CH636369A5 - Color-stable MIXTURES OF DISPERSION DYES. - Google Patents

Description

636369

2nd

The invention relates to disperse dye-1. Color-stable mixtures of disperse dyes, mixtures which have significantly better dispersion stability than the individual components. The new mixtures contain one or more compounds of the formula I.

PATENT CLAIMS: Mixtures of dispersions containing one or more compounds of formula I.

r

2nd

-r

(I)

ch2ch2-r4

and one or more compounds of the formula II

d - n = n

? ♦

- ch - r.

contain,

where D is a diazo component customary in the chemistry of disperse dyes,

Ri is hydrogen, alkyl, alkoxy or acylamino, R2 is hydrogen, alkyl or alkoxy, which may have a substituent,

R3 is hydrogen, alkenyl or alkyl, which may have one or two substituents,

R4 acyloxy or alkoxycarbonyl,

Rs and R'5 denote one hydrogen and the other methyl or phenyl,

wherein the proportion of the compound or compounds of formula I and the proportion of the compound or compounds of formula II is at least 5 mol percent each and the molecules only carry those substituents that are common in the chemistry of disperse dyes.

2. A process for the preparation of the dye-stable disperse dye mixtures according to claim 1, characterized in that a diazotized amine of the formula III

D-NH2

(III)

with a mixture containing one or more compounds of the formula IV

(iv)

ch2ch2-r4

and one or more compounds of the formula V R "

ch - ch - rr

(v)

contains, wherein the proportion of each component in the mixture of the compounds of formulas IV and V makes up at least 5 mol percent.

d - n = n 3

10th

R1

(I)

'CH2CVR4

15 and one or more compounds of the formula II

(ii)

d - n

, / R3

Jcfc-

N— <o> -

) - 'ch r rl

1 5

%

ch

(ii)

- R "

25th

where D is a diazo component customary in the chemistry of disperse dyes,

Ri is hydrogen, alkyl, alkoxy or acylamino, R2 is hydrogen, alkyl or alkoxy, which may have a substituent,

R3 is hydrogen, alkenyl or alkyl, which may have one or two substituents,

R4 is acyloxy or alkoxycarbonyl and Rs and R's are one hydrogen and the other is methyl 35 or phenyl,

wherein the proportion of the compound or compounds of formula I and the proportion of the compound or compounds of formula II is at least 5 mol percent each and the molecules only carry those substituents that are common in the chemistry of disperse dyes.

Suitable diazo components and substituents customary in the chemistry of disperse dyes are e.g. in German Offenlegungsschrift No. 2120089, the published French patent application 2 008 404 and the English 45 patent specification No. 1359741.

“Acyl”, also in acylamino, generally means radicals of the formula R-Y- or R'-Z-

where R is an optionally substituted alkyl, alkenyl, cycloalkyl, phenyl or heterocyclyl radical, so Y is a radical of the formula -O-CO-, -O-SO2- (oxygen in each case bound to R) or -SO2-,

R 'is hydrogen or R,

Z -CO-, -NR "-CO- or-NR" -S02- (nitrogen each bound to R ')

55 and R "are hydrogen or R.

Under alkyl, also in alkoxy, generally straight-chain or branched radicals having 1 to 8, preferably 1 to 4, in particular 1 or 2 carbon atoms, under alkenyl radicals having 2 to preferably 3 carbon atoms and under 60 cycloalkyl radicals having 5 to 7, are preferred 6 carbon atoms to understand. Examples of substituents on the alkyl radicals are Halogen atoms, in particular chlorine or bromine, hydroxyl, alkoxy, phenyl, phenoxy, cyano, acyl or acyloxy. An alkyl radical preferably bears only 65 such a substituent or substituent and a hydroxyl group.

Preferred mixtures contain one or more compounds of the formula I a

3rd

636369

R

(I a)

CVCH2-R14

(I b)

and one or more compounds of the formula II a and

R7- \ 0> —N = N- \ 0) - N

R0 RQ R

8 9 u in which Re is hydrogen, chlorine, bromine, iodine, nitro, cyano, Ci-2-alkoxycarbonyl or trifluoromethyl,

R7 nitro, Ci-2-alkylsulfonyl, aminosulfonyl, mono- or di- (Ci-2-alkyl) -aminosulfonyl, Ci-2-alkoxycarbonyl or phenylazo, wherein the phenyl nucleus is up to three times by methyl, methoxy, chlorine, bromine and / or nitro can be substituted,

Rs is hydrogen or, if R9 is hydrogen, also chlorine, bromine or Ci-2-alkoxycarbonyl,

R <) hydrogen, chlorine, bromine, iodine, cyano or Ci-2-alkylsulfonyl,

Rh is hydrogen, methyl, methoxy, ethoxy, formylamino, Ci-4-alkylcarbonylamino, Ci-2-alkylcarbonylamino, Ci-4-alkoxy substituted once by hydroxyl, chlorine, bromine, cyano, phenyl, Ci-3-alkoxy or phenoxy -carbonylamino, ethoxycarbonylamino, benzoylamino or Ci-2-alkylsulfonylamino substituted by hydroxy, Ci-3-alkoxy or Ci-2-alkoxy-ethoxy,

R12 is hydrogen, methyl, C1-2-alkoxy, C1-2-alkoxy or Ci-2-alkoxyethoxy substituted by chlorine, bromine, cyano or phenyl,

R13 is hydrogen, Ci-4-alkyl, C2-3-alkenyl or by Ci-2-alkoxy, cyano, formyloxy, Ci-4-alkyl-carbonyloxy, Ci-3-alkoxy-carbonyl, benzoyloxy or Ci-3-alkoxy- carbonyloxy substituted C2-3-alkyl, benzyl or phenylethyl and R14 formyloxy, Ci-4-alkyl-carbonyloxy, benzoyloxy, phenoxyacetoxy, Ci-3-alkoxy-carbonyl, Ci-3-alkoxy-carbo-nyloxy, mono- or di- (Ci-4-alkyl) -aminocarbonyloxy or phenylaminocarbonyloxy, where the phenyl nucleus can carry up to two chlorine, bromine, methyl or methoxy as substituents.

In particularly preferred mixtures of disperse dyes of the formulas I a and II a, Ro denotes hydrogen, chlorine, bromine or nitro,

R7 nitro,

Rs hydrogen,

R9 is hydrogen, chlorine, bromine, cyan or methylsulfonyl, R11 is hydrogen, methyl, Ci-2-alkylcarbonylamino, chlorine or bromine-Ci-2-alkylcarbonylamino, Ci-2-alkoxycarbonylamino or Ci-2-alkoxy -ethoxycarbonylamino, R12 is hydrogen, methoxy or ethoxy,

R13 C2-3-alkyl, C2-3-alkyl, which is substituted by cyano, Ci-2-alkyl-carbo-nyloxy, Ci-2-alkoxy-carbonyl or Ci-2-alkoxy-carbonyloxy, or allyl,

R14 Ci-2-alkyl-carbonyloxy, Ci-2-alkoxy-carbonyl or C 1-2-alkoxy-carbonyloxy and Rs and R's one hydrogen and the other methyl.

In other preferred mixtures, the coupling components correspond to the formulas I b and II b

(II b),

wherein R4 is acyloxy, in particular Ci-2-alkyl-carbonyloxy or Ci-2-alkoxy-carbonyloxy.

20 The preparation of the dye-stable disperse dye mixtures is characterized in that a diazo-tated amine of the formula III

D-NH2

(III)

25th

with a mixture containing one or more compounds of the formula IV

(IV)

CH2CH2 "R4

and one or more compounds of the formula V

* 4

CH

(V)

- R,

contains, wherein the proportion of each component in the mixture of the compounds of formulas IV and V makes up at least 5 mol percent.

It is often possible to produce two or even more modifications from an azo disperse dye 50. It is important for the dyer to have a modification that is stable under dyeing conditions. Such temperature-stable modifications are generally obtained by one of the thermal treatments as described in the following 55:

a) heating an aqueous suspension to temperatures between 70 and 140 ° C, preferably 80-100 ° C, for 10 minutes to 5 hours, preferably for 1 to 3 60 hours, optionally under pressure;

b) drying the water-moist mixture at 100-130 ° C;

c) heating in organic solvents, e.g. Ethanol, n-butanol, iso-butanol, glycols or glycol ethers, to temperatures between 80 and 140 ° C, optionally below

65 pressure;

d) heating in aqueous suspension with the addition of water-soluble organic solvents, e.g. Butanol, glycols, glycol ethers or dimethylformamide, on tempera

636369

4th

doors between 80 and 140 ° C, possibly under pressure;

e) heating in aqueous suspension with the addition of anionic, cationic or non-ionic surfactants to temperatures between 80 and 100 ° C;

f) grinding with the addition of conventional dispersants, e.g. Alkylnaphthalene-sulfonic acid-formaldehyde, phenol-form-aldehyde condensation products or alkali salts of lignin sulfonic acids or sulfite cellulose liquors, at temperatures between 50 and 100 ° C, preferably between 90 and 100 ° C.

The dyes are excellently absorbed from aqueous suspensions on textile material made from fully synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. They are particularly suitable for dyeing, padding or printing on textile material made from linear, aromatic polyesters, as well as from cellulose-2'A-acetate, cellulose triacetate and synthetic polyamides.

Dyeing, padding or printing according to known, e.g. the method described in French Patent No. 1,445,371.

In the following examples, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius.

example 1

17.3 parts of 2-chloro-4-nitro-l-aminobenzene are stirred overnight in a mixture of 44 parts of concentrated hydrochloric acid and 100 parts of water. After adding 60 parts of ice, a solution of 6.9 parts of sodium nitrite in 25 parts of water is added dropwise at 0-3 ° within 30 minutes. The diazotization is complete after 2 hours. A little undissolved product is filtered off and a mixture of 11.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) aminobenzene, 12 is added dropwise to the clarified diazonium salt solution at 0-3 ° within 45 minutes , 3 parts of N- (2'-acetoxypropyl) -N- (2'-cyanoethyl) aminobenzene and 20 parts of acetic acid. The coupling reaction is completed by adding 50 parts of sodium acetate. The precipitated dye mixture is filtered off, washed with 4000 parts of water and dried.

A dye preparation produced therefrom according to customary methods with the addition of dispersants satisfies all technical requirements.

Example 2

6.9 parts of sodium nitrite are slowly introduced into 150 parts of 95% sulfuric acid at 60-70 ° with vigorous stirring. The mixture is stirred at 60-65 ° for 10 minutes, then cooled to 5-10 ° and 16.3 parts of l-amino-2-cyano-4-nitrobenzene are added at this temperature. The diazotization is complete after 3 hours. The sulfuric acid diazonium salt solution is poured into a mixture of 300 parts of ice and 100 parts of water, filtered off from some undissolved product and a mixture of 11.6 parts of N- (2'-acetoxyethyl) -N is added dropwise to the clarified diazonium salt solution at 0-3 ° - (2'-Cyanoethyl) aminobenzene, 12.3 parts of N- (2'-acetoxypropyl) -N- (2'-cyanoethyl) aminobenzene and 30 parts of acetic acid. After three hours, the separated dye mixture is filtered off, washed acid-free and dried. A finely dispersed dye preparation produced therefrom by customary methods with the addition of dispersing agents satisfies all the application requirements.

Example 3

16.3 parts of l-amino-2-cyan-4-nitrobenzene are introduced into 100 parts of 95% strength sulfuric acid at 5-10 ° C. 32 parts of 40% strength nitrosyl sulfur are added dropwise in the same temperature interval.

rock acid and stir for 3 hours at 5-10 °. The sulfuric acid diazonium salt solution thus obtained is discharged onto a mixture of 300 parts of ice and 100 parts of water. A mixture of 4.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) aminobenzene, 19.7 parts of N- (2'-acetoxypropyl) - is added to the aqueous diazonium salt solution clarified by filtration. Drop in N- (2'-cyanoethyl) aminobenzene and 30 parts of acetic acid. The temperature is kept at 0-3 ° during the coupling by adding ice. The excreted mixed dye is filtered off and washed acid-free with water. It is in a dye-unstable modification. The water-moist press cake is then mixed in 300 parts of water. The homogeneous dye suspension is poured into a steel autoclave and kept under stirring for 3 hours at 105-110 °. After cooling and filtering, a dye mixture which is stable against thermal influences is obtained. The mixed dye, which has been finely divided by adding dispersing agents, meets all application requirements.

Example 4

13.8 parts of l-amino-4-nitrobenzene are dissolved in 80 parts of water at 70-80 ° with the addition of 28 parts of concentrated hydrochloric acid. It is cooled to 0-2 ° with the addition of 200 parts of ice and diazotized rapidly with a solution of 6.9 parts of sodium nitrite in 14 parts of water. Some solid product is filtered off and a mixture of 4.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) aminobenzene, 19 is added dropwise to the clarified diazonium salt solution at 0-3 ° within 60 minutes , 7 parts of N- (2'-acetoxypropyl) -N- (2'-cyanoethyl) aminobenzene and 20 parts of acetic acid. The coupling reaction is completed by adding 40 parts of sodium acetate. The separated dye mixture is filtered off and washed with water. The moist presscake of the thermally unstable mixed dye is stirred in 400 parts of water, heated to 90-95 ° and stirred at this temperature for 3 hours. The dye mixture, which is now in a thermally stable form, is then isolated by filtration, washed and dried.

The dyestuff mixture, which has been finely divided by adding dispersing agents, meets all application requirements.

Example 5

A mixture of 18.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) -amino-benzene, 4.9 parts, is added to a diazonium salt solution prepared according to Example 1 within 45 minutes at 0-3 ° Run in N- (2'-acetoxypropyl) -N- (2'-cyanoethyl) aminobenzene and 20 parts of acetic acid. The coupling reaction is completed by adding 50 parts of sodium acetate. The precipitated dye mixture is filtered off, washed with 4000 parts of water and dried in vacuo at 100-105 ° for at least 48 hours. As a result of this treatment, the dye mixture is converted into a thermostable form which is excellently suitable for all purposes.

Example 6

- In 120 parts of concentrated sulfuric acid 6.9 parts of sodium nitrite are added in portions at 60-70 ° with vigorous stirring. The mixture is stirred for a further 10 minutes at 60-65 °, then cooled to 30 ° and 20.7 parts of 2,6-dichloro-4-nitro-l-aminobenzene are added. The diazotization is complete after 3 hours. The yellow-brown solution is poured onto a mixture of 340 parts of ice and 250 parts of water. The aqueous diazonium salt solution obtained is allowed to

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

636369

with good stirring at 0-5 °, a mixture of 11.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) aminobenzene, 12.3 parts of N- (2 '-acetoxypropyl) -N- Add dropwise (2'-cyanoethyl) aminobenzene and 20 parts of acetic acid. The separated dye mixture is isolated by filtration, washed acid-free, dried and finely divided by conventional methods with the addition of dispersants. The dye preparation obtained in this way meets all the application requirements.

Example 7

20.7 parts of 2,6-dichloro-4-nitro-l-aminobenzene are introduced into 95 parts of concentrated sulfuric acid and stirred. 32 parts of 40% nitrosylsulfuric acid are run in at 15-20 ° and the mixture is subsequently stirred at 20-30 ° for 3 hours. The diazonium salt solution thus obtained is poured into 600 parts of ice water with thorough stirring. A mixture of 4.6 parts of N- (2'-acetoxyethyl) -N- (2'-cyanoethyl) aminobenzene, 19.7 parts of N- (2'-acetoxypropyl) is added dropwise to this template at 0-5 ° ) -N- (2'-cyanoethyl) aminobenzene and 20 parts of acetic acid. The precipitated dye is filtered off and washed acid-free with water. The dye present as a moist press cake is then mixed with 300 parts of water. The homogeneous dye suspension is poured into a steel autoclave and kept under elliptical shaking movements, the frequency of which is 120-140 / min. is 105-110 ° for 3 hours. After cooling and filtering, a dye mixture is obtained which is stable against thermal influences and which, in the form of a dye preparation prepared by customary methods, meets all the application requirements.

Example 8

600 parts of water and 194 parts of 1-acetylamino-4-ethoxy-3-aminobenzene are placed in a V4A autoclave. The autoclave is then flushed with nitrogen until it no longer contains atmospheric oxygen. The mixture is then heated to 55 ° and the amine initially charged is mixed with a mixture consisting of 52.8 parts of acetylene oxide and 69.6 parts of propylene oxide over the course of 2 hours, the temperature rising to 62 °. The mixture is stirred at 60 ° for a further 6 hours and then the reaction mixture is cooled to 5 °. To remove the excess ethylene and propylene oxide, the reaction vessel is evacuated for a few minutes using a water jet pump and then flushed with nitrogen. The autoclave is then opened and the product which has precipitated in crystalline form is filtered off, washed with a little cold water and dried in vacuo at 60 °.

148 parts of the dried product are dissolved in 150 parts of glacial acetic acid in a sulfonation flask. 122 parts of acetic anhydride are added dropwise to the resulting solution at 80-90 ° in the course of 1 hour. The reaction mixture is then heated to 110 ° and stirred for a further 3 hours at this temperature, after which no unesterified portions can be found in the thin-layer chromatogram. The coupling component mixture obtained is cooled to room temperature and can be used without further treatment for the preparation of the dye mixture described in Example 9.

Example 9

31.1 parts of sodium nitrite are slowly added to 540 parts of concentrated sulfuric acid at 60-70 ° with vigorous stirring. The mixture is stirred at 60 ° for a further 10 minutes, then cooled to 10 ° and 117.9 parts of l-amino-2-bromo-4,6-dinitrobenzene are added. The diazotization is complete after 3 hours.

The diazonium salt solution thus obtained is added at -5 to + 2 ° in the course of 30-40 minutes, with vigorous stirring, to a mixture of the coupling component solution obtained according to Example 8, 450 parts of glacial acetic acid, 3000 parts of ice and 9 parts of aminosulfonic acid. The dye mixture forms quickly and precipitates. The reaction mixture is stirred at 0-2 ° until the detection of diazo-binding is negative. The dye suspension is then adjusted to pH 6.0 to 7.0 by dropwise addition of 30% sodium hydroxide solution. The mixture is then heated to 85 ° in the course of one hour, maintained at this temperature for 1 hour and stirred at 90 ° for 1 hour, during which the individual dye components change into a thermostable form. The dye is then filtered off, washed with 5000 parts of hot water and then dried in vacuo at 80 °.

Example 10 (application examples)

a) In a beaker with 2000 parts by volume, 78 parts of the dye mixture obtained according to Example 9 and 222 parts of a commercially available lignin sulfonate in 100 to 150 parts of water with 800 parts by volume of silica quartzite beads and a two-plate stirrer for about 6 hours at 20-30 ° milled at 2000-2500 revolutions per minute. The batch is then diluted with approx. 300 parts of water and filtered through a G 1 glass filter in a suction bottle. The dye and dispersant particles adhering to the silica quartz beads are rinsed quantitatively into the feeding bottle with a little water. The dispersion thus obtained is adjusted to pH 6 to pH 6.5 with 10% phosphoric acid and then atomized on a laboratory atomizing dryer (hot air 130 °, internal temperature 55-60 °). 3 parts of the dye preparation thus obtained are stirred with 4000 parts of 60 ° warm water. With this dye liquor, 100 parts of polyester fiber fabric are dyed for 1 hour at 98 ° with the addition of 20 parts of ortho-phenylphenol. After cooling, rinsing, soaping, rinsing and drying again, a navy blue dyeing of high fastness level is obtained.

b) 7 parts of the dye mixture prepared according to Example 1 are ground in a ball mill for 48 hours with 4 parts of sodium dinaphthylmethane disulfonic acid, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate to a fine powder.

1 part of the dye preparation thus obtained is pasted with a little water and the suspension obtained is added through a sieve to a dye bath containing 3 parts of sodium lauryl sulfate in 4000 parts of water. The fleet ratio is 1:40. 100 parts of cleaned polyester fiber material are then added to the bath at 40-50 °, 20 parts of a chlorinated benzene emulsified in water are added, the bath is slowly warmed to 100 ° and dyeing at 95-100 ° for 1-2 hours. The red colored fibers are washed, soaped, washed again and dried. The level dyeing has excellent fastness properties.

Analogously to the preceding examples, the disperse dye mixtures from the following table are also prepared.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

nBjqauuBui

Sfr EH0 = X es H = X

utiBjqqpS

3§UBJ0

tiBiq tu -) - = ÎY

unBjq OS

H H = 'X

nBiqauuBui

OS EHO = X OS H = X

OS £ HO = X OS H = X

OS £ HO = X OS H = X

CHD = ZX Q7 H = ZX EHD - »X H - lX

OS EHO = X OS H = X

% \ on% iow% i ° w

J3) S3jÇ) Od jnE aouen ^; ajusuoduio ^ f ■ £ ajusuoduiojj ajuauodtiio)} (

npv> i

X HOOOHR as eHD03HD3HD0DHDZHDHN = N "\ C ^ ~ N30

'HOC

'ON

91

sh9d ~ ôoohdzhd-nozhozho-

10th

; n- © -K - H-O- ^ 0

TO

SI

sh9o-ozhoooohozho.

7 7 /

NO HO HO

N = N - {^ - NZ0

n

Ç 17

HOOOOHO HO-

eHDJHOZBOSID

0ZX

£ "'7

HOOOOHO HO.

£ hoodohdzho ■ "T '

'HO NO

= N-fe> "NZ0

NO

0 10.

"N - \ 0) - N = N-y N 0 10

0 X

egg

ZI

o X £ z - H000HN

ag

H00 H0 H000-HO-HO ^> -a 7

3 ^ n- <Q> -N = N- <0) -N 0

Vro ^ zM

II

| 31UJ0J 3UJ3U13§HV "° N

Example No. General formula

17th

V-®-. =

nhcoch.

chch2cooch3 'ch2ch2cooch3

18th

° 2N ~ ^) ~ N "N" © ~ N:

-ch „choco-c h 2. 6 5

-ch2ch2cn

19th

Cl n n

X1 °

t X II

• ci ^ chococh * ch chococh

^ i ti 3

X2 °

20th

Cl

ON-a- * = N ^> - N

Cl

Xi 0

^ ch2chococh2ch3 ch chococh „ch

L i ,, ^ J

x2 °

21st

02n- <o> -n

X10

I II

ch2chococh3 ch chococh z t ,, Ó

x2 °

Table (continued)

1st component 2nd component 3rd component Nuance on polyester

Mol% mol% mol%

Xi = H XI = CH3 XI = CH3, ft,,,

X2 = H 25 X2 = CHj 25 Xz = H 50 scarlet fever

Xi = H 50 Xi = CH3 50

orange

^ 25 CH3 Xi - H ..

Xa = H ° Xi = CH3 25 X2 = CHj 50 yellow-brown

X, = H X. = CH3 Xi = H "

X2 = H 23 X2 = CH3 25 x2 - CHj 50 yellow-brown

Xi = H X, = CH3 "X, = H". ,,

X2 = H 25 X2 = CH3 25 X2 = CH3 50 man blue

Table (continued)

Example No. General formal 1 component

Mole%

24th

X2

CN

/ ^ CH „CHOCOCH,

22 0 nÄN «N - ^) - N ^ 2 3 X> = H 25

^ CH CHOCOCH 2.t 3

X2

Ï1

-CH CHOCOCH

23 0 N-UJ) "N = N- (0) -N ^ = H 25

52N ~ @ "N = n- ^ 5) -n

CH2CHOCOCH (CH3) 2

X1

Xz = H

VCH CHOCOCH NHCO-C.H. 2 <3

6 5 X2

CN X1 m

// CH CHOCOCH

O2N- <Q) -N = N ^ VN ^ X. = H 25

CH CHOCOCH 2, "3

X2 °

CN

r-f "^ -CH" CH "CN

25 02N "^ / N = 2 2 Xi = H 55

N. s CH CH CN

(gf VN ^ - ^ - N ^

0 CH-CHOCOCH

2 l * 0

X,

2nd component 3rd component nuance on polyester

Mol% mol%

X! = CH3 Xi = H

X2 = CHî X2 = CHS 30 red

Xi = CH3 XI = H ",,.

X2 = CH3 25 X2 = CH3 50 scarlet

X, = CH3 X.-H

X2 = CH3 5 X2 = CH3 50 red

Xi = CH3 45 - red

Xi = CH3 50

red

tiBjq

JJ3J0IA Siipijs; oj

JOJ

JOJ

uiqru

OS

ehd = zx

H = 'X

çz

EHD = ZX £ H3 = "x

OS EH3 = 'X

OS EH3 = 'X

OS EH3 = 'X

OS EHD = 'X

3c. | ° N

JS] S3. {| OJ jnESDUEnf *; SlUSUOdUIO ^ I £ siusuoduio »-J

* X c

C '7 HO 7

HOOOOHO HO— _J MO

p1 "

sz H = 'x C 7 = K-if | [le

H = IX HOOOOHOHO ^ Il «

ZON '

~ P *

OS H = lX n O £ 0

Z N O

Tx e

CH00ZH0ZHOOO03H0HÔ roçxmN

OS H = 'X 7 7 / K- (OyK = K- {QhR0 6Z

NO HO HO- ^ y ~ ^

10th

OS H = 'X

NOZHOZHO-CHOOOOHOZHO

XN - ^^ ~ N = N - ^^ - NZ0

2Z

NO

OS H = 'X

CHOZHO ^

Ç 9 Z Z

H 0-0 HOOOOHO HO-

N = N ~ ^^ ~ nZ ° LZ

£ 7. /

£ hozos ol <HS '

siusuodujo'x i puiJOj sutsuisSiiv on dsg

(SunzidSiJOj) sijaqvx

Example No. General formula

32

33

ci xx ci ^ vA,.

ch ch0cn 2 2

X1 °

CN '1 »

, ^ -CH CHOCOCH

ON N = N- <g) -NC "L 3

CH CHOCOCH

II ^

34 ° 2N N = N - ^) - N '

Br x2 0

Î1

-CHCH.COOCH, 2 3

~ CHCH "COOCH

, 2 3 x2

Cl

/ ✓CH CH CN

35 O N-O-H = N ~ (5V

zw w QHCHCOOCH

L | 3rd

xi

CN Xi 0

»* - n r-J f-. s ch.chococh.

36 0 "N— \ OV ~ N = N- <OVN. 2 3

02N - ^> - N = N - / p) ~

ch "chococh, CH" 2 "and 3

3 X 0

Table (continued)

1st component 2nd component 3rd component Nuance on polyester

MolVo MoI% MoI%

Xi = H 50 X2 = CH3 50 - scarlet fever

X: = H - Xi = CHa X: = H. .

X2 = H 25 X2 = CH3 X2 = CH3 50 ruby

Xi = H 0, Xi = CH3 0, XI = H, n ".IM, ™ ,,"

X2 = H X2 = CH3 X2 = CH3 0 yellow-brown

Xi = H 50 Xi = CHj 50 - Scarlet xi = H -, Xi = CH3 », X. = H X2 = H 5 X2 = CH3 5 X2 = CH3

Example No. General formula

38

39

X,

cn i1

/ _ ^ ch0 chococh "

^ ^ 2 3

choch0c0ch „2, 3

X2

37 0 ^ - ^ - N = N— ^ 3 ^ -!

NO OCH3 Î1

/ 2 _ / / chch cooch

V-0- N - N ~ 0 ~ N

/ chch.cooch nhcoch i 2 3

3 X2

X1

0 t1

.. / —n / chch cooch h3coc - @ - n = n 2 3

4c0CH ^ CH2COOCH3 X2

'ch ch cn

40 -

02n-§-n = n— ^ 5} -n:

* ch chocn (ch -) -

£ f ff J /

V

r— \ ch ch cn

4i 02N "^ Ö) -N - 2 2

^ choch0cnhc, h 2. 4 9

Table (continued)

I. component 2. component 3. component shade on polyester

Mol% mol '/ o mol%

^ 25 CH3 »c Xi - H

X2 = H 25 X2 = CH3 25 X2 = CH3 50 rubm

Xi = H Xi = CHs 0, Xi = H. ,. . ,.

X2 = H 25 X2 = CH3 25 X2 = CH3 50 reddish male blue

Xi = H ,, Xi = CHs -, Xi = H

X2 = H 25 X2 = CHa 25 X2 = CH3 50 ° range

Xi = H 55 Xi = CH3 45 - red

Xi = H 55 Xi = CHs 45

orange

Example No. General formula

Cl

42

° 2n ~ \ 2) -n = n- <o> -n. ^ C1

• ch2ch3

'ch chocnh-c.h- ^ i u 6 5

xi0

r-f1 / CH CH CS

^ 2 "M = M - / () \ ^

NHCOCH, -CH2® «° ™ 3

X1

44 <y- © -H - N- ^ 5) -

Ï1

^ ch chococh N ": •

^ • ch „ch„ cn

2 5

nh coc h 22

45 <Q> -N = N- ^ 5) -N = N- '

Î1

ch2chococh3

/ ch ch cn nh coch 2 2

3rd

46

Cl och.

02n "O" n = N - ^) ~ N '

?!

■ ch2chococh

\ / -ch.chococh no? nhcoch chc1 2i 3

2 2 x "

Table (continued)

I. component 2. component 3. component shade on polyester

Mol% Mol «. Mole%

Xi = H 50 Xi = CH3 50 - brown

Xi = H 50 Xi = CH3 50 - red

Î1 25 v 'SS 25 50 scarlet fever

X2 = H Ä2 = Bh3

Xi = H 50 Xi = CH3 50 - scarlet fever

Xl = H ,,, Xl = CH3 -, Xl = H, n marinphlaii

X2 = H X2 = CHs 5 X2 = CH3 5 navy blue

Table (continued)

Example No. General formula

I. component

Mole%

2nd component

3rd component

MoI%

Mole%

Nuance on polyester cn

47

och ch och3 * 1

^ -ch -chococh „2 3

0_n <1

z ■ ch -chococh "

n

0

Xl = H X2 = H

25th

Xi = CHs Xa = CHs

25th

Xi = H X2 = CHs

50

brown

48

Cl

02n- ^ ~ n = n- ^ 5) -n

• ch2ch2cn ctlchococh nhcoch choch 2, 3

»2 3 Xl

0 1

Xl = H 50

Xi = CHs 50

red

49

Cl

02n - <^ - n - n - * ^ ö) -n:

Cl

■ ch2ch3

* ch chococh

I ^

Xl = H

50

Xi = -CÓH5 50

brown