GB2167427A

GB2167427A - Monoazo dyestuffs

Info

Publication number: GB2167427A
Application number: GB08526750A
Authority: GB
Inventors: Kiyoshi Himeno; Junji Yoshihara
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Kasei Corp
Priority date: 1984-10-31
Filing date: 1985-10-30
Publication date: 1986-05-29
Also published as: JPS61106669A; DE3538835A1; GB8526750D0; JPH0556388B2

Abstract

Novel monoazo dyestuffs (I) impart yellow hues to polyester fabrics, and the dyed fabrics are suitable for alkaline discharge or alkaline resist printing. <IMAGE> wherein A represents: <IMAGE> R is alkyl, allyloxyalkyl, alkoxyalkyl, phenoxyalkyl or benzyl; R<1> is hydrogen, alkyl, allyloxyalkyl, alkoxyalkyl, phenoxyalkyl, benzyl, cyanomethyl, allyloxycarbonylmethyl, alkoxycarbonylmethyl, phenoxyalkoxycarbonylmethyl, or benzyloxycarbonylmethyl; and in which the total number of carbons in R and R' is 6-16.

Description

SPECIFICATION Monoazo dyestuffs FIELD OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to monoazo dyestuffs, particularly, the monoazo dyestuffs in yellow series having excellent properties such as alkaline resist printing, alkaline discharge printing, and wet color features.

DESCRIPTION OF THE PRIOR ART Recently, as new steps in dyeing processes for polyester fibers, alkaline discharge printing process has been widely applied. A general process for discharge printing comprises hydrolyzing a dyeing which has dyed once on a fiber or a fabric to be dyed, so as to lose an affinity of the dye for polyester fibers thereby effecting a resist printing or discharge printing in a restricted part thereof.

For such a process, a dyestaff capable of treating sufficient resist printing and discharge printing with a smail amount of alkaline reagents is preferred in view of prevention for denaturing alkaline resistive dyestuff (color for shading) which is used for colored discharge style and prevention for deteriorating polyester fabric. Recently, there has been increased demand for the dyestuff having an excellent properties in discharge printing.

On the other hand, generally, the dyestuff having an excellent property in discharge printing is liable to have inferior properties in wet color fastness and heat resistance. These phenomena are easily understood in consideration of a chemical formula of the dyestuffs.

That is to say, the fact that the dyestuff possesses an excellent properties in alkaline resist printing and discharge printing, means that a constitution per se of the dyestuff will have a strong affinity for alkaline agents and will be liable to be decomposed. Accordingly, the dyestuff having such a remarkable property may be inherently inferior to other properties such as wet color fastness, heat resistance, and the like when the dyeing contacts with water.

In particular, recently a post-treatment of dyed material, such as polyurethane treatment, silicone treatment, etc., is often applied for the purpose of providing, for example, water proofing, preventing for statical electric charging, improving feeling of fabric and the like, however, these treatments tend to deteriorate the wet color fastness, such as color fastness to washing, color fastness to perspiration, color fastness to water, after treatment.

Needless to say, there are other excellent dyestuffs, only when slight attention is given to those of wet color fastness, while these dyestuffs have inferior properties in alkaline discharge printing.

For example, dyestuffs having formula, stated below and exhibiting relatively higher properties in the alkaline resist and discharge printing have been proposed in the specifications of Japanese Patent Publication No. 19716/1971, Japanese Patent Publication No. 35934/1984 and British Patent No. 2010888, in which it is stated that these dyestuffs also exhibit inferior properties in wet color fastness and heat resistance without exception.

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel dyestuff capable of exhibiting an excellent property in discharge printing even with a small amount of alkaline agents, and having a good wet color fastness and heat resistance. In other words, the dyestuff of the present invention satisfies the aforesaid conflicting effects concurrently.

According to the present invention there is to provide monoazo dyestuff obtained by combination of a specific diazo component and a specific coupling components, having a formula:

(wherein A represents

R represents alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl or benzyl;R' represents hydrogen, alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl, benzyl, cyanomethyl, allyloxycarbonylmethyl, alkoxycarbonylmethyl, phenyloxyalkyloxycarbonylmethyl, or benzyloxycarbonylmethyl; and total number of carbons in R and R' is 6-16) An alkyl group represented by R and R' in the above general formula (I) may be either straight or branched, and total number of carbons in R and R' is preferably 8-12, R' is preferably hydrogen, C, s alkyl, or C, 9 alkyloxy C13 alkyl, wherein R is selected from the group consisting of C1 10 alkyl, allyloxyethyl, C14 alkyloxyethyl, phenyloxyethyl or benzyl so that a total number of carbons in R and R' may be 8-12.

According to the present invention the dyestuffs having alkaline resist printing, alkaline discharge printing and wet color fastness may be obtained only when a specific diazo component and a specific coupling component are used in combination. Thus, provided that a total number of carbons in R and R' may be 5 or less, or a position of substituents in diazo component, i.e.

-NO2 and -COOR may not be in proper positions, technical advantages of the present invention will not be expected.

The monoazo dyestuffs represented by the aforesaid formula (I) may be prepared, for example, according to the following steps.

A compound of the following formula:

(wherein R is the same as defined in the formula (I)) is diazotized in a conventional manner, and is coupled with the compound of formula (III) which is coupling component: H-A.. (Ill) (wherein A is as defined in formula (I)) Examples of the fibers to be dyed with the dyestuffs of the present invention include polyester fibers composed of polymers or condensation products such as polyethylene terephthalate, poiymerized condensate of terephthalate and 1 ,4-bis-(hydroxymethyl)cyclohexane, or mixed spinning fiber or mixed woven products thereof with naturally occuring fibers, such as cotton silk, wool, and the like.

The dyestuffs of the present invention may be used according to a conventional process in a dye solution or a dye paste, in which the dyestuff of the general formula (I) is dispersed into an aqueous medium with dispersing agent For instances, the dyestuff of the present invention may be colored on polyester fiber, mixed spun fiber or a mixed spun fabric thereof, by conventional dyeing process, such as high temperature dyeing, carrier dyeing, thermosol dyeing and the like, to provide dyeing having excellent color fastness. Alternatively, more preferable results may be obtained by adding acidic substance in a dyebath.

A discharge printing using the dyestuff of the present invention will take place practically as follows: At first, a polyester fabric, etc., is dyed by the process which comprises immersing the fabric into a dyebath and holding it at 1300C for 60 minutes and drying at 80-150"C to complete ground dyeing.

In the next step, the dyed fabric is subjected to a discharge printing step which comprises printing a desired part of the fabric with a paste for discharge printing, drying at 1 000C for 2-3 minutes, heat-treating at 180"C for 7 minutes to decompose the dyestuff at the printed part of the fabric and to fix the dyestuff rest part of ground dyed fabric.

Subsequently, the fabric is washed with water, reducing agent and water, and is dried finally to obtain printed fabric completed by the discharge printing.

The monoazo dyestuff of the present invention may be used in combination with a dyestuff of the same or different series.

The present invention is more fully described in detail by the following examples which do not restrict the scope of the claimed invention.

In the Example the percentages are by weight.

Example 1 5.6 grams of n-butoxyethyl 4-amino-3-nitrobenzoate was diazotized with 42% nitrosylsulfuric acid in a mixed solvents (phosphoric acid/acetic acid 1/1) at 0 C for one hour to obtain diazosolution.

3.6 grams of N-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-on was dissolved into a 400 mls of water with 5.2 grams of sodium acetate and 2.4 grams of sodium hydroxide, into which the diazo-solution was added at 0-3"C, pH 4-5, and stirred for 3 hours, to form crystalline precipitates.

The crystals was filtered, washed and dried to obtain a monoazo dyestuff of the general formula stated below (yield 94%).

The maximum absorption wavelength, A- max (aceton) of the monoazo dyestuff obtained was 440 nm.

0.5 gram af the monoazo dyestuff, thus obtained,

was dispersed into 3 liter of water containing 1.0 gram of condensate of naphthalene sulfonic acid-formaldehyde and 2.0 grams of sulfuric acid ester of higher alcohol to prepare a dyebath.

100 grams of polyester fabric was immersed into said dyebath at 130"C for 60 minutes, thereafter treated with soaping, washing and drying to obtain yellow colored fabric having excellent light color fastness, sublimation color fasteness and wet color fastness.

Furthermore, the dyestuff of the invention exhibited excellent alkaline discharge printing and other excellent properties such as various wet color fastnesses and heat resistance as shown on Table 1, after polyurethane treatment.

Example 2 A dyestuff having a formula:

was prepared by the similar process to that of Example 1. The dyestuff was mixed with 0.5 gram of a condensation product of napthalene sulfonic acid-formaldehyde, and finely ground in a paint shaker to obtain pulverized dyestuff. A fine dyestuff, thus obtained, was then thoroughly mixed with a paste material to obtain dye paste.

Composition of the past material: A paste of carboxymethyl cellulose 30.0 grams (CMC) Tartaric acid 0.2 Carrier of aromatic compounds 0.3 (Sunflowren SN, trade name of Nikka Chemical Ind. Co., Ltd.) Water 68.5 Total 99.0 grams A polyester fabric was printed with a dye paste obtained, was dried intermediately at 100"C, was maintained in a superheated steam at 17000 for 7 minutes to develop color and subsequently, treated with soaping, washing and drying. A yellow-colored fabric having excellent properties in light color fastness, subiimation color fastness and wet color fastness. Regarding alkaline discharge printing, a similar test took place on a dyestuff to that of Example 1 and obtained results as shown on Table 1.

The maximum absorption wavelength, A max (aceton) of the monoazo dyestuff obtained was 440 nm.

Comparative Examples 1-4 The test procedure described in the Example 1 was repeated using four types of dyes which were outside of the claimed invention, and results are stated on Table 1.

In the Examples, each test was conducted according to the following procedures.

(1) Property for alkaline discharge printing A dyed fabric previously colored with the dyestuff in question is locally coated with a paste for discharge printing, is maintained in a superheated steam at 18000 for 7 minutes, and is washed with reductive solution. A whiteness of a part of the cloth which is discharged is determined according to grey scale.

Composition of the paste for discharge printing: A paste material of carboxymethyl 55% cellulose A hygroscopic reagent of poly- 15% ethyleneglycohol type (Manufactured by Nikka Chemical Ind., trade name, Sunresist AL-2) A carrier of aromatic type 5% (Manufactured by Nikka Chemical Ind.

Co., Ltd., trade name, Dispent PC-5) Na2CO3 0.5% Water 24.5% (2) Polyurethane treatment A fabric is treated with finished treating reagent of "Hydran F-24K", manufactured by Dainippon Ink and Chemicals Inc.) and cured at 16000 for 2 minutes.

(3) Color fastness to washing A dyed cloth treated with polyurethane, on which multi-fiber of nylon is attached, is subjected to a washing test substantially according to AATCC method, washing IIA, and a contamination on the nylon of the multi-fiber is determined based on a grey scale.

(4) Color fastness to perspiration Dyed fabrics treated with polyurethane, on which a patch of nylon cloth and silk cloth are respectively attached, are subjected to a test of color fastness to perspiration substantially according to JiS L-0848A, and a contamination on the silk patch is determined based on a grey scale.

(5) Color fastness to water A dyed fabric treated with polyurethane, on which a patch of silk cloth in place of nylon cloth, is subjected to a test of color fastness to water substantially according to JIS L-0846A, and a contamination on the silk patch is determined based on a grey scale.

(6) Heat resistance A dye cake is mixed with a condensation products of naphthalene sulfonic acid-formaldehyde and heat-treated at 1 300C for one hour. A heat resistance is determined as a remaining rate of the dyeing calculated by the following equation.

A remaining rate (%)= Absorbance of dye post treatment X100 Absorbance of dye pre-treatment Table 1 Color Fastness After Heat Polyurethane treatment Alkaline Re Discharge Perspi- sist Dyestuff Chemical Formula Printing Washing Ration Water ance (grade) (grade) (grade) (grade) (%)

u, o a\ ro cy CV VI VI of (n)C4}OC2H4OOCN=N3 the invention 4-5 4-5 5 4-5 95 1 I 1) IO C2H5 NO2 eN the invention 4-5 4-5 5 4-5 97 I 2) N I CH3 CDOH3 CH3 6 o 6 o o -u" Ho N1 C3HOI3 c c c o o o v < o v N xe c c av H UJ > H tl4 > H C s U c z U c ffi tH veE E ve &commat; aJ x aJ a x q SS X > 1; li3 &commat; X cx v n 4 continued Table 1 (cont'd)

o o o c CH3 OOC -N=N I 2* 4-5 2 3 2-3 60 10 l NO2 CH Example 3* Reference CH20OCN=N)(13; 4-5 2-3 3 2-3 50 C2H5 cu CHO(C}{O)OC-NN3CN N I N C2H5 l t sr v u O D W; O iN v V V a) es a X a) sr Q C) C) c as c &commat; c &commat; aJ E aJ E &commat; g &commat; x O x a) x * Comparative Example 1 Dyestuff disclosed in the specification of Japanese Patent Publication No. 19716/1971 Comparative Example 2 Dyestuff having diazo and coupling components disclosed in the specification of Japanese Patent Publication No. 19716/1971 Comparative Example 3 Dyestuff disclosed in the specification of Japanese Patent Publication No. 35934/1984 Comparative Example 4 Dyestuff disclosed in the specification of British Patent Publication No. 2010888 Examples 3-84 A polyester fabric was dyed according to the process of Example 1 using monoazo dyes listed in Tables 2 and 3, and colored fabric was tested and evaluated according to a standard as stated in Example 1. The results are shown on the Tables 2 and 3 below.

Table 2

4J JJ av ~ N o N v c9 0 N es m D HO aJ~ N t4 as " Color Fastness After Hue I r C Treatment W e t = Re W! A m v ample R- R'- (nm) ester Printing Washing ration Water ance Q, (grade) (grade) (grade) (grade) (%) m (n)C5H11- CH3 *8 Yellow 4-5 4-5 4-5 4-5 92 Ci, S P k cn 5 H- N II N N N '1 90 A i ci w g > t e Eg rell"m C2H5- I. II N N 5 92 9 (n)C6H13- 'I I' N N N 5 1. 95 10 t' zy N N N 5 92 3 & Ç s a) ~ o 13 C2H5- N N sr N II 5 96 v ,o S Xv Xz N Z 2 zA u 8 N C i S & 6 e i v 5 i U C) v 'v U Uv V &commat; C C C C C C rv a X g t 0 > O ~ N nj continued Table 2 (cont'd)

u CH3 (n)C4H9CHCH2- f Yellow 4-5 4-5 5 5 95 C2H5 u n In C II 45 4-5 88 16 N (i)C3H7OC3H6- II II N N 45 90 17 '1 Th2 U II N N 5 4-5 93 18 C H - 'I II I' N S' N 5 95 19 '1 (n) C4H9CHCH2 II II U N N N 96 C2H5 20 '1 (i) C3H7OC3H6- U II 'I N N r = 90 21 (n)C4H9OC3H6- II II II 'I 5 N 92 22 '1 (n) C6H13OC2H4- N '1 4-5 II II 5 I ' ' 95 23 (n) C4H9CHCH2OC3H6- 'I G C2H5 24 '1 r = N 1' 4-5 t N = 95 ax 25 '1 (n)C4H7OOCCH2- 'I II 5 N 45 1' 90 26 '1 fficH2OOCC2 'I '1 4-5 II 5 5' 92 27 = D = = II II II II 0 II 92 28 (n)C4H9- 222 N II C' 1' 4-5 'S 90 29 (n)C4H9CHCH2- NcCH2 11 'I 5 II II ' II 90 CH2H5 Iy I v I E N Uo 1s z g n tsl KD tO N tD tD = N I SC D O O t v U D v O V = x I C C) CJ 5 r C) D :: blU U N e blU U O UU O O = UU O O U-U U O SC U U b ls cs a o g cs o c.> c) c)^rt = uv c c.)t C&commat; c.) P) cD Y mS c c U c < c c c U c < 9 8 K N un ur u u c c Table 2 (cont'd)

N ur o 00 440 Yellow 4-5 4-5 o H s o o co 31 '1 (n)C6H13OCCCH2- II II N 5 1' 95 32 a' (n)C3H7OOOCH2- N II U N t t 1' 90 33 II C2H5CH2- N II 5 4 N '1 88 34 CH2=CHH2OC2H4- C2H5- II II U N N II 90 35 1' (n) C4H9- N = 4-5 4-5 5 '1 92 36 (n)C4H9CH1CH2- I' I' U N N N 95 C2H5 sr ~ t 38 CH3OC3H6- N II 5 II 4 88 39 1' H - II r N y) 90 C2H5OC3 6 40 CH3OC2H4- (n)C4H9- N N II N N N 91 41 t (n)C4H9CH1CH2- N t N U 5 N 94 C2H5 42 C2H5OC2H4- U U I N N N II II 95 43 N (n)C4H9- U N I. N II II 96 44 (n)C3H7OC2H4- C2H5- U r 5 N t r a' 90 cs lS H n N W N 8 4 n ^ 5 8 I -U Uo W W | tu 1o x 8n 1 ut ut un Ou 4} ut ut ú u | w C C cUN cUN C C 's 8 UN C C C cUn 6 O t c9 1 N z N 8 = u c O ~I 0 ~I N v U continued Table 2 (cont'd)

46 (n)C3HOC2H4 C4H9- O Yellow m 4-5 5 4-5 un 47 II (i)C2H7OC3H6- I '1 r er N U 94 48 (n) C4H9OC2H4- U U N U U N N 96 49 U Thij2 II N U ,II II 5 95 50 ffC2H4- H- II U U U II 45 90 ur 52 1' C H - II II N N U 5 97 53 a' CH30C3H6- U I' 'I N II 45 92 54 S (i)C3H7OC3H6- = II N N II 5 94 55 '1 = = = o 'I II 45 U U '1 98 C2H5 r t t r = = t = = r O t = = Q, 58 a' C2H6- N U II 11 1' II 95 59 = = = = = = = = t = 5 = = 96 60 CHOCH- U I' U N II 336 4-5 94 j cs (n)C3H7OC3H6- U j N I ) ) o u crJ ) i = A I I uX X 8~cDs I I = a CD /, ur aa o u a sU = 4 I i = c u vc u u 6 u =: 8 U u 6 P: = 1v > o o u W b o ,q N e v ur vo F co o o < continued Table 2 (cont'd)

0000 7 ur ur C2H5 63 N W2 'I U 5 N U U 90 u, o a o r nU t)u N a sr n u z tr:: cs v Table 3

u c1 o cu ca 1 m I o\ v Formula ROOC u u, W 0 W ur ur He N 0! g v v ui g l Hue Alkaline Polyurethane Treatment Re fi A max Poly- Discharge Perspi- sist ample sv ffi (nm) ester Printing washing ration Water ance Cr og 3 (grade) (grade) (grade) (grade) (%) 65 (n) C4H90C2H4- C2H5- 423 Yellow 4-5 4-5 5 4-5 93 66 (n)C2H5OC2H4- N U I' N N N N 90 67 (n)C3H7OC2H4- N U N N N N N 92 68 (n) CJ3130C2H4- U I N 45 N N 5 96 69 (n) C4H9CHCH2OC2H4 II a N ail ! N 98 3 H W H = =R C2H5- (n) C4H9OC2H4- a II 45 N N 45 93 71 1' ThC2H4- N N N I. N N 95 a' = N t t 5 t U ,c C U v 73 CH2=CH-CH2OC2H4- C2H5- U N U N U 'I 92 X 8NN O N < Ú U I cs g A v g w t 8N U Dt i U C C C C C i 6 U I &num; S b o H N X continued Table 3 (cont'd)

sr 2H4- C2H5- 423 Yellow 4-5 4-5 5 = 75 GcH2- U a' N N N N N 98 76 (n)C4H9- N N N N 1N II N 94 77 (n)C5H11- N II II 45 N N 5 96 r ~t t r r t o t 79 (n) C4H9CH2CHHS2 I N N U N I' '1 98 80 U (n)C3H7- 'I N N N N N + 98 81 2H4- N 'I I' 45 N N 45 97 = = t t t = r t = as > 1 t & 2H4 N N = = + t t D UC U As stated in the above Examples, a polyester fabric which was dyed with dyestuffs of the invention and processed by discharge printing, has an excellent property in alkali discharge printing. Particularly, it is clear from the Table 1 that the dyestuff of the invention exhibits excellent property in discharge printing, even when an amount of alkaline agent will be as little as 1/10 of conventional amount.

Furthermore, the dyestuff of the invention has a remarkably superior property in wet fastness and heat-resistance after treating with polyurethane. Even though these properties generally conflicts with the property in the alkaline discharge printing, the dyestuff of the present invention surprisingly satisfies both properties in higher level.

Thus, in consideration of the prior art, a technical advantage of the present invention is unexpected and surprisingly.

Furthermore, a colored fabric according to a dip dyeing or printing dyeing with the dyestuff of the invention has an excellent property in degree of exhaustion, build up property, and temperature dependency, as well as various color fastness such as light color fastness, sublimative color fastness and the like.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

1. Monoazo dyestuffs of the formula:

(wherein A represents

R represents alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl or benzyl; R' represents hydrogen, alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl, benzyl, cyanomethyl, allyloxycarbonylmethyl, phenyloxyalkyloxydicarbonylmethyl, or benzyloxycarbonylmethyl; in which total number of carbons in R and R' is 6-16).

2. Monoazo dyestuffs according to Claim 1, whein the total number of carbons in R and R' is 8-12.

3. Monoazo dyestuffs according to Claim 1, wherein R' is selected from hydrogen, C16 alkyl, or C14 alkyloxy-C, 3 alkyl.

4. Monoazo dystuffs according to Claim 1, wherein A

(in which R' is as defined above).

5. Monoazo dyestuffs according to Claim 1, wherein R is alkyl and A is

(in which R' is as defined above).

6. A monoazo dyestuff as defined in Claim 1 substantially as hereinbefore described particularly with reference to the Examples.

CLAIMS Amendments to the claims have been filed, and have the following effect: Claim 1 above has been deleted or textually amended.

New or textually amended claims have been filed as follows:1. Monoazo dyestuffs of the formula:

(wherein A represents

R represents alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl or benzyl; R' represents hydrogen, alkyl, allyloxyalkyl, alkyloxyalkyl, phenyloxyalkyl, benzyl, cyanomethyl, allyloxycarbonylmethyl, alkoxycarbonylmethyl, phenyloxyalkyloxydicarbonylmethyl, or benzyloxycarbonylmethyl; in which total number of carbons in R and R' is 6-16).