JP3355814B2 - Method for dyeing or printing hydrophobic fiber material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing or printing a hydrophobic fiber material using a specific benzodifuranone compound. More specifically, 3-phenyl-7- [4- (tetrahydrofurfuryloxy) phenyl] -1,5-dioxa-s-indacene-2,6-
Dione [hereinafter referred to as benzodifuranone compound (I)]
And a method of dyeing or printing a hydrophobic fiber material to a deep color using the method.

[0002]

BACKGROUND OF THE INVENTION Benzodifuranone compounds (I) are described in JP-A-3-72571 and JP-A-4-64967, and are known to dye hydrophobic fiber materials, for example polyester fiber materials, in red. Have been.

[0003]

In recent years, with the trend toward higher-grade clothing for consumers, the fastness of dyed goods has been improved.
In addition, there is a great need for a disperse dye having excellent dyeability, particularly capable of dyeing a clear and deep color. An object of the present invention is to provide a method for dyeing or printing a hydrophobic fiber material using the benzodifuranone compound (I) to give a clear and sufficiently dark dyed product.

[0004]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that the benzodifuranone compound (I) is a polymorphic crystal, one of which can be dyed to a dark color. However, it was found that when another crystal modification was used, a sufficient dark color could not be obtained, and the present invention was completed.

[0005] That is, the present invention provides a method for producing X-rays using Cu-Kα radiation.
By a line diffraction, a crystal modification (hereinafter referred to as α-crystal modification) of the benzodifuranone compound (I) having a crystal structure showing a strongest peak at 2θ = 4.7 ° among peaks having a diffraction angle 2θ in the range of 3 ° or more. (Hereinafter referred to as the method of the present invention), which is applied to a hydrophobic fiber material.

The benzodifuranone compound (I) can be produced, for example, as follows. That is,
5-hydroxy-2-oxo-3-phenyl-2,3-
Dihydrobenzofuran and the general formula (II) or (III)

[0007]

Embedded image

[Where X is COOR¹, CONR^TwoR^Three
Or cyano, wherein R ¹, R^TwoAnd R^Three
Are each independently a hydrogen atom or C_1-4An alkyl group
Express. ]

[0009]

Embedded image

[In the formula, L represents COR ⁴ , COOR ⁵ or SO ₂ R ⁶ , wherein R ⁴ , R ⁵ and R ⁶ each independently represent a C _1-4 alkyl group or a phenyl group. ]

The benzodifuranone compound (I) can be obtained by reacting with a mandelic acid derivative represented by the formula (1), then performing an oxidation reaction, and after the reaction is completed, mixing the reaction mixture with a hydrophilic organic solvent.

5-Hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran can be produced, for example, according to the method described in the above-mentioned JP-A-3-72571. Further, the mandelic acid derivative represented by the general formula (II) can be produced according to the method described in JP-A-3-72571, and the mandelic acid derivative represented by the general formula (III) is The aforementioned JP-A-4-164907
Can be produced according to the method described in Japanese Patent Application Publication No.

In the general formula (II), X is COOR
¹ or CONR ² R ³ , wherein R ¹ is a C _1-4 alkyl group and R ² and / or R ³ is a C _1-4 alkyl group, and in the general formula (III), L is COR
⁴ , COOR ⁵ or SO ₂ R ^{6 wherein} R ⁴ is C
_{When 1-4} alkyl groups, R ⁵ and / or R ⁶ are C _1-4 alkyl groups, these C _1-4 alkyl groups may be selected from halogen, alkoxy, phenyl, alkoxyphenyl, phenoxy, hydroxy, cyano and the like. May be substituted with a group. When R ⁴ is a phenyl group and R ⁵ and / or R ⁶ is a phenyl group, the phenyl group is
_It may be substituted with a group such as _1-4 alkyl, C _1-4 alkoxy, halogen, nitro and the like.

In the general formula (II), examples of the group represented by X include, in addition to carboxy, an alkoxycarbonyl group such as methoxycarbonyl, a carbonylamide group such as carbamoyl, and cyano.

In the general formula (III), the group represented by L includes an alkylcarbonyl group such as acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloyl; benzoyl, o
Benzoyl groups such as-, m- or p-methylbenzoyl, o-, m- or p-methoxybenzoyl, o-, m- or p-nitrobenzoyl; methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl Alkoxycarbonyl groups such as, n-, iso- or t-butoxycarbonyl; phenoxycarbonyl groups such as phenoxycarbonyl, p-methylphenoxycarbonyl, m-nitrophenoxycarbonyl;
Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso- or t-butylsulfonyl; and phenylsulfonyl, p-methylphenylsulfonyl, 4-
A phenylsulfonyl group such as methyl-2-nitrophenylsulfonyl is exemplified.

The reaction between 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran and the mandelic acid derivative represented by the general formula (II) or (III) is carried out in substantially stoichiometric amounts, respectively. Used, in the absence or preferably in the presence of a solvent, preferably at 30-180 ° C.
More preferably, it can be carried out in a temperature range of 50 to 120 ° C.

Solvents that can be used in this reaction include, for example, hydrocarbons such as benzene, toluene, xylene, mesitylene and low-boiling petroleum fractions;
Or tri-chlorobenzene, bromobenzene, chloronaphthalene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, tetrachloroethylene, dichloromethane, chloroform, carbon tetrachloride, bromoform Halogenated hydrocarbons such as; nitrohydrocarbons such as nitrobenzene, nitrotoluene and nitromethane;
Ketones such as methyl isobutyl ketone; cyclic sulfonyl compounds such as sulfolane; lower alkanoic acids such as formic acid, acetic acid, propionic acid and acetic anhydride and anhydrides thereof. Among these, aromatic hydrocarbons and halogenated hydrocarbons, especially toluene, monochlorobenzene, dichlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,1
Preferred are 2,2-tetrachloroethane, trichloroethylene, dichloromethane, chloroform and the like.

This reaction can be advantageously performed in the presence of an acidic catalyst. Acid catalysts that can be used include:
Unsubstituted or substituted benzenesulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, benzene-m-disulfonic acid; alkanesulfonic acids such as methanesulfonic acid; halogenated lower alkanoic acids such as trifluoroacetic acid; Titanium chloride, aluminum chloride, stannous or stannic chloride, ferrous or ferric chloride, zinc chloride,
Examples thereof include Lewis acids such as boron trifluoride; mineral acids such as sulfuric acid and hydrochloric acid. The amount of the catalyst used is arbitrary, but is preferably at least 0.01 mole times, more preferably 0.1 to 1 mole times, more preferably 0. 1 mole times, relative to the mandelic acid derivative of the general formula (II). 0.1 to 0.5 times by mole, and preferably at least 0.5 times by mole, more preferably 0.8 to 1 times by mole with respect to the mandelic acid derivative of the general formula (III).
The range is 2 mole times, more preferably 0.9 to 1.5 mole times.

Thus, after reacting 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran with the mandelic acid derivative represented by the general formula (II) or (III), Perform an oxidation reaction. This oxidation reaction is preferably performed in the presence of a solvent at a temperature in the range of 0 to 70 ° C. The solvent used here can usually be the solvent used for the reaction between the benzofuran compound and the mandelic acid derivative.

This oxidation reaction can be advantageously performed in the presence of an oxidizing agent. Oxidizing agents that can be used include:
Chloranil, bromanil, thiosulfate, nitrite, hypochlorite, chlorite, chlorate, perchlorate, persulfate, periodate, perborate, permanganate, Examples include vanadate, dichromate, nitric acid, iodine, tetrachlorohydroquinone, lead dioxide, manganese dioxide, vanadium pentoxide, nitrobenzene, dicyanodichlorobenzoquinone, hydrogen peroxide, atmospheric oxygen, and the like. These can be used alone or in combination of two or more.

After completion of the reaction, the reaction mixture containing the benzodifuranone compound (I) is mixed with a hydrophilic organic solvent,
The benzodifuranone compound (I) is precipitated. The hydrophilic organic solvent used here may be any organic solvent having a hydrophilic group, for example, alkanols, lower alkyl ketones such as acetone, tetrahydrofuran,
Examples thereof include ethers such as dioxane and 1,2-dimethoxyethane, lower nitriles such as acetonitrile, and lower carboxylic acids. Among them, alkanols, particularly C _1-4 alkanols are preferable, and methanol is particularly preferable.

The benzodifuranone compound (I) is obtained by the above-mentioned reaction and post-treatment, but the crystal form of the benzodifuranone compound obtained varies depending on the reaction conditions and post-treatment conditions. These crystal modifications can be easily distinguished by X-ray diffraction measurement using Cu-Kα radiation. Therefore, in the present invention, among the benzodifuranone compounds (I), as a crystal modification capable of dyeing a hydrophobic fiber material in a dark color, when subjected to X-ray diffraction using the previously defined α-crystal modification, ie, Cu-Kα ray, When the diffraction angle 2θ is 3 ° or more, 2θ =
Choose the crystal modification that shows the strongest peak at 4.7 °.

The α-crystal modification employed in the present invention is Cu-K
According to X-ray diffraction measurement using α-rays, when the diffraction angle 2θ is in the range of 3 ° or more, a sharp peak characteristic at 2θ = 4.7 °, that is, the strongest peak is given. Although the overall X-ray diffraction pattern, particularly the intensity of the peak slightly varies depending on the production conditions, the X-ray transformation using the Cu-Kα ray
FIG. 1 shows a typical diffraction pattern obtained by line diffraction. Medium intensity peaks at 2θ = 17.3 ° and 19.2 °, and 2θ = 7.1 ° and 9.4 °
Is also characteristic of the α-crystal transformation.

X using the Cu-Kα ray of the α-crystal modification
Peaks that commonly appear in the line diffraction pattern can be generally summarized as follows.

Strong peak: 4.7 ° Medium intensity peak: 17.3 °, 19.2 °, 26.0 °, 27.0
°, 27.4 ° Small intensity peaks: 7.1 °, 9.4 °, 14.4 °, 23.0
°

In the α-crystal modification of the benzodifuranone compound (I) used in the present invention, in synthesizing the benzodifuranone compound (I) by the above-mentioned method, particularly, an oxidation reaction and a subsequent mixing with a hydrophilic organic solvent are carried out. It can be obtained by carrying out under appropriate conditions. For example, it can be obtained by performing the oxidation reaction under relatively mild conditions, and performing the mixing with the hydrophilic organic solvent under relatively mild conditions. If the conditions of the oxidation reaction and / or the conditions at the time of mixing with the hydrophilic organic solvent are severe, the crystal form may become another crystal form or a mixed crystal with another crystal form. No α-crystal transformation can be obtained.

The dyeing or printing method using the α-crystal modification of the present invention is useful for hydrophobic fiber materials, especially polyester fiber materials. Useful for dyeing to color. Also, as the fiber diameter generally becomes smaller, for example,
It becomes difficult to dye ultra-fine fibers such as microfibers in a dark color, but when the α-crystal modification of the present invention is used, it is possible to relatively easily obtain a dark dyed product.

For example, the α-crystal modification of the present invention is pulverized into fine particles in an aqueous medium together with a suitable dispersant such as a condensate of naphthalenesulfonic acid and formaldehyde or ligninsulfonic acid by a conventional method. Thus, a dye dispersion is obtained. This dye dispersion can be used in a liquid state as it is or in a powder form by spray drying or the like. Dyeing, especially dip dyeing, is carried out in an aqueous medium using
-If necessary, a pH adjusting agent, a dispersion leveling agent and the like are added to the dyeing bath in which the crystal modification is dispersed, and then the hydrophobic fiber material is immersed. C. or higher, preferably 110 to 140C. Dyeing can also be performed at a relatively high temperature, for example, in the boiling state of water, in the presence of a carrier such as o-phenylphenol or methylnaphthalene. Furthermore, after padding the dye dispersion onto a cloth,
A dyeing method in which steaming or dry heat treatment is performed at a temperature of 100 ° C. or more is also applicable.

On the other hand, printing can be carried out by kneading a dye dispersion with an appropriate paste, printing and drying this on a cloth, and then performing steaming or dry heat treatment.

According to the present invention, when the α-crystal modification of the benzodifuranone compound (I) is applied to dyeing or printing, it may of course be mixed and dyed with other dyes. Various compounding agents may be added.

The red dyeing of a hydrophobic fiber material, for example, a polyester fiber material obtained by the method of the present invention has a dark and vivid hue, and has a light fastness, a sublimation fastness,
Excellent in various fastnesses such as wet fastness. Therefore, the present invention exhibits various excellent effects as a method for dyeing or printing a hydrophobic fiber material in red. In particular, by selecting a specific crystal modification among the benzodifuranone compounds (I), that is, the α-crystal modification, the hydrophobic fiber material can be constantly dyed or printed to a deep color stably.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Parts and% in the examples represent parts by weight and% by weight, respectively, unless otherwise specified.

Reference Example 1 4-tetrahydrofurfuryloxymandelic acid 5.30
Part and 5-hydroxy-2-oxo-3-phenyl-2,
A mixture of 4.52 parts of 3-dihydrobenzofuran was kept at 80 ° C. for 6 hours in a mixed solvent of 76 parts of acetic acid and 4 parts of sulfuric acid, and then 4.68 parts of ammonium persulfate was added.
Incubated at 2 ° C. for 2 hours. After cooling to 35 ° C., 100 parts of methanol was added at the same temperature, the generated crystals were separated by filtration, washed with water and dried to obtain crystals of the benzodifuranone compound (I). When the obtained crystal was subjected to X-ray diffraction by Cu-Kα ray, the X-ray diffraction diagram of FIG. 1 was shown.
It was confirmed that it was a crystal modification.

Reference Example 2 3.37 parts of 1-benzoyloxy-1- (p-tetrahydrofurfuryloxyphenyl) -acetonitrile
2.26 parts of -hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran and 2.28 parts of p-toluenesulfonic acid (monohydrate) were added to 33 parts of monochlorobenzene, and the mixture was added at 80 ° C with 3 parts. After incubation for 2 hours, chloranil 2.4
6 parts were added and the mixture was kept at 30 ° C. for 5 hours. After the temperature was raised to 55 ° C., 50 parts of methanol was added at the same temperature, the generated crystals were separated by filtration, washed with water and dried to obtain crystals of the benzodifuranone compound (I). The obtained crystal was subjected to an X-ray diffraction method using Cu-Kα radiation, and as a result, an X-ray diffraction diagram similar to that in FIG. 1 was shown, and it was confirmed that the crystal was a modified α-crystal.

Example 1 1.0 part of the α-crystal modification obtained in Reference Example 1 was atomized and dispersed in an aqueous medium together with 3.0 parts of a condensate of naphthalenesulfonic acid and formaldehyde. 10 parts of a tetron jersey (polyester cloth, manufactured by Teijin Limited) is immersed in 200 parts of a dye bath containing 0.6 part of a powder obtained by drying the dye dispersion, and the mixture is heated at 130 to 135 ° C. under pressure. Staining was performed for 60 minutes. Next, 3 parts of caustic soda, 3 parts of hydrosulfite, betaine-type amphoteric surfactant 3
And immersed in a treating solution consisting of 3000 parts of water and 3000 parts of water, subjected to a reduction washing treatment at 85 ° C. for 10 minutes, and then washed with water and dried to obtain a high-density clear red dyed matter. This dyed product was also excellent in various fastnesses such as light fastness, sublimation and wet fastness.

Example 2 3.7 parts of ligninsulfonic acid was added to 1.3 parts of the α-crystal modification obtained in Reference Example 1 and atomized and dispersed, and 35 parts of hot water and a half emulsion paste having the following composition were added. The printing paste was prepared by mixing 60 parts.

O / W emulsion 300 parts Maypro gum NP 12% paste 694 parts [Ether type locust bean gum type original paste, manufactured by May Hall, Switzerland] Sodium chlorate 4 parts Tartaric acid 2 parts １０００ 1000 copies

Using this printing paste, tetron tropical (polyester cloth, manufactured by Teijin Limited) was printed, dried, and then steamed and fixed at 170 ° C. for 7 minutes using a high-temperature steamer at normal pressure. Further, according to the method described in Example 1, reduction cleaning treatment, water washing, and drying were performed, and then a flexible and antistatic treatment was performed by a known method. The dyed product thus obtained was bright red with high density and excellent in various fastnesses such as light fastness, sublimation and wet fastness.

Example 3 In place of the tetron jersey used in Example 1, 0.0
Fabric using 3-denier polyester yarn (Toray) 1
When exhaustion dyeing was carried out using 0 parts, a sufficiently dark and clear red dyed product was obtained. The light fastness and wet fastness of this dyed product were equivalent to those of a dyed product having a normal fiber diameter.

[0040]

According to the dyeing or printing method of the present invention, a dyed product of a hydrophobic fiber material having a dark and clear hue can be obtained.

[Brief description of the drawings]

FIG. 1 is a benzodifuranone compound (I) used in the present invention.
2 is an X-ray diffraction pattern of the α-crystal transformation of Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-39434 (JP, A) JP-A-6-200178 (JP, A) JP-A-6-143840 (JP, A) JP-A-4- 143840 (JP, A) JP-A-3-72571 (JP, A) JP-A-6-306302 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 67/48 CA ( STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. X-ray diffraction by Cu-Kα ray, among peaks having a diffraction angle 2θ of 3 ° or more, 2θ =
3-phenyl-7- [4- (tetrahydrofurfuryloxy) phenyl] -1,5-dioxa-s-indacene-2,6 having a crystal structure showing the strongest peak at 4.7 °
A method for dyeing or printing a hydrophobic fiber material, characterized by applying a crystalline modification of dione to the hydrophobic fiber material. 2. Medium intensity peaks appearing in a range where the diffraction angle 2θ is 3 ° or more are 2θ = 17.3 ° and 19.2 °, and small intensity peaks are 2θ = 7.1 ° and 9 °. .
The method of claim 1, wherein the angle is 4 degrees. 3. The method according to claim 1, wherein the dyeing method is dip dyeing.