respect to the polyester cloth and the nylon cloth in each of the above dyed products was judged on a gray scale, and the results are shown in Table 4 below.

[0050]

[Table 4]

As a result, the dyed product of the composite yarn fabric containing the polyamide of Example 4 had considerably less color transfer to the polyester cloth and the nylon fabric than the dyed product of the composite yarn fabric containing the polyamide of Comparative Example 4. And the dyeing fastness in the polyamide part was improved.

(Example 5 and Comparative Examples 5 and 6) In Example 5 and Comparative Examples 5 and 6, a polyamide molded product extruded from 6-nylon was used as a fastener element, and a fastener tape was used. Also, a fastener using polyethylene terephthalate in which 4.8% by weight of polyethylene glycol # 600 was copolymerized with the sewing machine thread was dyed.

Here, in Example 5, as the disperse dye, Miketon Po was added to the above fastener.
2.1% owf of Lyester Red 3B-SF (manufactured by Mitsui Toatsu Dyestuff Co., Ltd.), Foron Brilliant
t Blue SE-CTLY (manufactured by Sandoz) at 0.005% owf, Dianix Orange G-
Using SE (manufactured by Mitsubishi Kasei Co., Ltd.) 0.93% owf, dyeing was carried out for 60 minutes at a bath ratio of 1:30 and a dyeing temperature of 110 ° C.

Then, 2 g each of caustic soda, hydrosulfite and a cleaning agent (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: amylazine D) were applied to the fastener dyed in this way.
/ L was used for reduction cleaning at 80 ° C for 30 minutes.

Thereafter, when fixing treatment was performed on this fastener using a fixing agent for nylon acid dye, first, 6% of tannic acid (manufactured by Dainippon Pharmaceutical Co., Ltd .: tannic acid extract) was used.
6 using an aqueous solution containing owf adjusted to pH 4 with acetic acid
The mixture was treated at 0 ° C. for 30 minutes, and then treated at 60 ° C. for 30 minutes with an aqueous solution containing 6% owf of tartarite (Dainippon Pharmaceutical Co., Ltd., New Poweron).

On the other hand, in Comparative Example 5, the above Example 5 was used.
Dyeing and reduction washing were carried out in the same manner as, but fixing treatment was not carried out.

In Comparative Example 6, the above Example 5 was used.
Reverse the order of reducing cleaning and fixing treatment from the case of
After dyeing with a disperse dye in the same manner as in Example 5, the fastener thus dyed was first subjected to the above fixing treatment, and then subjected to the above reduction cleaning.

Next, in order to examine the state of color transfer in each of the dyed products of Example 5 and Comparative Examples 5 and 6 obtained as described above, these dyed products were sandwiched together on a vinyl chloride sheet, and This was sandwiched between 12 × 5 cm plastic plates and a load of 4.5 kg was applied, and in this state, this was placed in a thermo-hygrostat adjusted to a temperature of 37.5 ° C. and a humidity of 90% and left for 48 hours. The color transfer to the vinyl chloride sheet in the elements of the fasteners of Example 5 and Comparative Examples 5 and 6 dyed as described above was judged on a gray scale, and the results are shown in Table 5 below.

Furthermore, the light fastness of dyeing on the tape portion of each fastener of Example 5 and Comparative Examples 5 and 6 dyed as described above was measured according to JIS L 0842, and the discoloration of washing and the staining of washing were observed. JIS L 0
844 A-2, and the results are shown in Table 5 below.

[0060]

[Table 5]

As is clear from these results, in Example 5 above, the color transfer to the vinyl chloride sheet in the element portion made of polyamide is considerably smaller than in Comparative Examples 5 and 6. The dyeing fastness of the polyamide is considerably improved as compared with those of Comparative Examples 5 and 6, and the dyeing fastness of the tape portion of the fastener is different from that of Example 5 and Comparative Examples 5 and 6. There was no adverse effect on the dyeing in the tape portion.

[0062]

As described in detail above, when the method for producing a polyamide dyed product according to the present invention is used, the disperse dye is prevented from falling off on the polyamide molded product, and the disperse dye is used to give a polyamide dyeing having high dyeing fastness. Goods are now available.

When the method for producing a polyamide dyed product according to the present invention is used, a product obtained by combining a polyamide and another synthetic resin such as polyester can be dyed with a disperse dye to obtain a high dye fastness. After the dye is obtained with a disperse dye as in the conventional case, the disperse dye in the polyamide is decolorized, and then it is not necessary to perform the troublesome work of dyeing the polyamide part again with an acid dye, and its production is easy. I can do it now.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihide Tomikawa 1-65-201, Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka

Claims (2)

[Claims] 1. A method for producing a polyamide dyed product, which comprises dyeing a polyamide molded product with a disperse dye, reducing and washing the dye, and further fixing the product using a fixing agent for a nylon acid dye. 2. The method for producing a polyamide dyed product according to claim 1, wherein the nylon acid dye fixing agent comprises:
A method for producing a polyamide dyeing product, characterized by using a combination of tannic acid and tartarite or a synthetic tannin.