JPS584116B2 - Resist dyeing method for modified polyester fibers - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for resist dyeing modified polyester fibers.

The purpose is to perform resist dyeing on modified polyester fibers with a high resist dyeing effect and clear outlines.

Conventionally, it has been extremely difficult to perform resist dyeing when applying disperse dyes to polyester synthetic fibers and the like.

Most attempts have been made to use mechanical resist dyes, such as glue, clay, activated carbon, etc., in combination with disperse dyes, but disperse dyes have the lowest resisting power and require a corresponding increase in the thickness of the resist paste layer. It is unsuitable for roller printing because it needs to be made thicker, and screen printing has many practical problems, such as clogging of the shears caused by the resist agent.

The present inventors have already proposed a method for resist dyeing hydrophobic fibers using a disperse dye that has a structure that forms a chelate compound with a metal, and a metal compound that has chelate-forming ability as a resist dye (Tokuko Showa). 40-20516).

However, especially when polyester fibers are targeted, even such methods are not always sufficiently effective.

The present inventors have conducted intensive research on an excellent resist dyeing method for polyester fibers, and found that the above-mentioned drawbacks are due to the low affinity between ordinary polyester fibers and metals, and that polyester fibers are used in the form of metal salts. The inventors have discovered that when modified polyester fibers containing sulfonate groups are used, the affinity for metals becomes significantly greater, and as a result, extremely excellent resist dyeing effects can be obtained, and the present invention has been achieved.

That is, the present invention involves resist dyeing a modified polyester fiber containing a 5-sulfoisophthalic acid component in the polymer molecule using a disperse dye having a structure that forms a chelate compound with a metal and a metal compound having a chelate-forming ability. This is a resist dyeing method for modified polyester fibers.

The modified polyester fiber in the present invention has 5
- As long as it contains a sulfoiphthalic acid component, there are no limitations on its manufacturing method or the form in which it is contained.

Such modified polyester fibers are usually produced by adding 5-sulfoisophthalic acid or an ester-forming derivative thereof to the reactant before completing the synthesis of the polyester to be modified, then completing the synthesis of the polyester, and then It is manufactured by melt spinning according to the method.

The polyester that becomes the base of the modified polyester is composed of terephthalic acid or its ester-forming derivative and HO(CH2).
polymethylene glycol represented by nOH (where n is an integer from 2 to 10), and polyethylene terephthalate is particularly preferred.

Particularly preferred modified polyester fibers are modified polyethylene terephthalate containing a small proportion of the structural units shown below.

It is desirable to use at least about 0.5 (mol) percent sulfonate salt, based on the terephthalic acid content in the polymer.

This is because less than this amount results in polyester fibers that have a relatively low affinity for chelate-forming metal compounds used as resists.

Preferably, the sulfonate salt concentration is within the range of 2 to 5 (mol)%.

The metal in the metal salt is preferably an alkali metal or an alkaline earth metal.

The resist dyeing method for the modified polyester fiber will be explained in detail.

Disperse dyes with certain chemical structures have the property of forming chelate compounds with metals.

As a result, it was found that the dyeability of the dye to the dyed object was significantly reduced, especially when applied to the modified polyester fiber.

The method of the present invention attempts to perform resist dyeing by applying the properties of such disperse dyes.

For example, one or two metal compounds capable of forming chelates.
After printing a sizing agent containing at least one seed on the modified polyester fiber, a disperse dye is uniformly applied by a method such as padding, draw dyeing, ironing, or spraying, and then a dry heat or steam heat treatment is performed.

In the printed area of the paste containing a metal compound, the dye forms a chelate compound with the metal, and its affinity for the fibers is significantly reduced, making it impossible to dye the fibers even after heat treatment.

On the other hand, in the non-printed areas, a good coloring effect can be obtained in the heat treatment process.

In this way, effective anti-staining becomes possible.

In this case, a dye may be applied to the fibers in advance, a paste containing a metal compound may be printed on the fibers, and then heat treatment such as dry heat or steaming may be performed.

It is also possible to perform colored resist dyeing by using a dye that does not have chelate-forming ability in combination with the white resist dyeing paste.

To explain in more detail, when a dye molecule contains a group having several unshared electron pairs, it has the property of forming a chelate compound with a metal such as Cu, Cr, Co, Fe, or AI.

For example, in the case of a 1-oxyanthraquinone dye, one metal (trivalent) is chelated to three dye molecules as shown in the drawing below, resulting in a large molecular structure, which significantly reduces the dyeability of the dye to be dyed.

In the above drawings, Me represents metal.

The tendency of this chelation depends on the structure of the dye, the type of metal, and the pH.
etc., it is significantly influenced by

The method of the present invention is a resist dyeing method that takes advantage of the properties of such dyes, and is especially effective when applied to the modified polyester fibers.

In other words, the sulfonate groups in the modified polyester fibers have a high affinity with metals, and when a metal compound with chelate-forming ability used as a resist dye is printed, the metals bond with the sulfonate groups in the modified polyester fibers. However, the metal forms a monomolecular film and covers the fiber surface, and then the disperse dye and metal form a chelate, which greatly increases the resisting effect.

In the case of the modified polyester fiber, a sufficient resisting effect can be obtained even if the concentration of the resisting agent is small.

However, unmodified ordinary polyester fibers have little affinity with metals, so it is difficult to coat the polyester fibers with metals.

Therefore, a considerable portion of the disperse dye passes through the gaps between the metals and dyes the fibers, so a large amount of resisting agent is required, and the resisting effect is inferior to that of the modified polyester fibers.

The modified polyester fibers used in the method of the present invention are in the form of woven fabrics, knitted fabrics, films, etc., and can also be effectively applied to blended and interwoven fabrics.

As the dye in the present invention, any disperse dye that can be chelated with a metal can be used.

The disperse dye referred to herein is a dye that is insoluble or poorly soluble in water and is used to dye hydrophobic fibers such as modified polyester fibers from a suspension dispersed in water.

Examples of disperse dyes that can be chelated include the following registered trademark products.

Seriton Fast Yellow G (manufactured by B.A.S.F.) Seriton Yellow 5G (manufactured by B.A.S.F.) Seriton Fast Pink RF (manufactured by B.A.S.F.) Seriton Fast. Pink FF3B (made by B・A・S・F) Seriton Fast Pink B (made by B・A・S・F) Seriton Fast Plug Green B (made by B・A・S・F) Duranol Plug G ( (manufactured by I.C.I.) Duranol Brilliant Blue CB (manufactured by I.C.I.) As the metal compound, any metal compound having chelate-forming ability can be used.

For example, metal compounds such as chromium, iron, cobalt, nickel, copper, and aluminum can be used, and the most effective are copper and chromium compounds.

Chromium compounds include chromium chloride, chromium fluoride, chromium formate, chromium hydroxide, monochrome acetate, dichromium sulfate, monochrome chloride, potassium dichromate, etc.; copper compounds include copper formate, copper acetate, Copper hydroxide, cupric chloride citrate steel, copper nitrate, copper oxalate, copper sulfate, copper tartrate, etc. Iron compounds include ferric chloride, ferrous sulfate, etc. Nickel compounds include nickel formate, oxalic acid, etc. Nickel, nickel acetate, nickel hydroxide, etc. are used, cobalt compounds include cobalt hydroxide, cobalt chloride, etc., and aluminum compounds include aluminum chloride, aluminum sulfate, etc.

The amount used is not particularly limited, depending on the amount of the corresponding dye.

In the method of the present invention, a paste containing one or more of the metal compounds described above is printed on the fibers in advance, and the dye is applied thereto by a method such as padding, dyeing, ironing, spraying, or coating. , and then subjected to steam treatment or dry heat treatment.

In this case, a dye may be applied to the fibers in advance, the dye paste is printed, and then a dry heat or steam heat treatment may be performed.

In order to promote the reaction between the metal and the dye, alkaline or acidic compounds may be used in combination, or substances having a mechanical resisting effect, such as water repellents such as paraffin emulsion, activated carbon,
Clay etc. can also be used together.

Furthermore, in the case of blending or interweaving with other fibers, more effective resist dyeing can be achieved by simultaneously using a resist dyeing agent for the other fiber.

As described above, the method of the present invention exhibits a resist dyeing effect because the modified polyester fiber has good affinity with metals and the dye forms a chelate compound with metals.
This reactivity is extremely high, making it possible to obtain prints with high resistance dyeing power and clear outlines.

Furthermore, since the method of the present invention is a chemical resist dyeing method, there is no need to make the glue layer particularly thick, so it can be applied to roller printing machines, and even when applied to screen printing, there are no problems such as clogging of the printer. .

Chelate products are extremely selective, and while dyes without chelate-forming ability are not affected by metal laxatives, dyes with chelate-forming ability have extremely high reactivity; therefore, white resist dyeing can be achieved by selecting an appropriate dye. , color resist dyeing can now be done freely.

Disperse dyes without chelate-forming ability include, for example, the following registered trademark products.

Seriton Fast Yellow RR (manufactured by B・A・S・F)
Seriton Fast Orange GR (manufactured by B.A.S.F.) Seriton Scarlet B (manufactured by B.A.S.F.) Seriton Fast Plug FFR (manufactured by B.A.S.F.) Dyes and metals The stability of the chelate compound formed by p
Significantly influenced by H, as the pH decreases, competition for binding of metal ions and hydrogen ions to the dye becomes disadvantageous for the metal ions as the concentration of hydrogen ions increases, resulting in dissociation of the chelate bond.

Therefore, if the value of 1 is low, the resist dyeing effect will be lost.

It has also been found that by utilizing this phenomenon, cleaning after color development can be effectively carried out.

That is, it has been found that by washing at a low pH after color development, the insoluble chelate compound in the printed area of Kinmanshio paste is easily dissociated and the washability is improved.

By applying the above phenomenon, the following resist dyeing method is also possible.

That is, a metal salt, a dye, and an acid are applied to the fabric in advance, and after drying, an alkaline sizing agent is printed on the fabric, followed by color development.

As a result, in the paste-printed area, color development was reduced due to the formation of chelate compounds, making effective resist dyeing possible.

Examples will be described below.

All parts and units in the examples are based on weight.

Example 1 [Production of modified polyester fiber] 10 parts of 5-sulfoisophthalic acid is dissolved in 100 parts of a mixed solution of 85% methanol and 15% benzene, and 1 part of sulfuric acid is added.

A mixture of benzene, water, and methanol is slowly distilled out over 24 hours, and the liquid level of the esterification mixture is maintained constant by constantly adding the methanol and benzene mixture.

Potassium acetate is added to the reaction mixture and the resulting solid product is filtered off.

The product is dissolved in boiling water, neutralized with potassium carbonate and decolorized with charcoal.

When the solution is filtered and cooled, crystals of potassium 3,5-di(carbomethoxy)benzenesulfonate are obtained.

49 parts dimethyl terephthalate, 34.5 parts ethylene glycol, 0.067 parts calcium acetate, 0.0
1.6 parts of the above product are added to 15 parts of antimony trioxide to give a ratio of diester sulfonate salt to dimethyl terephthalate of about 2 (mol) %.

The mixture is heated for 3 hours, during which time the temperature rises to 165-220° C. with methanol evolution.

The pressure is then reduced to 1 mmHg and the temperature is increased to 275°C.

A polymer is obtained after 5 hours.

A modified polyester fiber is obtained by spinning this polymer at 290° C. through a 34-hole spinneret and then subjecting it to a stretching heat treatment.

[Resist dyeing]

Copper acetate 5 parts Water and base glue (British Gum) 95 total
100 was printed on the taffeta made of the modified polyester fibers, and after drying, 4% of 1,4-dihydroxyethylamino-5,8-dihydroxyanthraquinone (having chelate-forming ability), disper. A dispersion of 0.5% TL (manufactured by Meisei Chemical Co., Ltd.) was pad-dried, and then heated in a star steamer at 120°C for 2 hours.
Steam for 0 minutes, wash with water, soap, wash with water and dry.

As a result, good white resist dyeing was obtained on the blue background.

In addition, 4'nitro.4-N-ethyl-N-hydroxyethylamino-1,1'-azobenzene (
By adding the compound (which does not have chelate-forming ability) in a dispersed state, a colored resist dye with a red pattern on a blue background was obtained.

Example 2 Copper formate 5 parts water and base paste (
Yuzen paste) 95 (total: 100) The resist dyeing paste made of 100 yen was printed on the taffeta made of the modified polyester fiber shown in Example 1, and after drying, 1,4-diamino-
2-Methoxyanthraquinone 4%, Disper TL (
A dispersion of 0.5% (manufactured by Meisei Chemical Co., Ltd.) was pad-dried,
Thereafter, it is steamed in a star steamer at 120°C for 40 minutes, washed in a 1% acetic acid solution at 80°C for 20 minutes, reduced, washed with water, and dried.

As a result, a white resist dye was obtained on the reddish-purple ground.

In this case, the heat treatment may be performed by a thermosol method at 180° C. for 60 seconds.

In the case of colored resist dyeing, as in Example 1, a disperse dye having no chelate-forming ability is used in combination with the resist dyeing paste.

Example 3 Copper acetate 5 parts Glycolic acid (40%) 10 Schauftragant glue 50 Water 35 Total 100 A resist dyeing paste consisting of 65% modified polyester fiber and 35% cotton shown in Example 1 was used as a broad K mark consisting of 65% modified polyester fiber and 35% cotton. Print and dry.

Next, pad a dye paste with the following composition and add 1-amino-2-methoxy-4 4 parts hydroxyanthraquinone Remazol Red B (sodium hexalginate + water 92 total)
100 After drying, perform thermosol treatment at 180°C for 1 minute, wash with water, soak, and finish with water.

As a result, good white resist dyeing was obtained on the red ground.

Example 4 A dye solution containing 5% of a dye obtained by diazotizing m-nitroaniline and coupling it to methylquinolone, 0.2% of Disper-TL (manufactured by Meisei Chemical Co., Ltd.), and 0.2% of sodium alginate was prepared in Example 1. It is padded onto taffeta made of modified polyester fiber shown in , and dried.

Next, a resist dyeing paste with the composition shown below is printed on top of this, and cuprous chloride is applied.
Part 5 Schoft Lagant Glue
50 water 45 total
100 After drying, perform thermosol treatment at 180°C for 60 seconds, then finish by washing with water, soaping, washing with water and drying.

As a result, good white resist dyeing on yellow ground became possible.

Example 5 A printing paste consisting of 5 parts of copper acetate, 7 parts of m-sodium nitrobenesulfonate, 60 parts of raw tragacanth paste, 28 parts of water, and 100 parts in total was printed in the form of polka dots on the fabric shown in Example 3 by a screen method and dried. do.

Next, a dye solution having the following composition is padded with a mangle, dried, and then steamed at 120° C. for 30 minutes using a star steamer.

1-amino, 4-hydro 4 parts oxyanthraquinone indanthrene red 3 FBB (manufactured by B・A・S・F) Al, sodium ginate + water 93 total
100 Afterwards, apply an alkaline reducing agent glue with the following composition to the entire surface.
Immediately after printing, it is steamed for 30 seconds in a flash ager, followed by oxidation, soaping, and washing with water.

Flotex (9%) (product of National Starch Products) 35 parts water
45 caustic soda (35%)
15 Hydrosulfite 5 total
100 As a result, a white polka dot pattern was obtained on the red ground.

Example 6 In advance, only the cotton side was coated with direct dye Durazol or -2R (I
A dye solution as described below is padded onto the fabric shown in Example 3K which has been ground-dyed using C.I. Co., Ltd. and dried.

Resolin Blue FBL (manufactured by Bayer) 4 parts (with chelate-forming ability) Sodium alginate + water 96 total
Next, a resist dyeing paste consisting of 100% cuprous chloride 5 parts hydrosulfite 5% raw tragacanth paste 50% water 40% in total was printed in the shape of polka dots using a roller printing machine, dried, and then dried in a star steamer at 120°C for 30 minutes. Steam treatment, followed by washing, soaping, and rinsing.

As a result, the direct dye on the cotton side was discharged by the action of the reducing agent, and the disperse dye on the modified polyester fiber side was resist-dyed by chelation, resulting in a white polka dot pattern on the blue ground.

Example 7 6 parts of the disperse dye Shibaset Dark Blue RB (manufactured by Shiba Co., Ltd.) was added to 20 parts of water on the modified polyester fiber fabric shown in Example 1, which had been previously printed with a resist dyeing paste containing copper formate and dried. After dispersing well, add naphka crystal gum (30% solution) 7
A dye paste solution in which 4 parts are mixed is dyed using a floating method using a coating machine.

After drying, steam treatment is performed at 120° C. for 20 minutes.

Then acetic acid (98%) 2C. C. /l of liquid at 50℃1
Monogen (higher alcohol sulfate ester salt) after 0 minutes treatment
2 g/l, soda ash 1 g/l, soaping for 20 minutes at 70-80°C.

In this way, a homogeneous and robust print with a navy background color was obtained.

Example 8 A plain weave made of the modified polyester fiber of the present invention produced in Example 1, a plain weave made of a modified polyester fiber made by copolymerizing 4 parts by weight of polyethylene glycol 4000 with polyethylene terephthalate, and a regular polyester fiber made of polyethylene terephthalate. In order to compare the resist dyeing properties of the three plain weaves, resist dyeing was carried out in the same manner as in Example 1, and the whiteness of the resist dyed pattern was compared.

Whiteness is JIS0804-65 gray scale (for contamination)
Shown in

Grade 5 is the oldest. Modified polyester fiber of the present invention
5th grade polyethylene glycol copolymerized modified polyester fiber 3rd to 4th grade regular polyester fiber The 3rd to 4th grade resist dyeing effect was that the modified polyester fiber of the present invention was 5th grade and pure white.

However, the other two were grade 3-4 and had low commercial value.

Claims (1)

[Claims] 1. A modified polyester fiber containing a 5-sulfoisophthalic acid component in the polymer molecule is resist-dyed using a disperse dye having a structure that forms a chelate compound with a metal and a metal compound having a chelate-forming ability. Resist dyeing method for modified polyester fibers.