US3508855A - Process for pad-dyeing and printing - Google Patents

Description

United States Patent US. Cl. 8-32 7 Claims ABSTRACT OF THE DISCLOSURE A process for pad-dyeing or printing textile fabrics of synthetic or semi-synthetic fibers by applying thereto a quinone-dihaloimine having the formula,

wherein X is a halogen atom and nucleus A may have a halogen atom or a lower alkyl or alkoxy group as a substituent, under the pH more than 8 inclusive in the pres ence of an inorganic alkaline agent, at a pH exceeding 8. Preferred compounds are 1,4-quinone-dichloride or 1,4- quinonedibromide. The medium may include substituted aroamtic amines or hydrocarbons such as phenols, cresols and naphthols.

The present invention relates to a novel process for pad-dying or printing textile fabrics in black shade. The present process is useful for single or blended textile fabrics of synthetic and/or semi-synthetic fibers. More particularly, it is useful for textile fabrics comprising polypropylene fibers. The printing bath or printing paste contains as ingredients a compound of the following forwherein X is a halogen atom and nucleus A may have a halogen atom, a lower alkyl or lower alkoxy group as a substituent, together with inorganic alkaline substances, the pH being kept at 8 or more.

The present inventors have found that a deep black colored print with desired fastness can be readily obtained by pad-dyeing or printing the textile fabrics with the above mentioned compound and an inorganic alkali. The step may be effected at any stage of the process.

A black colored print on hydrophobic substances is well known. To obtain this effect, the dyeing is performed using aniline orthotoluidine, 4-amino-diphenylamine and the like. Japanese patent publication Nos. 10,382/63 and 19,639/63 disclose a two bath dyeing process wherein dyeing is carried out with the use of the compound of the above-mentioned general formula after hydrophobic fibers are treated with aromatic compounds having two amino groups or azomethine compounds obtained by condensation of aromatic amine and aromatic aldehyde. Another method for obtaining a black colored print on polypropylene fibers is described in Example 1 of Japanese patent publication No. 24,658/64. The method is that the compound of the general formula,

wherein X and A have the same meanings as mentioned above, is used together with an aromatic amine. In this case, however, the printing paste has poor stability since the two components react readily with on another to produce a black color, with consequent problems such as ice poor dye-fixing, particularly where there is the usual intermediate drying step. In the usual printing method, the printed woven fabrics are usually subjected to drying and then to steaming in order to fix the dye. However, no matter how rapidly the printing is performed, the blacking reaction proceeds during the drying process of the dyed Woven fabric with so-called lake formation. In such lake formation, the dye forms large molecules which do not fix onto polypropylene fibers even in the subsequent steaming process. Even if it fixed onto said fibers, the reproductibility is not good. The same defect is seen when benzene, naphthalene or quinoline derivative having one or more hydroxyl radical besides the above-mentioned aromatic amine are used. Stability of printing paste or storage of dried cloth are requested in pattern print.

The present inventors have succeeded in providing a pad-dyeing or printing method of notable characteristics which comprises conducting the dyeing or printing with the use of a dyeing bath or a printing paste comprising inorganic alkali and the compound of the general formula,

wherein X and A have the same meanings as mentioned above, keeping pH at 8 or more. The bath or paste may further have aromatic amines and/ or compounds selected from benzene, naphthalene and quinoline derivatives. As to the benzene and naphthalene and quinoline derivatives. As to the benezene and naphthalene, at least one of hydrogen atoms capable of being substituted should be replaced by hydroxyl group and the other remaining hydrogen atoms may be substituted by the other groups than sulphonic group. The present paste or bath is completely stable, and furthermore even if a dried cloth printed with this paste is allowed to stand for a long period of time, polycondensation does not proceed instantaneously and black coloring reaction does not take place. Polyolefin fibers are dyed in black only when they are subsequently steamed or dry-heated.

Color shade obtained by the method of this invention is illustrated by the revised Munsell remotation as follows:

Hue

According to this invention, such neutral black color as mentioned above can always be obtained with good reproducibility.

Quinonedihalimine derivative represented by the general formula, which can be used in the present invention, includes, for example, 1,4-quinone-dichlorimine, 1,4- quinone-dibromimine or their 2-chloro, 2-bromo, 2-methyl, Z-ethyl, Z-methoxy, Z-ethoxy, 2,6-dichloro, 2,5-di. chloro,2,5-dimethyl, 2,5-dimethoxy or 2,5-diethoxy substituted compound alone or a mixture thereof. Inorganic alkaline agent includes hydroxides of alkali metal or alkaline earth metal, their basic salts or a mixture thereof. For example, there are sodium carbonate, potassium car.- bonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium tertiary phosphate, sodium silicate, quicklime and the like. The amount of these alkaline agents to be used varies according to the kind of alkaline, however, in the case of potassium carbonate, for example, about 120% by Weight, preferably about 5% by weight is added to a padding bath or a printing paste.

The aromatic amines include aniline, 0- or m-toluidine, or m-xylidine, 2,3-dimethylaniline, 0- or m-chloroaniline, por m-aminophenol, 4-aminodiphenylamine or the like.

Benzene and naphthalene should have at least one bydroxyl group but may further have the other group than sulfonic acid group. Such benzene and napthalene or quinoline derivatives include phenol, mor p-cresol, 0- or p-butylphenol, oor p-octylphenol, oor p-cyclohexylphenol, 2,4-xylenol, 3,5-xylenol, 2-butyl-4-cresol, 4-amino- Z-cresol, 6-butyl-3-cresol, op-phenylphenol,'o-, mor pchlorophenol, o-, mor n-nitrolphenol, 0- or p-hydroxy benzoic acid or methyl, ethyl or butyl ester thereof, N- dimethyl or diethyl-m-aminophenol, 0-, mor p-acetylaminophenol, m-hydroxydiphenylamine, 3 -hydroxy-2- methyldiphenylamine, catechol, resorcinol or hydroquinone or mono-methyl or mono-ethyl ether, pyrogallol, a-naphthol, B-napthol, 4-methyl-u-napthol, 4-methoxy-anaphthol, 4,8 dimethoxy-a-naphthol, 5,8 dlChlOl'O-Otnaphthol, 1,5 or 2,3-dihydroxynaphthalene, 04- or ,G-hydroxymaphthenic acid, or methyl or ethyl ester thereof, 5- hydroxynaphthenic acid anilide or alkyl-, alkoxyand/or halogen-substituted compound thereof, 8-hydroxyquinoline, 2,4-dihydroxyquinoline, N-methylor N-butyl- 2,4-dihydroxyquinoline or the like. These can be used in the form of sodium or potassium phenolate, etc., too. They are used either alone or in the form of a mixture.

The present process will be illustrated hereinunder referring to printing. To 10 g. of p-dichloroquinonediimine powder (effective ingredient: 84%), a small amount of water is added and said power is sufiiciently kneaded. Afterwards, a suitable amount of a viscosity promoting agent such as British gum is added thereto and 5 g. of potassium carbonate powder as the inorganic alkaline agent is further added to prepare 100 g. of a uniform and viscous paste. The paste thus obtained is printed onto polypropylene woven fabric and dried at about 50 C. Then, it is subjected to steaming for about minutes, washing with water and soaping and finished to obtain a print of deep black color. Furthermore, a printing paste prepared by adding a suitable amount of the aromatic amines or phenol derivatives to the above-mentioned printing paste is printed onto polypropylene woven fabric and dried at about 50 C. Then, it is subjected to steaming and sub jected to water washing and soaping according to the usual method to obtain a print cloth of black color.

The amount of p-dichloroquinonediimine to be used in accordance with the method of the present invention can be optionally decided, preferably about 10%, by weight based on the weight of the paste, judging from the condition of paste-status of the printing paste or color value.

The amount of the inorganic alkaline to be added varies according to the kind thereof. For example, in case of potassium carbonate, its effective amount is 110% by weight based on the weight of the paste, preferably 5%. Furthermore, when alkaline is of little amount, for example, less than 2% by weight, the printing paste becomes to give no dye-fixing onto woven fabric.

Stability of printing paste greatly varies, particularly according to the kind of the alkaline to be added. From the point of the storage stability, sodium carbonate, sodium phosphite, sodium cyanide, sodium silicate, potassium carbonate, sodium bicarbonate are preferred, and they do not damage the paste for as long as one week.

When the aromatic amines or phenols are used, the most preferred ratio of p-dichloroquinonediimine to aniline, for example, is about 1:1 by weight ration. The ratio naturally varies depending on the kinds of the amines, phenols and the other component, quinonedihaloimide. Although color shade varies according to the kind of the above-mentioned aromatic amines or phenols or the material to be dyed, for example, on polyolefin fibers, aromatic amines usually give reddish color shade, and phenols bluish color shade.

The printed cloth with, for example, p-dichloroquinonediimine tends to stain white ground due to sublimation of the dye fixed on said cloth in steaming. Reduction cleaning with hydrosulfite and sodium hydroxide is effective to remove the stains and a printed cloth having favorable white ground can be obtained Moreover, by the pretreatment of the fabric with organic acid such as tartaric acid, formic acid, citric acid, etc. and inorganic acid such as sulfuric acid, phosphoric acid, etc., drying and after-treatment such as steaming, etc., the effect to improve the white ground of printed cloth can be sufliciently displayed even when the amount of acids used is as little as 5-20 g./1. or so.

Since the present method is carried out at alkaline side, the viscosity promoters used in the present invention are natural or synthetic starch agent such as alkaline resisting tragacanth gum, British gum, crystal gum, Meypro gum (locust bean gum), starch, etc. These can basically be applied singly or in admixture, as well as alkali resisting water-in-oil type and oil-in-water type emulsions containing the above-mention starch agents.

On the other hand, the amount of inorganic alkaline to be added and the structure of fabric influence the steaming as dye-fixing, but generally a period of from 5 to 30 minutes is sufficient. If required, the steaming at a practically high temperature below the softening point of fiber enables sufficient dye diffusion into the interior of fibers, and deeper black color can be obtained. Furthermore, the dry heat treatment and curing or baking at a temperature of l00l40 C., which is below the softening point of fiber, for ll0 minutes are carried out and then washed with water and soaped to obtain 'black color on the objective goods.

Still more, by dry heat fixing, a carrier or swelling agent or hygrometric agent usually used for the dyeing of synthetic fibers, may be added to the prescription of the printing paste, by which a deep and fast black color can be obtained. As compounds therefor, there are benzonitrile, trichlorobenzene, urea, thiourea, sodium chloride, glycerine, triethanolamine, diethyleneglycol, etc., which can be used singly or in a mixture comprising several of the above.

Next, the pad-dyeing by the present invention can be also carried out in a similar manner to that of printing to dye the objects black.

That is, p-dichloroquinonediimine powder (effective ingredient: 84%) and a dispersing agent, for example, a small amount of formalin condensation product of an anionic alkylnaphthalenesulfonic acid are sufficiently kneaded, and dispersed in the padding bath aqueous solution and a suitable amount of potassium carbonate, for example, as inorganic alkaline is added thereo. The polypropylene fabric is immersed therein, and then subjected to steaming or dry heat treatment at a temperature below the softening point of the fibers to obtain good black color. When polypropylene fabric is immersed in a uniform padding solution in a padding bath containing aromatic amines such as aniline, etc. or the above-mentioned phenols, and after removing the solution therefrom, subjected to the same treatments as mentioned above a deep black color is obtained on the fabric.

Although the amount of p-dichloroquinonediimine powder (effective ingredient: 84%) to be used in the paddyeing of the present invention varies according to the mangle pick up rate, the preferred amount is 15-20% by weight based on the weight of the dyeing bath in case of the mangle pick up rate of Furthermore, the dispersing agent is not always necessary, but is effectively used in the dispersion of p-dichloroquinonediimine and the stabilization of dyeing bath and carrying out a uniform dyeing. For this object, for example, a formalin condensation product of alkylnaphthalenesulfonic acid can be used.

The amount of inorganic alkaline to be used varies according to the amount of p-dichloroquinonediimine used. For example, potassium carbonate in an amount of 2-20% by weight, preferably about 5% by weight or so based on the weight of a dyeing bath, is effective for that object.

Furthermore, the ratio of the above-mentioned aromatic amines and phenol derivatives to quinonedihalirnide is not definitely fixed since it depends on the two components or the desired color shade and depth of the dyed objects. For example, in the combination of p-dichloroquinonediimine and aniline, the most favorable black color can be attained, when the ratio of the two components is close to 1:1 by weight ratio.

Moreover, the present method can be applied to the yarn by an adsorption printing method to provide a black color to polypropylene yarn. However, it is not commercially advantageous, because 2025% by weight of p-dichloroquinonediimine is required to the yarn weight which is quite large.

In the present invention, the dyeing mechanism and the structure of the dye fixed on the dyed cloth are quite complicated and obscure, because in the present method the reactants proceed through an oxidation or condensation of dye. For example, it is assumed that the dehydrochloric acid condensation of p-dichloroquinonediimine takes place by the action of inorganic alkaline to form linear or reticulated polybenzoquinone derivative on the fibers.

Still more, regarding the mechanism of dye fixing, it is considered that the low polycondensation product of p-dichloroquinonediimine itself or the low polycondensation product of p-dihaloquinonediimine and decomposition product thereof, or the low polycondensation product of pdihaloquinonediimine and phenol reacts with itself to form a higher polycondensation product on the fibers and thus give fast dye fixing to the fabric.

The dyeing of present method can be applied to fibers including the synthetic fibers such as polyolefin, polyester, polyamide, polyacrylonitrile, polyvinyl chloride, etc. as mentioned above and the semi-synthetic fibers such as acetate and triacetate etc. Particularly, according to the present method, a good black color can be given to polyolefin fibers.

The following examples are given merely to illustrate the method of the present invention, but they should not be construed as limitative.

EXAMPLE 1 To prepare a paste, 20cc. of water was added to 10 g. of p-dichloroquinonediimine. Then, 65 g. of tragacanth gum (a 6.5% paste) was added to the paste to be homogeneously stirred, g. of potassium carbonate further added thereto to obtain 100 g. in total of viscous paste. The printing paste thus obtained was printed onto polypropylene taifeta with screen paper stencil. After drying, it was steamed at100 C. for 20 minutes, washed with Water and soaped and a printed fabric of black color was obtained. Color fastness to sunlight and washing of the thus obtained print cloth were in the 8th grade and the 5th grade respectively. (Hereinafter, same results as in this example were obtained in each of the subsequent examples.) 7

EXAMPLE 2 To obtain a paste, 20 cc. of water was added to g. of p-dichloroquinonediimine. Then, 65 g. of British gum (a 60% paste) was added to the resulting paste to be uniformly stirred, and 5 g. of a 35% sodium hydroxide further added to the resultant mixture to obtain 100 g. of viscous paste in total. The thus obtained printing paste was printed onto polypropylene knitted goods as in Example 1. After post-treatment such as steaming, etc., a fast, black colored printed fabric was obtained.

EXAMPLE 3 To obtain a paste, 20 cc. of water was added to 10 g. of p-dichloroquinonediimine. Then, 60 g. of tragacanth gum (a 60% paste) was added to the resulting paste to be stirred with each other. 5 g. of potassium carbonate was further added to the resultant mixture to obtain a uniformly prepared paste and 5 g. of o-cresol was lastly added to the thus prepared paste to obtain 100 g. of viscous paste. The printing paste thus obtained was printed onto polypropylene knitted goods with screen paper stencil. After drying, it was subjected to steaming at 100 C. for 20 minutes, washed with Water and subjected to soaping. As a result, fast and black colored printed fabric was obtained.

EXAMPLE 4 To obtain a paste, 20 cc. of water was added to 7 g. of p-dichloroquinonediimine. Then, 61 g. of British gum (a 60% paste) and 5 g. of sodium silicate (No. 1 product according to I IS K-1408) to obtain a uniformly prepared paste and, lastly 7 g. of an aniline oil was thereto added to prepare 100 g. of paste in total. The thus obtained printing paste was printed on polypropylene knitted goods according to the same method as in Example 1. After drying, it was subjected to steaming at 100 C. for 20 minutes, washed with water and subjected to soaping. The resulting knitted goods printed was further subjected to reduction cleaning in a treatment bath containing 200 cc. of water to which 0.5 g. of hydrosulfite and 0.5 cc. of a 35% sodium hydroxide, and as a result, black colored printed fabric having high color fastness was obtained.

EXAMPLE 5 To obtain a paste, 20 cc. of water was added to 10 g. of 2-methoxy-1,4-diehloroquinonediimine. Then, 63 g. of British gum (a 60% paste) was added to the paste to be uniformly prepared, and 7 g. of slaked lime was further added thereto to obtain 100 g. of viscous and uniform paste in total. The thus obtained printing paste was printed onto blended yarn cloth of acetate/polyester (70/30). After drying, it was subjected to after-treatment such as steaming and so forth according to the same method as in Example 1, and as a result, fast and black colored printed fabric was obtained.

EXAMPLE 6 To obtain a paste, 20 cc. of water was added to 10 g. of p-dichloroquinonediimine. Then, 63 g. of British gum (a 60% paste) was added to the paste to be uniformly prepared. 5 g. of potassium carbonate and 2 g. of carbolic acid were further added to the resulting paste to obtain 100 g. in total of viscous paste. The thus obtained printing paste was printed onto blended yarn cloth of polypropylene/polyamide (/20) with screen paper stencil. After drying, it was subjected to after-treatment according to the same method as in Example 1, and as a result, bluish black colored and fast printed fabric was obtained.

EXAMPLE 7 1 g. of Formalin condensation product of naphthalenesulfonic acid and 20 cc. of Water were added to 15 g. of p-dichloroquinonediimine. After being sufficiently kneaded, 20 g. of British gum (a 60% paste) and 10 g. of potassium carbonate were thereto added to prepare cc. of uniform solution. Into the thus prepared solution, polypropylene knitted goods was immersed. After pressing out the solution from the processing knitted goods with a mangle, it was subjected to water-washing and soaping, and to the same reduction cleaning as in Example 1, and as a result, a fast and black colored printed fabric was obtained.

EXAMPLE 8 20 cc. of water was added to 10 g. of p-dichloroquinonediimine to obtain a paste. Then, 54 g. of British gum (a 60% paste) was added to the paste to be uniformly stirred with each other. 10 g. of sodium silicate ('No. 1 product according to I15 K-1408), 3 g. of triethanolamine and 3 g. of m-cresol were added to the resulting paste to prepared 100 g. in total of viscous paste. The thus prepared printing paste was printed onto blended yarn cloth of acrylic fiber-polyester. After drying, it was subjected to heat treatment at 200 C. for 1 minute, washed with water and subjected to soaping, and

as a result, a fast and black colored printed fabric was obtained.

EXAMPLE 9 0.5 g. of Formalin condensation product of naphthalenesulfonic acid and 10 cc. of water were added to 10 g. of p-dichloroquinonediimine. After kneading sufficiently, 10 g. of British gum (a 60% paste) and 70 cc. of water were added thereto. To the thus prepared solution, g. of sodium carbonate and 5 g. of m-cresol were added and water was added to make up the same 100 cc. in the total.

Polypropylene knitted goods was pad-dyed in the bath, pressed ofi? the solution dried. After steaming at 100 C. for minutes, it was washed with water, soaped and then subjected to reduction cleaning as in Example 2. A fast printed fabric of black color was obtained.

EXAMPLE 10 To obtain a paste, cc. of water was added to 10 g. of 2-chloro-l,4-dichloroquinonediimine. Then, 62 g. of Meypro NP gum (a 12% paste, a product of Meyhall, Switzerland) and 5 g. of potassium carbonate was added to the paste to be uniformly prepared. 3 g. of fine powder of o-phenylphenol was further added thereto to prepare 100 g. in total of uniform printing paste. The thus prepared printing paste was printed with pattern onto nylon cloth. After drying, it was subjected to steaming at 100 C. for 10 minutes. Then, it was washed with water and subjected to soaping and as a result, a print cloth of black color was obtained.

EXAMPLE 11 20 cc. of water was added to 10 g. of p-dichloroquinonediimine to obtain a paste, and then 60 g. of Meypro NP gum (a 12% paste) was added thereto and 5 g. of potassium carbonate was further added thereto to prepare a uniform paste. To the thus prepared paste, 5 g. of 4-aminodiphenylamine dispersed in 20% was added to obtain 100 g. in total of a uniform and viscous paste.

The thus obtained printing paste was printed onto Tetoron taffeta (trade name for polyethyleneterephthalate fibers, Teijin, Japan). After being dried, it was subjected to steaming at 130 C. for 10 minutes and subjected to the same after-treatment as in Example 2, and a fast print cloth of black color was obtained.

EXAMPLE 12 20 cc. of water was added to 10 g. of 2-chloro-1,4- diohloroquinonediimine to prepare a paste. Then, 65 g. of British gum (a 60% paste) was added to the paste to be uniformly prepared, and 5 g. of sodium bicarbonate was thereto added to prepare 100 g. in total of a viscous and uniform paste. The thus prepared printing paste was printed onto Teviron woven fabric (trade name for polyvinylchloride fibers, Teijin, Japan) with screen paper stencil. After drying, it was subjected to steaming at 100 C. for 15 minutes, washed with water and soaped, and a fast printed fabric of black color was obtained.

EXAMPLE 13 0.5 g. of Formalin condensation product of naphthalenesulfonic acid and 10 cc. of water were added to 10 g. of p-dichloroquinonediimine after being sufficiently kneaded, 10 g. of British gum (a 60% paste) and water were added thereto to make it 100 cc. and 10 g. of sodium silicate (Class I according to I15 K-l408) was further added thereto to prepare a uniform dyeing bath solution. Polypropylene knitted goods was subjected to pad-dyeing in the bath to which 10 g. of sodium silicate (No. 1 product according to I18 K-1408) was further added. After mangling the solution, it was steamed for 10 minutes, washed with water, soaped, and subjected to the same reduction cleaning as in Example 4; a fast printed article of black color was obtained.

EXAMPLE 14 20 cc. of water was added to 10 g. of p-dibromquinonediimine to prepare a paste. Then, 63 g. of British gum (a 60% paste) was added to the paste to beuniformly prepared. 5 g. of potassium carbonate and 2 g. of mcresol were thereto added to obtain g. in total of viscous paste. The thus obtained printing paste was printed onto Cashimilon F (an acrylic fiber manufactured by Asahi Kasei) with screen paper stencil. After drying, it was subjected to the same after-treatment as in Example 1, and a fast printed article of bluish black color was obtained.

What we claim is:

1. A process for pad-dyeing or printing textile fabrics of synthetic or semi-synthetic fibers, which comprises treating the fabrics with a dyebath or a printing paste consisting essentially of a compound of the following formula,

wherein X is a halogen atom and A may have a halogen atom or a lower alkyl or a lower alkoxy group as a substituent, and an inorganic alkali selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium tertiary phosphate, sodium silicate and quicklime, the pH of the bath or paste being kept at more than 8 inclusive.

2. A process according to claim 1, wherein the fiber is made of polypropylene.

3. A process according to claim 1, wherein the said compound is l,4quinonedichlorirnine, 1,4 quinonedibromimine or their 2-chloro-, 2-bromo-, 2-methyl-, 2- ethyl-, 2-methoxy-, 2-ethoxy-, 2,6-dichloro-, 2,5-dichloro-, 2,5-dimethyl-, 2,5-dimethoxyor 2,5-diethoxysubstituted compound.

4. A process according to claim 1, wherein the said inorganic alkaline substance is, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium tertiary phosphate, sodium silicate or quicklime.

5. A process according to claim 3 wherein said compound is p-dichloroquinoned'iimine and the inorganic alkaline substance is selected from the group consisting of sodium hydroxide, sodium bicarbonate, potassium carbonate, and sodium silicate.

6. A process according to claim 3 wherein said compound is p-dibromoquinone diimine and the inorganic alkaline substance is potassium carbonate.

7. A process according to claim 3 wherein said compound is 2-chloro 1,4 dichloroquinonediimine and the inorganic alkaline substance is selected from the group conslsting of sodium bicarbonate and potassium carbonate.

References Cited FOREIGN PATENTS 5/1964 Canada. 1964 Japan.

OTHER REFERENCES Beilstein, vol. VII, pp. 621, 622 (1920).

US. Cl. X.R. 8-62