JP2003501490A - Crystal modification of a water-insoluble monoazo dye. - Google Patents

Abstract

(57) [Summary] It is represented by the following structural formula [I] and shows one strong peak at a diffraction angle (2θ) of 11.1 ± 0.1 °, and 8.1 ± 0. 1 °, 21.8 ± 0.1 °, 23.1 ± 0.1 °, and 25.2 ± 0.1 ° X-ray diffraction pattern showing four peaks moderate in the diffraction angle (Cu K _alpha) A water-insoluble monoazo dye having a crystalline modification characterized by:

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a monoazo dye, and more particularly to a blue monoazo dye having a novel crystal modification with excellent dispersibility. Furthermore, the present invention also relates to a method of using this monoazo dye for dyeing fibers, particularly polyester fibers, and more particularly to a method of dyeing fibers, especially polyester fibers, under more severe conditions than before.

[0002]

[Prior art]

In recent years, various dyeing methods have been rationalized in the dyeing industry. For example, when dyeing polyester fibers with disperse dyes, there are jet dyeing methods for textiles, cheese dyeing methods and package dyeing methods for yarns, and these methods are widely used. Has been done.

These dyeing methods have a system in which a large number of layers of fibers are wound and dyeing is carried out by forcibly circulating a dye dispersion solution through a tightly packed fixed layer. Therefore, it is particularly important that the dispersibility of the dye in the dye bath is better than before. If the dye particles agglomerate with each other due to insufficient dispersion to form a relatively large agglomerate, the filtration phenomenon of the dye particles by the fiber layer occurs and the permeability of the dye into the fiber is poor. As a result, aggregates are attached to the surface of the material to be dyed, so that problems such as uneven dyeing depth between the inner and outer layers and a decrease in fastness such as friction fastness occur.

Particularly, more recently, from the viewpoint of saving resources and energy, more stringent dyeing conditions,
That is, (1) lower the bath ratio of the dyeing bath (for example, the ratio of the dyed material to the dye solution is 1:
(30) to 1:10), (2) reduce the proportion of dispersant used (eg reduce the ratio of Cake: Dispersant from 1: 3 to 1: 1), (3)
Raise the dyeing temperature and shorten the dyeing time (for example, change the dyeing condition from 1 hour at 130 ° C to 0.5 hour at 135 ° C), and (4) increase the heating rate (for example, 1 ° C per minute). To 2 ° C. per minute) there is a move towards more stringent dyeing conditions, shortening the heating time. However, all of these conditions adversely affect the dispersion stability of the dye. From this point of view, therefore, there is an even greater need for dyes with better dispersibility.

Due to such a situation, an extremely large number of dyes which have been relatively satisfactory in dispersibility have been insufficient in dispersibility in recent severer dyeing methods and dyeing conditions. For example, the acetanilide type monoazo dye represented by the structural formula [I] of claim 1 can be obtained by carrying out a coupling reaction between a diazo component and a coupling component, which is a conventional mild dyeing. Under the conditions, the polyester fiber is dyed uniformly, and it is excellent in various criteria of fastness, but under the more severe conditions as mentioned above, the dispersion is insufficient and the dyeing depth is uniform. That is extremely difficult.

Furthermore, this dye also has problems with its compatibility with various dyeing auxiliaries. For example, the high temperature dispersion stability in the presence of Glauber's salt (Na ₂ SO ₄ ) is extremely poor,
As a result, when a polyester / cotton blended product is dyed with a reactive dye or the like in the presence of Glauber's salt, a non-uniform dyeing results. In addition, when used as a mixture with other dyes, there is a problem that color change or uneven dyeing occurs due to poor compatibility with the mixed dyes. As a result, there is an ever-increasing need for dyes that are highly dispersible and that provide uniform dyeability with excellent fastness even when using more stringent dyeing methods and conditions.

[0007]

[Problems to be Solved by the Invention]

Therefore, the problem to be solved by the present invention is to solve the conventional problems described above and to provide a dye having excellent dispersibility. As a result of careful study on the above-mentioned problems, the present inventor has found that the acetanilide type monoazo compound represented by the structural formula [I] of claim 1 has at least two kinds of crystal modifications. One is a crystal modification obtained by a conventional conventional method, and the other is a new crystal modification; the stability of a dispersed state in a dye-dyeing bath exists not only in the size of dye particles. Strongly related to crystal transformation;
When this compound exhibits the above-mentioned novel crystal modification, it is remarkably excellent in dispersibility as compared with the conventional crystal modification; furthermore, by using this compound as a dye, both in conventional dyeing conditions and more severe dyeing conditions. It was also found that a dye capable of more satisfactory dyeing can be obtained. The present inventors have arrived at the present invention based on these findings.

[0008]

[Means for Solving the Problems]

Therefore, the present invention is represented by the structural formula [I] of claim 1 and exhibits one strong peak at a diffraction angle (2θ) of 11.1 ± 0.1 °, and 8.1 ± 0.1. °, 21.8 ± 0.
Water with a crystalline modification characterized by an X-ray diffraction pattern (CuK _α ) showing four moderate peaks at diffraction angles of 1 °, 23.1 ± 0.1 °, and 25.2 ± 0.1 ° An insoluble monoazo dye is provided.

[0009]

DETAILED DESCRIPTION OF THE INVENTION

The novel crystal modification of the present invention (hereinafter referred to as α-type crystal modification) can be obtained by the following method. For example, the above-mentioned monoazo compound represented by the structural formula [I] is prepared by diazotizing 6-chloro-2,4-dinitroaniline by a usual method, and then in an aqueous medium at 5 to 15 ° C, preferably 0 to 10 ° C. The temperature is 0.5 to 15 hours, and the coupling agent 3- (N
, N-Diallyl) amino-4-methoxyacetanilide is synthesized and the cake is converted to the α-form modification by further treatment under specific conditions. This treatment method is carried out by, for example, dispersing a formaldehyde condensate of (1) naphthalene sulfonic acid or a concentrated cake of a sulfide pulp waste liquor whose main component is sodium lignin sulfonate, and then 60 to 130 ° C., preferably A method of stirring at a temperature of 80 to 100 ° C. for 0.5 to 30 hours, preferably 1 to 10 hours, and (2) alcohols such as methanol, ethanol and butanol, dioxane, ethylene glycol and glycol ether. The method of dispersing a β-type crystal modification cake in an organic solvent such as ether and performing stirring treatment at a temperature of 15 to 100 ° C., preferably 20 to 80 ° C. for 0.5 to 10 hours.

Next, the α-type crystal modification and β-type crystal modification of the monoazo compound represented by the above structural formula [I] will be described with reference to the drawings. Figures 1 and 2 show a model RAD-R manufactured by Rigakudenki under the following conditions by X-ray powder diffractometry recording the diffraction of CuK _alpha radiation using a proportional counter.
It is an X-ray diffraction pattern obtained by using B. (X-ray radiation) CuK _α1 / 40kV / 100mA (counter monochromator) Curved crystal monochromator (divergence slit) 1 ° (scattering slit) 1 ° (light receiving slit) 0.15mm (scanning mode) continuous (scanning speed) 5 0.0 ° / min (scan step) 0.1 ° / min (scan axis) 2θ / θ The horizontal axis is the diffraction angle (2θ) and the vertical axis is the diffraction intensity. FIG. 1 is a diffraction pattern of an α-type crystal modification which is a novel crystal form of the present invention, and particularly has one strong peak at a diffraction angle (2θ) of about 11.1 ° and also about 8. 1 °, about 21.8 °, about 2
It has four moderate peaks at diffraction angles of 3.1 ° and about 25.2 °. FIG. 2 is a diffraction pattern showing a conventional β-type crystal modification, and this diffraction pattern is shown in FIG.
It is clear that it is different from that.

For the same crystal form, the diffraction angles based on the X-ray diffraction method always agree within an error range of about ± 0.1 °, so these diffraction patterns clearly show different crystal transformations. There is. Due to this difference in crystal modification, the novel α-type crystal modification monoazo compound of the present invention has properties different from those of the conventional β-type during dyeing, and as can be seen from Experimental Examples 1 and 2 below, Excellent dispersibility.

The present invention also provides a method of using the novel monoazo dye having the α-type crystal modification for dyeing fibers, particularly polyester fibers. Dyeing is carried out by dispersing the monoazo dye of the present invention in an aqueous medium in the presence or absence of a dispersant to form a dye bath or a printing paste, and then, if necessary, dip dyeing under more severe conditions. Or it is performed by printing. For example, in the case of dip dyeing, a high temperature dyeing method, a carrier dyeing method, a thermosol dyeing method, or other dyeing treatment can be applied. In such a situation, the above-mentioned jet dyeing method, cheese dyeing method, or package dyeing method can be used. A dyeing method can be preferably used.

Regarding the dyeing conditions, the conditions usually used in the field of dispersion dyeing can be used, and particularly, the conditions severer than the conditions conventionally used can be advantageously used. An example of a common condition is that the dispersant to dye ratio is at least 3 times the weight of the dye, preferably about 3 times and the dyebath ratio is 20 times the weight of the article to be dyed.
Conditions of about 40 times, preferably about 30 times can be used.

As an example of more severe conditions, the ratio of the dispersant used to the dye is not more than 3 times the weight of the dye, preferably 0.5 to 2 times, in particular almost the same ratio (1:
1), wherein the dyebath ratio is less than 15 times, preferably 8 to 13 times, the weight of the material to be dyed,
In particular, the condition of about 10 times can be used. The monoazo dye of the present invention exhibits excellent dispersibility even under such conditions and can perform uniform dyeing.

The dyeing temperature can be selected from a wide range. For example, in addition to the above-mentioned conditions, the dyeing temperature can be selected from the range of 100 to 150 ° C, especially 120 to 140 ° C. The dyeing time is not particularly limited and must be sufficient to achieve a satisfactory dyeing, but depending on the dyeing temperature used, it is usually 20 minutes to 90 minutes, especially 30 minutes to
A dyeing time of 60 minutes is used.

It is particularly advantageous that the dispersion stability of the monoazo dyes according to the invention can be retained even at dyeing temperatures above 130 ° C. or higher used in conventional dyeing processes, and Even under such conditions, less than 1 hour, preferably 20-4
Satisfactory dyeing is achieved within a relatively short dyeing time of 0 minutes, especially about 30 minutes.

Furthermore, in the case of the monoazo dye of the present invention, even when the temperature of the dyebath is raised to the dyeing temperature at a heating rate faster than conventional, the dispersion of the dye in the dyebath remains stable,
It has become clear that problems such as uneven dyeing and reduced fastness due to insufficient stability do not occur. Therefore, when the monoazo dye of the present invention is used, a heating rate of more than 1 ° C / minute, preferably 2 to 3 ° C / minute, particularly 2 to 2.5 ° C / minute can be adopted. Similar to the conventional method, first set the temperature of the dyeing bath to about 60-8.
The heating rate is raised to 0 ° C., usually about 70 ° C., regardless of the heating rate, and then the temperature is raised to the dyeing temperature at the heating rate described above. The more stringent conditions mentioned above can be used individually or in combination.

The dispersant used may be any dispersant commonly used in the field of dyeing using a disperse dye, and is not particularly limited, but examples thereof include a condensate of naphthalenesulfonic acid and formaldehyde, a sulfuric acid of a higher alcohol. Examples thereof include esters and sulfonates of higher alkylbenzene.

The types of fibers that can be dyed using the monoazo dyes of the present invention include those commonly used in the field of disperse dyes: acetate, nylon, polyester,
Other hydrophobic fibers, blended and woven products of these, or blended and woven products of these hydrophobic fibers and natural fibers such as cotton and wool, especially polyethylene terephthalate,
Alternatively, it is a polyester fiber containing a polymer condensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or a mixed fiber or a mixed woven product of these polyester fibers with a natural fiber such as cotton or wool.

Further, depending on the situation, an acidic substance such as formic acid, acetic acid, phosphoric acid, ammonium sulfate or the like may be added to the dye bath, whereby a better effect such as dyeing with higher uniformity can be obtained. Further, the novel crystal modification of the monoazo compound of the present invention represented by the above structural formula [I] includes various kinds of dyeing aids such as Glauber's salt and C.I. Reactive Blue 19 (C I. Reactive Blue 19), C-I-Reactive
It has excellent compatibility with other types of dyes such as reactive dyes such as Blue 225 (CI Reactive Blue 225), and when used with these dye auxiliaries and dyes,
Further, beneficial effects such as highly uniform dyeing and high reproducibility can be obtained. In particular,
The excellent compatibility with the reactive dye is advantageous when dyeing a blended fabric or a woven product of the above-mentioned hydrophobic fiber and natural fiber such as cotton and wool.

In a preferred embodiment of the method of the present invention, the polyester fiber is
In the presence of a dispersant, a dyeing temperature of 125 to 140 ° C., a dye bath ratio of 15 times or less by weight,
It is dyed until it is used up with the monoazo dye of the present invention, provided that the weight ratio of the dispersant to the dye is 3 times or less.

The particular crystal modification of the water-insoluble monoazo dye according to the invention exhibits very good properties with regard to dispersion when compared to conventional crystal modifications. By this property, for example,
Under the more severe dyeing conditions of a dye to dye ratio of 1:10 and a dye cake to dispersant ratio of 1: 1, the heating rate of the dyebath is 2 ° C / min and 135 ° C for 0.5 hours. Even under these dyeing conditions, the dispersion stability in the dyeing bath is maintained, and the dyed product obtained under such dyeing conditions is excellent in light fastness and abrasion fastness. As a result, such excellent dispersibility allows dyes of the present invention to be dyed with greater uniformity and with superior fastness. In particular, when dyeing is performed under more severe conditions as described above, this dye is extremely useful from the viewpoint of energy and resource conservation. Further, compared with the water-insoluble monoazo dye represented by the following structural formula [II], it has almost no metal ion sensitivity and good build-up property, and thus is very valuable as a disperse dye.

[0023]   Structural formula [II]

[Chemical 2]

[0024]

【Example】

Next, the present invention will be described in more detail with reference to examples. [Example 1] (Example of production of dye crystals) 13.0 g of 3- (N, N-diallyl) amino-4-methoxyacetanilide was dispersed in 217 ml of water at 0 to 2 ° C and used as a coupling component. did. next,
43% nitrosyl sulfuric acid 15.2 g was added to 98% sulfuric acid 14.6 g, 6-chloro-2,4-dinitro-aniline 10.9 g was slowly added with stirring,
Diazotization was performed to generate a diazonium compound solution. This solution was added dropwise to the above-mentioned coupling component solution at 0 ± 2 ° C. and stirred at the same temperature for 1 hour. The precipitated crystals are filtered off, washed with water, dried and the above structural formula [
22.7 g of dark green crystals represented by the formula [I] was obtained. When the monoazo dye obtained by this reaction was analyzed by X-ray diffraction in the form of powder, it was found to be about 8.9 ° and about 24 °.
． It was a β-type crystal modification having the X-ray diffraction pattern shown in FIG. 2 having a characteristic peak at a diffraction angle (2θ) of 7 °.

Next, the obtained β-type crystal was dispersed in 10 times the volume of water and stirred at 80 ± 2 ° C. for 2 hours to cause crystal conversion. Crystal conversion was followed by vacuum filtration using a Buchner funnel and filter flask followed by vacuum drying. When the obtained crystal was analyzed by an X-ray diffraction method, it was an α-type crystal having the X-ray diffraction pattern shown in FIG.

[Example 2] (Example of dyeing) 0.2 g of the α-type crystal modification of the monoazo compound obtained in the above Example 1 was converted into 0.2 g of a condensate of naphthalenesulfonic acid and formaldehyde and sulfuric acid of a higher alcohol. The ester was dispersed in 1 liter of water containing 0.2 g. Dip 100 g of polyester fiber into this dyebath and keep the temperature of the dyebath from 70 ° C to 135
The temperature was increased to 2 ° C / min at a rate of 2 ° C / min. After dyeing at this temperature for 30 minutes, soaping, washing with water, and drying were carried out. As a result, the dispersibility of the dye was excellent and the dyed product was level dyed. The fastness to light of blue-violet light of the obtained dyed product is 5-6.
The friction fastness was 4-5.

A similar dyeing test was carried out using the β-type crystal modification obtained in the middle of the above production example. As a result, the dye in the dyeing bath partially aggregated, and a non-uniform dyeing product was obtained. Was obtained.
Furthermore, the friction fastness was 1 which was extremely inferior.

[Example 3] (Example of dyeing) The amount of the condensate of naphthalenesulfonic acid and formaldehyde and the sulfate of a higher alcohol was tripled, that is, 0.6 g each, and the amount of water was tripled.
That is, the dyeing was carried out in the same manner as in Example 2 except that the dyeing condition was set to 3 liters and the dyeing method was set to be milder at 130 ° C. for 60 minutes. When the modification was used, excellent dyeing was possible as in Example 2, and the dyed article had excellent light fastness of 5-6 and abrasion fastness of 4-5. On the other hand, when the β-type crystal form was used, there was only a slight improvement as compared with Example 2, a non-uniform dyeing product was obtained, and the friction fastness was 3
Met.

[0029]

[Brief description of drawings]

[Figure 1]   The diffraction pattern of the α-type crystal modification which is the novel crystal form of the present invention.

[Fig. 2]   Diffraction pattern showing conventional β-type crystal transformation.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, TZ, UG, ZW ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI , GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, K Z, LC, LK, LR, LS, LT, LU, LV, MA , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, S K, SL, TJ, TM, TR, TT, TZ, UA, UG , US, UZ, VN, YU, ZA, ZW (72) Inventor Toshio Hinohara             2-11-40 Hachiman Nishiwakaba, Kitakyushu City, Fukuoka Prefecture F-term (reference) 4H057 AA02 BA08 BA24 DA01 DA17                       GA04 GA07

Claims (2)

[Claims] 1. A compound represented by the following structural formula [I]: 7. It shows one strong peak at a diffraction angle (2θ) of 11.1 ± 0.1 °, and
X-ray diffraction pattern showing four moderate peaks at diffraction angles of 1 ± 0.1 °, 21.8 ± 0.1 °, 23.1 ± 0.1 °, and 25.2 ± 0.1 ° Water-insoluble monoazo dye having a crystal modification characterized by (CuK _α ). 2. A method of using the monoazo dye of claim 1 for dyeing polyester fibers under the conditions that the dyeing bath ratio is 15 times or less by weight and the dispersant to dye ratio is 3 times or less by weight.