US3561913A

US3561913A - Method of dyeing synthetic fibers

Info

Publication number: US3561913A
Application number: US683827A
Authority: US
Inventors: Hideaki Munakata; Kazuo Watanabe; Yoshikazu Arimatsu; Toshiharu Sugihara
Original assignee: Toyobo Co Ltd
Current assignee: Toyobo Co Ltd
Priority date: 1966-11-25
Filing date: 1967-11-17
Publication date: 1971-02-09
Anticipated expiration: 1988-02-09
Also published as: CH503152A; DE1619647A1; CH1654767A4

Abstract

SYNTHETIC FIBERS-ESPECIALLY POLYESTER FIBERS, ARE DYED BY MEANS OF A REACTION PRODUCT OF A COMPOUND OF THE FORMULA

A-R-B-R''

AND A COMPOUND OF THE FORMULA

1-(Y=),4-(X-N=)-C

WHEREIN A IS AN AROMATIC NUCLEUS, B IS AN AROMATIC NUCLEUS OR A QUINOID RING, R IS -NH- OR -N=, R'' IS -OH OR =O, C IS A QUINOID RING, X IS A HALOGEN ATOM AND Y IS =O, =N-X,=N-OCCH3 OR

PHENYL-SO2-N=

THE DYED FIBERS, OF DARK SHADE, ARE OF EXCELLENT FASTNESS TO LIGHT, SUBLIMATION, WASHING AND DRY-CLEANING.

Description

United States Patent 01 3,561,913 METHOD OF DYEING SYNTHETHC FIBERS Hideaki Munakata, Kazuo Watanabe, Yoshikazu Arimatsu, and Toshiharn Sugihara, Otsn, Japan, assignors to Toyo Boseki Kabushiki Kaisha, Osaka, Japan No Drawing. Filed Nov. 17, 1967, Ser. No. 683,827 Claims priority, application Japan, Nov. 25, 1966, ll/77,417; Dec. 28, 1966, 42/861 Int. Cl. 1306p 1/32 US. Cl. 8-32 7 Claims ABSTRACT OF THE DISCLOSURE Synthetic fibersespecially polyester fibers, are dyed by means of a reaction product of a compound of the formula and a compound of the formula wherein A is an aromatic nucleus, B is an aromatic nucleus or a quinoid ring, R is NH or N=, R is -OH or 0, C is a quinoid ring, X is a halogen atom and Y is O, NX, NOCCH or The dyed fibers, of dark shade, are of excellent fastness to light, sublimation, washing and dry-cleaning.

This invention relates to fast dyeing of synthetic fibers, and more particularly fast dyeing of polyester fibers with oxidation dyes.

There have been proposed various methods for dyeing synthetic fibers with oxidation dyes; among which are (l) a method wherein fibers are treated with a compound having one or more reactive hydrogen atoms and N-halogeno- N'-phenyl-p-benzoquinone diimine, (2) a method wherein fibers are treated with an aromatic compound containing at least two primary and/or secondary amino radicals in para position and an N-halogenoquinone imine or N,N- dihalogenoquinone diimine, (3) a method wherein fibers are treated with an azomethin of an aromatic amine and a compound selected from the group consisting of quinones, N-halogenoquinone imines, N,N-dihalogenoquinone diimines and compounds represented by the general wherein each of R to R is hydrogen atom, halogen atom, alkyl radical or aryl radical; and (4) a method wherein fibers are treated with a primary aromatic amine or 2120- methin and N-halogeno-N-phenyl-p-benzoquinone diimine.

While these methods enable dyeing of synthetic fibers in considerably dark shade, they are not yet sufficient to obtain black dyed fibers. Further, the dyed articles of these known methods are somewhat poor in fastness. Another drawback of these known methods is in the difficulty of dyeing operation.

Therefore, an object of the present invention is to dye 3,561,913 Patented Feb. 9, 1971 synthetic fibers, particularly polyester fibers in dark shade, particularly in black shade with a very simple operation.

Another object of the present invention is to provide dark dyed synthetic fibers with excellent fastness to the light, sublimation, washing and dry-cleaning.

Other objects will become apparent from the following description.

The above mentioned objects are accomplished, according to this invention, by depositing a reaction product of a compound of the following general Formula I or N,N'- diphenyl-p-benzoquinone diimine and a compound of the general Formula II in or on synthetic fibers, particularly polyester fibers:

wherein the nucleus A is an aromatic nucleus, the nucleus B is an aromatic nucleus or a quinoid ring, R is NH- or N=, R is OH or =0 and each of the nuclei A and B may be substituted with at least one member selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, aryloxy, dialkylamino, diethanolamino, hydroxyl and halogeno radicals.

wherein the nucleus C is a quinoid ring, X is a halogen atom, Y is =0, =NX,

and the nucleus C may further be substituted with at least one halogen atom and/ or nitro radical and/ or alkyl radical.

Among the compounds represented by the above general Formula I are, for example,

-In the case of the compounds in which R in the general Formula I is OH, generally the rate of dyeing will be high, while when R is =0, generally the rate of dyeing will be lower but the loss of the dye will be less.

Among the above mentioned compounds, specifically preferable compounds in which R is OH are mor p-hydroxydiphenyl amines, compounds of the formula II; C 011 such as 4-methyl-4'-hydroxydiphenylamine, 3-methyl-4- hydroxydiphenylamine, 2-methyl 4' hydroxydiphenylamine and 4-methyl-3'-hydroxydiphenylamine, and compounds of the formula such as N-(p-hydroxyphenyl)fi-naphthylamine. Examples of preferable compounds in which R is 0 in the Formula I are N-phenyl-p-benzoquinone monoimine and N-(p-diethylaminophenyl)p-benzoquinone monoimine.

Examples of the compounds represented by the general Formula II are and mixtures of two or more of them.

Among the above enumerated compounds, N-chlorop-benzoquinone monoimine and N,N'-dichloro-p-benzoquinone diimine are preferable.

The method of dyeing of the present invention may be carried out by treating synthetic fibers or their products (yarns, threads, fabrics, articles of clothing, etc.) with a compound of the above mentioned general Formula I or N,N'-diphenyl-p-benzoquinone diimine and a compound of the general Formula II in any order or simultaneously. However, it is most preferable to treat the synthetic fibers first with the compound of the general Formula I or N,N- diphenyl-p-benzoquinone diimine and then with the compound of the general Formula II.

These compounds may be employed in the form of an aqueous solution or aqueous dispersion with or without the aid of a dispersing agent or emulsifier. The treating liquid may be applied to the synthetic fibers by any suitable method commonly employed in the art of dyeing, such as dipping, pad steaming, thermosol padding, spraying, etc.

The concentration of the respective compounds in the treating liquids varies depending on the desired thickness of the shade or color. However, for thick colors, the amount of each compound to be deposited on the fibers is in the range of 1 to by weight based on the things to be dyed. The proper concentration in the dyeing bath is usually 0.05 to 2.0% by weight in the dipping process, and 2 to 8% by weight in the padding process.

It is also possible to add any conventional such carrier such as dichlorobenzene, diphenyl, diphenyl ether, o-phenyl phenol or methylnaphthaline.

The temperature and time of the treatment may be varied over a wide range. Thus, for example, the treatment may be conducted at a temperature from the room temperature (e.g. C.) to 180 C. from 20 seconds to one hour depending upon the mode of dyeing. Thus, more particularly, in the dipping process, the fibers are treated in a treating bath at a temperature from the room temperature to 140 C., preferably from 60 to 130 C. for about 15 minutes to 1 hour, while in the padding process, the fibers are impregnated with the treating liquid usually at the room temperature, are then squeezed to a liquid content of about 50 to and dried if desired, and then heated with a suitably heating medium such as steam, hot air, infrared rays or hot inert liquid at 100 to 180 C. for about 20 seconds to 10 minutes.

In a preferable mode of working of the method of the present invention, synthetic fibers are dipped in a dyeing bath (SO- C.) which contains a compound of general Formula I and which, if desired, may also contain an emulsifier or dispersing agent, until a sufficient amount of the compound of the Formula I is absorbed in the fibers. Then the product is briefly washed, and dried if desired. Then it is dipped in an aqueous dispersion or aqueous solution of a compound of the Formula II at a temperature from the room temperature to C., pref erably 60 to 130 C. The treatment is conducted until the reaction proceeds to a desired extent, and then the dyed fibers are washed in the usual manner.

According to the method of this invention, the synthetic fibers can be dyed in a thick dark shade with excellent fastnesses.

Although the method of the present invention is particularly useful in dyeing fibers of polyesters such as polyethylene terephthalate, but it can be generally applied also to other synthetic fibers, filaments, films, fabrics, etc., such polyamides as 6-nylon and 6-6-nylon, polyacrylonitriles, polyvinyl alcohols, polyvinyl chlorides, polyure thanes and cellulose acetate.

The present invention will further be explained with reference to the following examples in which the parts are by weight.

EXAMPLE 1 Two parts of a woven fabric of polyethylene terephthalate-isophthalate (copolymerization ratio of 9:1) fibers were heated at a temperature of 100 C. for 30 minutes in 100 parts of an aqueous dispersion containing 0.1 part of p-hydroxydiphenyl amine, 0.4 part of an anionic surfactant (condensate of sodium naphthalene sulfonate and formaldehyde) and 0.1 part of a nonionic surfactant (addition product of p-alkyl phenol and ethylene oxide). The fabric was then washed with water, and then dipped in 100 parts of a separate bath containing 0.1 part of N- chloro-p-benzoquinone monoimine and 0.1 part of the above mentioned nonionic surfactant and treated therein at 100 C. for 30 minutes. Then the treated fabric was soaked at a temperature of 100 C. for 20 minutes with an aqueous solution containing 0.1% by weight of the above mentioned nonionic surfactant and 0.2% by weight of Na CO Then, the fabric was washed with water and dried. The fabric was dyed in a thick black shade with a high abrasion resistance and excellent fastness to light, sublimation, Washing and dry-cleaning.

EXAMPLE 2 A fabric of polyacrylonitrile fibers and a fabric of 6- nylon fibers were dyed in the same manner as in Example 1. In any case, the fabric was dyed in a thick black shade with excellent fastness as in Example 1.

EXAMPLE 3 When the procedure of Example 1 was repeated with m-hydroxydiphenylamine or o-hydroxydiphenylamine instead of p-hydroxydiphenylamine, the fabric was also dyed in a thick black shade with excellent fastness.

EXAMPLE 4 A woven fabric of polyethylene terephthalate-isophthalate (a copolymerization ratio of 9:1) fibers was treated with p-hydroxydiphenylamine under the same conditions as in Example 1. After being Washed with water,

the fabric was dipped in a bath prepared by kneading 0.1 part of N,N-dichloro-p-benzoquinone diimine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1, and dispersing the kneaded mixture in 100 parts of water, and was treated therein at a temperature of 100 C. for 30 minutes. The so treated fabric was then soaped in the same manner as in Example 1 and dried. The resulting fabric was dyed in a black shade with excellent fastness.

EXAMPLE 5 One part of a woven fabric of polyethylene terephthalate-isophthalate (a copolymerization ratio of 9:1) fibers was heated at a temperature of 120 C. for 1 hour with a dispersion prepared by kneading 0.1 part of N,N-diphenyl-p-benzoquinone diimine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1, and dispersing the kneaded mixture in 100 parts of water.

The fabric was cooled a little, washed with water, and was then dipped at the room temperature in a bath prepared by kneading 0.1 part of N,N'-dichloro-p-benzoquinone diimine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1 and dispersing the kneaded mixture in 100 parts of water. The temperature of the bath was gradually elevated to 100 C. and the treatment was further conducted at 100 C. for 30 minutes. Then the dyed fabric was soaped at a temperature of 100 C. for 20 minutes with an aqueous solution of 0.1% by weight of the above mentioned nonionic surfactant, and was rinsed and dried. The fabric was dyed in a thick black shade with high abrasion resistance and excellent fastness to light, sublimation, washing and dry-cleaning.

EXAMPLE 6 When the fabric was dyed in the same manner as in Example 5 with 0.1 part of N-chloro-p-benzoquinone monoimine instead of 0.1 part of N,N-dichloro-p-benzoquinone diimine in Example 5, a fast thick black fabric was obtained.

Also, when the procedure of Example 5 was repeated except that 2,6-dichloro-N-chloro-p-benzoquinone monoimine was employed instead of N,N-dichloro-p-benzoquinone diimine of Example 5, the fabric was dyed in a thick brown shade with excellent fastness.

EXAMPLE 7 One part of a woven fabric of polyethylene terephthalate fibers was treated in the same manner as in Example 5 with N,N-diphenyl-p-benzoquinone diimine and with N,N-dichloro-p-benzoquinone diimine, and was soaped to obtain a fabric dyed in a fast thick black shade.

When a polyacrylonitrile fiber fabric was treated in the same manner, the similar result was obtained.

EXAMPLE 8 Two parts of polyethylene terephthalate-isophthalate (copolymerization ratio of 85:15) fibers were dipped in a bath prepared by kneading 0.1 part of 4-methyl-4-hydroxydiphenylamine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1, and then dispersing the kneaded mixture in 100 parts of water, and heated therein at a temperature of 100 C. for 30 minutes. After washed with water, the fabric was then dipped in 100 parts of a bath containing 0.1 part of N-chloro-p-benzoquinone monoimine and 0.1 part of the nonionic surfactant in Example 1, and treated therein at a temperature of 100 C. for 30 minutes. Then the treated fabric was soaped with an aqueous solution of 0.1% by weight of the nonionic surfactant in Example 1 and was rinsed and dried. Thus a fast thick black fabric was obtained.

EXAMPLE 9 When the same procedure asin Example 8 was repeated except that 3 methyl 4' hydroxydiphenylamine or 2- methyl-4'-hydroxydiphenylamine was employed instead of 4-methyl-4'-hydroxydiphenylamine, the fabric was dyed in a black shade with excellent fastness.

EXAMPLE 10 The procedure of Example 8 was repeated except that 0.1 part of N-(p-hydroxyphenyl)-u-naphthylamine or N- (p-hydroxyphenyl)-/3-naphthylamine was employed instead of 4-methyl-4'-hydroxydiphenylamine. As a result, a fabric dyed in a black shade with excellent fastness was obtained.

EXAMPLE 11 Two parts of a Woven fabric of polyethylene terephthalate-isophthalate (a copolymerization ratio of 9:1) fibers were treated in a tumbler at a temperature of 120 C. for 30 minutes with an aqueous dispersion prepared by kneading 0.1 part of N-phenyl-p-benzoquinone monoimine, 04 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1, and then dispersing the kneaded mixture in 100 parts of water. Then the fabric was rinsed and dipped in a bath prepared by kneading 0.1 part of N,N-dichloro-p-benzoquinone diimine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1, and dispersing the kneaded mixture in 100 parts of water. The bath temperature was gradually elevated and the treatment was further conducted at 100 C. for 30 minutes. The treated fabric was soaped, rinsed and dried. There was obtained a fabric dyed in a black shade with excellent fastness.

EXAMPLE 12 The procedure of Example 11 was repeated except that N-(p-diethylaminophenyl)-p-benzoquinone monoimine or N-(p-diethylaminophenyl) -3-phenyl-p-benzoquinone monoimine was used instead of N-phenyl-p-benzoquinone monoimine. Similarly the fabric was dyed in a black shade with excellent fastness.

EXAMPLE 13 An acrylonitrile polymer fabric and 6-nylon fabric were dyed in the same manner as in Example 11. In any case the fabric was dyed in a deep brown shade with excellent fastness.

EXAMPLE 14 One part of a polyethylene terephthalate-isophthalate (a. copolymerization ratio of 9:1) fiber fabric was heated at 120 C. for 30 minutes in a tumbler with 50 parts of an aqueous dispersion containing 0.1 part of N,N-di chloro-p-benzquinone diimine, 0.4 part of the anionic surfactant in Example 1 and 0.1 part of the nonionic surfactant in Example 1. The fabric was then washed with water, was then dipped in 50 parts of an aqueous dispersion containing 0.05 part of p-hydroxydiphenylamine, 0.2 part of the above mentioned anionic surfactant and 0.05 part of the above mentioned nonionic surfactant. The fabric was treated therein at 100 C. for 30 minutes, soaped, water-washed and dried. The fabric was dyed in a black shade with excellent fastness.

EXAMPLE 15 Two parts of polyethylene terephthalate-isophthalate (a copolymerization ratio of :15) fibers were dipped in a bath of parts of an aqueous dispersion containing 0.1 part of N,N-dichloro-p-benzoquinone diimine, 0.1 part of N-phenyl-p-benzoquinone monoimine, 0.8 part of the anionic surfactant in Example 1 and 0.2 part of the nonionic surfactant in Example 1. The bath temperature was elevated gradually to 100 C., and the treatment was conducted at 100 C. for 30 minutes. The fabric was then soaped, water-washed and dried in the usual manner. The fabric was dyed in a brown shade with excellent fastness.

7 EXAMPLE 16 When 6-nylon fibers or acrylonitrile fibers were treated instead of the polyethylene terephthalate-isophthalate fibers in Example 15, there was obtained fabric dyed in a blackish brown shade with excellent fastness.

EXAMPLE 17 A polyethylene terephthalate-isophthalate (a copolymerization ratio of 9:1) fiber fabric was dipped at the room temperature in a liquid containing 4% by weight of p-hydroxydiphenylamine, 4% by weight of a dispersing agent, 4 g./l. of a chlorobenzene carrier and 1 g./l. of the nonionic surfactant in Example 1. The fabric was squeezed to a liquid content of 80% and was subjected to steaming at 108 C. for 1 minute. The fabric was then rinsed to remove the p-hydroxydiphenylamine deposited on the surface and was dried. Then the fabric was dipped in a liquid containing 5% by weight N-chloro-p-benzoquinone monoimine and 1.2% by weight of the anionic surfactant in Example 1, was squeezed to a liquid content of 80% and was subjected to steaming at 108 C. for 1 minute. When the fabric was soaped and dried, there was obtained the fabric dyed in a black shade with excellent fastness.

EXAMPLE 18 Polyethylene terephthalate-isophthalate (a copolymerization ratio of 9:1) fibers were put into an Ober Meyertype dyeing machine, and were dyed therein at a liquor ratio of 1:7 at 100 C. for 40 minutes with an aqueous liquid containing 6% OWF of p-hydroxydiphenylamine, 6% OWF of the dispersing agent and 1 g./1. of the nonionic surfactant in Example 1. After washed with water, the fibers were treated at a liquor ratio of 1:7 at 95 C. for 30 minutes with an aqueous liquid containing of 7% OWF of N-chloro-p-benzoquinone monoimine and 2% OWF of the anionic surfactant in Example 1, and were soaped, rinsed and dried. The fibers were dyed in a thick black shade with excellent fastness.

What we claim is:

1. A method of dyeing polyester fibers which comprises depositing in or on polyester fibers a reaction product of (a) a compound of the formula wherein the nucleus A is an aromatic nucleus, the nucleus B is an aromatic nucleus or a quinoid ring, R is NH- or N=, R is OH or :0 and each of the nuclei A and B may be substituted by at least one member selected from the group consisting of methyl, phenyl, methoxy, diethylamino and halogen, or the compound N,N'-diphenyl-p-benzoquinone diimine, and (b) a compound of the formula wherein the nucleus C is a quinoid ring, X is a chlorine atom, Y is =0 or =N-X in which X is a chlorine atom, and the nucleus C may be further substituted by one or more chlorine atoms.

2. The method of dyeing polyester fibers according to claim 1, wherein the polyester fibers are treated with a compound of the Formula I or N,N'-diphenyl-p-benzoquinone diimine and a compound of the Formula II in any order or simultaneously.

3. The method of dyeing polyester fibers according to claim 1, wherein the polyester fibers are treated first with a compound of the Formula I or N,N-diphenyl-p-benzoquinone diimine and then with a compound of the Formula II.

4. A method according to claim 1, wherein the compound of the general Formula I is References Cited UNITED STATES PATENTS 3,253,878 5/1966 Kruckenberg et al 8-32X 3,254,934 6/1966 Schwarz et a1 832X FOREIGN PATENTS 652,278 11/1962 Canada 8-32 0 GEORGE F. LESMES, Primary Examiner 5 T. I. HERBERT, ]R., Assistant Examiner US. Cl. X.R. 8179