DE2009390A1 - Dye, process for its preparation and its use for coloring polyesters - Google Patents

Description

PATENT LAWYERS DIlMOLLER-BORe-DR-MANITZ-DR ₁ DEUFgL iftrtn ^ At DIW - ING. FINSTERWALD'- DIPL-ING. QRÄMKOW 2009 390

■ "-. · MÖNCHEN 22, ROBERT-KOCH-STR. Ϊ́

• Telefon2251 IO 2 ?. February 1970

Lo./Sv - S 2122

SUMITOMO CHEMICAL CO., I / M). 15r 5-chome, KitahamaY Higashi ~ ku, Osaka JAPAN

Dye, process for its manufacture, and its uses for coloring polyesters

Priorities*. Japan from 2? February 1969 »& r. 15078/69 Japan το «August 12, 1969» Ar. 6 * 063/69 Jap ^ n from 12. S «pt but 69» 5r. 73016/69 ?: Japaa ^ S, January 1970, ^ · 276V70

The invention relates to the coloring of polyesters and. in particular novel dyes which are used for mass coloring of synthetic polyesters, processes for their production and their use for coloring a such material.

Thus a dye satisfactory for maea coloring ▼ Ott polyesters used verdea can, ailgenftinen meet the following conditions s

009S3S / 211?

{Λ ) the dye must be stable enough at the polymerization temperature or at the temperature at which the Pol; naeriEao is formed into the molded article, or at which such molded articles are processed;

(2) the volatility must be under the above conditions be low enough »since the coloration, if the volatility is high, is irregular or uneven and the neighboring object (e.g. a fabric) could be discolored;

(3) the dye should have high fastness or durability against light and the effects of cleaning solvents, Own sweat and bleach. ·

It has now been found that certain frerfcetoff · sit three

up to eight condensed or merged. Bingen dit above- ♦ * ■ ■

meet the specified conditions. . -

In particular, the dye is used for the coloration of Polyesters according to the invention represented by the general formula (Z):

CH ₂ -N- COR ₂

wherein A is the imino group or a sulfur atom, 2 is hydrogen atom, an alkyl group, an alkoxy group or a halogen atom and m and η each represent an integer from 1 to 4

BATH ORIGINAL

009838/2117

where A can be different if η is 2 or greater, and D represents a dye radical which consists of 3 to 8 fused rings, each of which has no sulfonic acid group, but with one or more hydroxyl, amino, nitro radicals , Halogen atom (s), alkyl, alkoxy, H-alkylamino, arylamino, Gycloheacylaaino- or carboxyl radical (s), etc. can be substituted, and R .. and R _{2 have} the meaning given below. The invention also relates to the use of one or more of these dyes. In the invention, the Auedrücke "alkyl and ^11" represent alkoxy reete "iolche alkyl" and Aikoxyreste »it Λ lenetoffatoeen to 5 Koh.

The dye of the foreel (I) can be produced inde »a · reproduced by the following general photo # 1 (H) ·

(II)

k -

where A, Z, D, ab * w. η have the meaning given above and in which, if η 2 is 2, A can be different with a compound which is represented by the following general formula (III):

(III)

BATH

008831/2117

wherein T eir.en HydroxyIreet, a halogen atom. an alkoxy or alkylamino radical, R, - mean a hydrogen atom, an alkyl radical or -CO-R, and if R ^ represents a hydrogen atom or an alkyl radical, R _{2 is} a saturated or unsaturated one, with a carboxyl group, a carboxyaryl group or their * Esters-substituted alkyl radical, an aromatic radical substituted with a carboxyl group, a carboxyalkyl group or their esters, or an aniline radical which means. is substituted with a carboxyl group and which can additionally be substituted with an alkyl radical, an alkoxy radical or a halogen atom, and fells IL

»Represents the radical -CO-R _x , R ₉ and R, Qj connected to one another. with the meaning -C «· C- or -CH p

I \ COOH

represent -

and Re and Rg each connected to each other represent a best, representing a benzene ring substituted with a carboxyl group or its ester, in a solvent and optionally reacts in the presence of a catalyst, or with one of the general formula (IV) reproduced connection:

HR - COR ₂ (IV)

wherein R ^ and R ^ have the meanings given above, in the presence of formaldehyde, paraformaldehyde or di (halo genmethyl) ether reacts, or with one by the general Formula (I) for the given compound:

NC - R ₁₇ (V)

BATH

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wherein R "is a saturated or unsaturated one, with a Carboxyl group, a carboxyaryi group, or their esters. 'Substituted alkyl radical or an aromatic, with a Carboxyl group, a carboxyalkyl group or their Ester-substituted radical means in the presence of Formaldehyde, paraformaldehyde or di (halomethyl) ether implements.

The solvent used in the above-mentioned condensation reaction can be JO to 98% sulfuric acid, 70 to 85% phosphoric acid or a lower fatty acid such as formic acid or acetic acid, among these compounds sulfuric acid is particularly preferred.

The reaction temperature is not critical. The reaction can be carried out at O ⁰ C to 12O ⁰ C, usually at room temperature.

As a catalyst, those can be used which for usually used in tfriedel-Crs.ft 's reactions, e.g. anhydrous zinc chloride, anhydrous aluminum chloride, Boron trifluoride or phosphorus oxychloride.

Examples of compounds of the formula (II) which are used in the Preparing the dyes of the invention can be used can, are? 1,4-, 1,5- or 1,8-dianilinoanthraquinone, 1 »4-, 1,5- or 1,8-di (phenylthio) anthraquinone, 1,4-, 1,5- or 1,8-di (2-, 3- or 4-toluidino) anthraquinone, 1,4-, 1,5 or 1,8-di (2-, 3- or 4-methylphenylthio) anthraquinone, 1Λ- »1-ϊ5- or 1,8-Di (2-, J- or 4-anisidino) anthraquinone, 1 »4-» 1,5- or 1,8-di (2-, 3- or 4-methoxyphenylthio) anthraquinone, 1,4-, 1,5- or 1,8-di (2-, 3- or 4-chloroanilino) anthraquinone, 1,4-, 1,5- or 1,8-di (2-, 3- or 4-chlorophenylthio) anthraquinone, 1i4? -, 1,5-oddr 1,8-dimesidinoanthraquinone, 1,4-, 1,5- or 1,8-di (vic-m-3qflidino) aathra-

■ ■■■ '■; . - 5 ■ -

001131 / ^ 11?

cbinon, 1,4-, 1,5- or 1,8 ~ di (2, S-diethylanilino) aathraquinone, 1,4-, 1,5- or 1,8-di {2,6-dimethyl-4- -t-but; planilino) ant; hrachinon, 1,4-, 1 »5- or 1,3-di (2,6-di ~ ethyl-4-n-butylanilino) anthraquinone _t 1,4-, 1, 5- or 1,8-di (2,3,5,6-t-tramethylanilino) anthraquinone, 1,4,5,8-tetraanilinoanthraquinone, 1,4,5,8-tetra'phenylthio) onthraquinone, 1-amino "2-phenylthio ~ ⁱ ! - anilinoanthraquinone, 1-AmiD.o-2-phenylthio-4- (2-, 5- or 4-toluidino) anthraquinone, 1 ~ amino-2,4-di (phenylthio) anthraquinone, 1 ~ aiiino ~ 2,4-di (2-, 3- or 4-methylphenylthio} anthraquinone, 1-amino-4- (4 «methylphenylthio) anthraquinone, 1" fiethylamino ~ 4 ~ (phenylthio) anthraquinone, 1- ^ nilino -4-, 5 "or ö-pheuylthioanthr.iquinon, 1,4-üihydroxy -. '5-aniIiEo ~ 8 ~ phenylthioanthraquinone, 1 ^ -dianiline-4,8-dihydroxyant; hraquinone, 1,8-dianilino-4,5- dibydroxyanthraquinone, 1,4 ~ dianilino ~ 5-nitro-8-hydroxyanthraquinone »1» 5-di (phenylthio) -4,8-dihydroxyanthraquinone, 1,8-di (phenylthio) -4,5-dihydroxyanx; hrachinon, i- Cyciohexylainino-4-toluid inoanthraquinone, i-methylamino - ^ - aniaidinoanthachinone, 1-methylamino-4-toluidinoanthraquinone, i-cyclo-hexylamino-4-aniaidinoanthraquinone, 1-kesidinoanthraquinone, 1-0xy-4-mesidinoanthraquinone, 1-oxy-4-mesidinoanthra-4- ( -xylidino) anthxachinon, 1 '4 ~ diamino-2,3-di (phenylthio) anthraquinone, S-anilino-3 ^1, 4'-phthaloylacridone, 6-phenylthio-3'"4·" phthaloxylacridon, 4-anilino-2 -methyl-l '(N), 9 ¹ -anthrapyridine, 6- (4-toluidino) -3 * »4 ^> -phthaloylacridone, 6- (4-chlorophen33thi.o) -3', 4'-phthaloylacridone, 6- Anilino-1 ', 9'-anthrapyrimicon, 6- (4-anisidino) -3-methyl-I (N), 9'anthrapyridone, 5-anilino-l', 9 '(N) -isothiaz leenthron, 7- Hienylthio- ¹ , 9 '(N) -isothiazolan-throne iind 4', 5'-di (4-methylphenylthio) -1 ', 8' -naphthoylenebenzimidazole.

008838/2117

All compounds represented by the general Jtoruel (III), which can be used in the hexification of the dyes according to the invention, may be mentioned, for example: H-methylolmalonic acid-monoainld, N-Msthyloibernet; one-acid-mono-amide, N-methylol-tere (or iso) phthalic acid monoafflid, N-methylol-4-cBxboxyphenylacetamide, H-methylol-4-carboxyinethylberizaiiid, N-methylol ^ -methyl-terephthalic acid monoamide, N-methylol-trimellitimide, N-methylol-C ^ -carboxybenayl) succininide Chloro- or bromo-methyl) -malonic acid-monoamide, N- (chloro- or brom-methyl) succinic acid-monoamide, N- (chloro- or bromomethyl) -trimellitimide, N-methylol-lf-i-methylterephthalic acid-monoamide, N ₁ H '-Methylene ^ bis (carboxyacetamide), bis (malonic acid-iaonoamidomethyl) ether, N-methylol-2-, 5- or 4-ureidobenzoic acid, N-methylol-ft-ureido-2-methylbenzoic acid, N-methylol-3- " ureido-benzoic acid, N-methylol-4-ureido-: 2-methoxybenzoic acid and its lower alkyl esters

The above-mentioned N-methyloleic acid amide compounds or H-ltethyloleaureimide compounds can be easily prepared by heating the compound represented by the formula (IY) in an aqueous solution of foraalin. ^:

As compounds represented by the general Porsel (IT), which are used in the production of the compounds according to the invention Dyes can be used, aeien the Seureamide and acid imides listed * which are the precursors of the above all examples of the compounds represented by the general formula (III) have been mentioned *

009831/111?

Examples of represented by the general formula (V) Compounds which are used in the preparation of the invention Dyes that can be used are: cyanoacetic acid, ß-oyanpropionic acid, T-cyanobutyric acid, 3- or 4-cyanobenzoic acid, 4-cyanomethyl benzoic acid, 4-cyanophenylacetic acid, ß ~ (4-cyanophenyl) propionic acid, 4-cyanosilbene-4'-carboxylic acid, 2-methyl ~ 4-cyano-benzoic acid, 4-chloro- or 4-Methoxy-3-cyanobenzoic acid and its lower alkyl esters.

The one shown by D in the general formula (I) Dye residue includes the following two groups:

* (1) Anthraquinone or derivatives thereof, which by the the following formula can be reproduced:

wherein X is a residue of a heterocyclic Hingee containing a nitrogen atom or a nitrogen and sulfur atom, and more specifically, the groups represented by the following formulas: 9

N-CH ₃ ; H ^ N; - H ₅ NS or

N-NH

Il I

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or by the formula:

(2) Naphthalene derivatives represented by the following formulas:

or

In the case of the above-mentioned dye residues, the anthracite

j ^ erne

quinone and naphthalene substituted s * in with hydroxyl, Amino, Vitro, a halogen, alkyl, alkoxy, N-Alkylaiiino, Arylamino, cyclohexylamino or carboxyl.

001131/2117

The dye of the present invention can be used in a usual manner. Thus, one or more of the dye (s) represented by the general formula (I) given above can be added to a polyester in a manner known for mass dyeing and mixed therewith. For example, a finely comminuted dye can be applied in a foiling drum to coat chips made of polyester and the resulting colored mixture can then be melted and shaped into single threads or other objects. If necessary, the above-mentioned mixing or application in the polishing drum can be carried out using a dispersion of the dye in a volatile liquid such as water, alcohol or ethylene glycol ether (Cellosolve), or such a liquid can be used to moisten the mixture of dye and polymer. It is also possible to produce the polymer in the presence of such dye / s. For example, monomers such as terephthalic acid or dimethyl terephthalate, a glycol, 7..B. Ethylene glycol, and one or more of the above-mentioned dyes are mixed and heated to carry out the polymerization, whereby a colored polymer is obtained. The colored polymer produced can be shaped into objects such as threads or films in a known manner. In addition, it is also possible to produce a prepolymer or precondensation and then add the fax element. The mixture is then subjected to further polycondensation until a desired degree of polymerization is achieved.

Polyester which can be colored according to the invention is, for example, one by the polycondensation of terephthalic acid and / or isophthalic acid or esters thereof with glycol of the formula:

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009131/2117

HO - (CH ₂ ) _W - OH

(where w is an integer from 2 to 10 bedsutet) or 1,4-di (hydro: <ymefchyl) cyclonexaja "obtained polyester. The term "polyester" as used herein includes copolyesters. Such a copolyester can be obtained by making part of the above-mentioned dicarbon. acid by another dicarboxylic acid or an oxycarboxylic acid and / or by part of the above-mentioned glycol be replaced by another glycol. Since these polyesters and copolyesters and their manufacture good in itself are known, further explanations are not required. '

The colored products obtained by the process according to the invention have good resistance to light, vapors under pressure, perspiration and rubbing steaming and heat treatments in the case of ironing. The color has a deep tint and the coloring can without deleteriously affecting the desired properties of the polyester or meraus molded articles.

The invention is illustrated with the aid of the following examples, without thereby limiting it. In the examples, the parts of the data and percent always relate on weight. '

example 1

4 TIe. 1,5-Dianilinoanthraquinone are available in 60 TIn. 95% iger Dissolved sulfuric acid. 4.4 TIe. Cyanoic acid become. To given to the solution and completely dissolved. Then will

0 098 38/2117

while the solution is cooled with water, 1.6 TIe. Paraformaldehyde one after the other in small amounts to the solution
admitted. This reaction solution is stirred at room temperature for 20 hours. The solution is in 600 ¹ JJIe .. cold water
poured. The crystals produced are filtered off,
washed with water until neutral and dried.
The yield is 5.6 TIe. This dye has the following formula:

HC _o CCH _o C0NHCH

Example 2

100 tie. Dimethyl terephthalate, 71 Tie. Ethylene Glycol, 0.05 Tie. Manganese acetate and 0.04 Tie. Phosphoric acid are ^{stirred together at 197 °} C. for 4 h. The methanol formed as a by-product is distilled off. Then add 3 teas to this mixture. of a dye as it was prepared in Example 1 and previously with 12 TIn. Ethylene glycol had been moistened by grinding in the ball mill for about 30 minutes, was added. Then the temperature becomes the
Mixture increased to 277 ⁰ G and the pressure decreased to 0.3 mm Hg. Under these conditions, the increased
Maintain temperature for 6 h to eliminate any excess
To distill off ethylene glycol. The melt is formed into threads that are drawn. The drawn threads thus obtained are colored in a reddish purple color, which
has high lightfastness and heat resistance. ·

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009838/2117 _ßAD

At CDlel 5

4.7 tie. 1,4-Dimesidiaoanthraquinone are in 70 TlQ. Dissolved 85% sulfuric acid. It will be 7.5 TI. ··. 4-chloro-1-cyanobenzoic acid is added to the solution and the solution is stirred until completely dissolved. Then there will be a 5.7 tie. Di (chloromethyl) ether was added dropwise to the solution one after the other. After the dropwise addition, the solution is stirred at room temperature for 20 hours. The reaction solution is allowed to flow into 700% cold water. The crystals produced are filtered off and washed with water until neutrality. When the cake is dried, 7 * 9 TIe. blue crystal · preserved. _; . .

This dye has the formula ί shown below

CH ₂ NHCO -

-CH,

0 NH - 6} -CH,

CH ₃ Nm ₂ ETHCO -

009638/2117

Example 4

1 part of the dye prepared in Example 3 is together with 100 TIn. Polyethylene?; Srophthalate in the form treated by chips in. the polishing nuisance. If the The mixture thus produced is melt-spun in a known manner blue-colored threads are obtained, which have excellent lightness and heat resistance exhibit.

If chips of a copolyester of 75 % ethylene terephthalate and 25 % ethylene phthalate are used instead of polyethylene terephthalate and these are dyed by the same process, a dyed product is obtained from them by molding them into polyester filament in the form of a dyed product which has excellent fastness.

Example 5

4.2 TIe. 1,5 ~ I ⁾ iCphenylthio) anthraquinone are completely in 84 TIn. Dissolve 95% sulfuric acid, and while this solution is cooled with water, 7.7 Tie. N-methyloltrimellitimide was added one after the other in small proportions. Then the solution is stirred for 15 hours while being kept at room temperature. The reaction solution is in 800 TIe. cold water poured in. The crystals produced are filtered off, washed well with water until neutral and dried. The yield is 11.3

This dye possesses the. following formula:

BAO

009838/2117

When V-bronethyl triaellitimide is used in place of the H-methyiol triaellitimide in this example and the Treatment is carried out in the same manner, the same compound as in this example is obtained.

Example 6

1 part of the dye produced according to Example '} and 3 parts. Ethylene glycol monoethyl ether (JLt hyl-Gel Io solve) are _: line with 100 TIn. granular polyethylene terephthalate treated in a polishing mill until a uniform mixture is produced. Venn stained "mixture at 120 ⁰ C in a vacuum, and melt-spun dried geIbgefärbtβ threads are obtained of good stability.

Example 7 .

4.5 TIe. 1,4-Di (4-toluiöino) -5,8-diliydroTyanthraquinone are sold in 70 TIn. 85% phosphoric acid dissolved. Εε become

- 15 · - "■". ■ '

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4.9 Tie. A — cyanobenzoic acid entered in d.io solution »while the solution is cooled with water, 1.5 Tie «paraformaldehyde given in small amounts one after the other. The solution is stirred at 30 to 35 ° C. for 15 h. This implementation solution becomes slow * in 700 tIe. Let ice water flow in. After this Was stirred for 1 h, the mixture is filtered to separate the crystals, these are washed with water until neutral washed. After drying, 7 »O TIe. green Get crystals. They have the following formula:

HO

If 2-pethyl-4-cyanobenzoic acid instead of 4-cyanobenzoic acid is used in the example, and the treatment is carried out in the same way, a compound obtained with a similar shade with the following porael:

- 16 -

BATH

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HO O NH-

HO (j)

- CO ₂ H

Example 8

100 tie. Dimethyl terephthalate, 71 Tie. ethylene glycol, 0.05 manganese acetate and 3 ϊΐβ. the dye obtained by the method of the example is stirred for 4 hours at 197 ° C. while methanol produced as a by-product is removed. 0.5 TIe. Triphenylphosphate and 0.05 ti-intimony triooxide are added. The temperature of the ItL se hung is increased to 277 ⁰ C, and the pressure is reduced to 0.3 to Hg. The mixture is kept under these conditions for 6 hours. Meanwhile, excess ethylene glycol is distilled off. Then the mixture is shaped into threads which are drawn. The drawn threads obtained are colored green and have excellent fastness properties.

Example 9 :

4.2 TIe. i-Amino ^ -phenylthio- ^ i-anilinoanthraquinone, in 63 TIn. Dissolved 85 # sulfuric acid. It will be 8.0 TIe. 4-cssranfflethylbenzoic acid added and completely dissolved. While the solution is cooled with water,

Paraden 1.5 TIe ./formaldehyde added in small amounts.

The solution is ^{kept at 50 °} C. for 20 h. The reaction solution

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will tie in 700. Let water flow in. The generated Crystals are filtered off, washed with water and dried, 7.2 TIe. blue crystals are obtained. The compound obtained has the structure represented by the following formula:

Beiapltl 10

75 TI ·· Dimethyl terephthalate, 2? TIe. MeethyUiophthelat, 100 TIe. Ethylene glycol, 0.035 teas. Hanganaeetat and 1 tsp. Of the dye obtained in Example 9 are heated raaoh until the temperature to 100 ⁰ C 105 bia rises and 5 held h at this temperature, while a by-product produced methanol is distilled off. Ss were 0.03 TIe. Antimony trioxide and 0.4 TIe. Triphenylphoephate added here. The temperature of the mixture is increased to about 285 ° C and its pressure is reduced to 0.3 »» Hg. The mixture is held under these conditions for 6 hours while excess ethylene glycol is removed. If the polymer obtained is shaped in a known manner, a green-colored polyester film is obtained which has excellent fastness properties.

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In the following table / are those made using the same procedure as in Example 1, 3 »5» 7 or 9 synthesized - Dyes listed in the second column and the color tints of polyester dyed with these stains by the dyeing process of Examples 2, 4, 6, 8 or 10 are given in the third column:

Table I. example

dye

hue

11 12 13

15th

16 17 18 19 20 21 22

I ₁ ^ -DiCcarboxyacetamidomethyl ^ ani lino) anthr aquinone ^, B-Di ^ carboxyacetamidomethylanilino) anthraquinone i ^ iCmiioey methoxyanilino) enthraquinone 1, ^, 5 »8-tetra (carboxyacetamido methylanilino) anthraquinone

i ^ -DKcarboatyacetanidomethyl ani lino) -5-nitΓθ-8-hydroxyanthraquinone

toluidino) anthraquinone

1,4-di (trimellitimidomethyl-4 tοluidino) anthraquinone i.e-DiCtrimellitimidomethylphenylthio) anthraquinone

1-amino-2,4-di (trimelli-timido -methyl ani lino) anthraquinone

methyiphenylthio) anthraquinone 1,4-Di ^ (4-carboxyacetainido- · methyl) masidino J anthraquinone i ^ -DKtrimellitimidomethylphenylthio) anthraquinone

greenish blue

purple green

greenish blue

green yellow green red

blue

bluish red

-19 -

0 09838/2117

_ΒΛ0

greenish blue

blue

1, A-Di C ^ -carboxybenaamido- ·.

methyl) anilinoj anhydrous quinone

'!, ^ - DiCcai-boxyacetamidomethylvic-m-xylidino) anthraquinone

Ί, 4-Di Γ (3-carbomethoxybenzamido ~ "

Diethyl) -2,6-diethylaniIinoJ anthraquinone

1,8 ~ Dif (J-methyl - ^ - carboxybenaamido- blue methyl) -4-toiuidino ^ -4,5 ~ dihydroxyanthraquinone

1-amino-2- (trimellitiflidomethylphenylthio 5-4- (trimellitimidomethylanilino) anthraquinone

1-Amino-2,4-di £ (4-carboDcyphenylacetamidomethyl) phenylthioj anthraquinone

1,5-Di Γ (J-carboxybenzamidomethyl) -3-toluidino] [anthraquinone 1,5-di [ (3-carboxybenzainidomethyl) -4-oalortnllinoJ anthraquinone 1,4-01 Γ (3-c «? Boxyb« aMÄidoaethyl) -4-toluidinoJ anthrnquinone

(4-c ": boatybeutaaid (mrthyl) 7 tihi

, / Cy phenylthloj anthraquinone i-Cycloheaqjrlaaino - ^ - Ctrimellitieido-: methyl-4-anieidino) antbxachinon i-methylamino-4- / "C4-carbo3tybenzamido methyl; -4-toluidinoJ anthraquinone 1 _t 8-carboethoxy -

methyl) ~ 4-methylphenylthiq7 anthraquinone

i ^ -DiCcarboxyacetamidonethyl ^ - methylphenylthio) anthraquinone

i ^ -DiCtrimellitimidoaethylmeβidino) anthraquinone

bluish green

Red

purple

green

blue

bluish green

yellow

2, y anthraquinone

bluish red

blue

- 20 -

BATHROOM OBlGlNAL

009131/2117

1 ^ -DiCcarboxypropionaiiidomethyl-

2,6-dimethyl-4-n-butylanilino)

anthraquinone

ij ^ -DKcarboxybutyramidomethylvie-m-xylidino ) anthraquinone

1,4-di (4-trimellitimidomethyl-2,3 »5» 6-tetramethylanilino) anthraquinone

i-Hydroxy - ^ - Ccarboxyacetamidomethylmeeidino; anthraquinone

i-Hydroxy ^^ Ccarboxyacetamidomethylvie-m-sylidino) anthraquinone

1-Erdro3ty-4- (4-carboethoxybenzamidometnylmeaidino) anthraquinone

1,5-Di. (3 ^ carbomethoxybenzamidomethyl mesidino) anthraquinone 1,4-di (trimellitimidomethyl-2,6- ' dimethyl -A-t-butylaniline-oanthraquinone

.JKliao ph * nylthio) tnthTBquinone

i ^ -DiCtriBemtinidoae ph # aylthio) «ntaf achinon.

bluish red

blue

bluish red

jJDiCtrliwlUti dino) anthr «ßhinon

blue yellow

purple

Example 51

2 tie. 1,8-Dianilinoanthraquinone come in 30 tin. 95% iger Dissolved sulfuric acid. 3.5 tie. (4-0arboxybenzyl) succinimide are added to the solution in small amounts. 0.45 TIe. Faraformaldehyde are added to the solution in small amounts. The solution is stirred for 20 h at 20 to 25 ° C and then in 300 tIe. poured cold water. The generated Krietal-Ie are filtered off until neutral with Vasser wash and dry. The yield is 3 * 3

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This dye has the following JTormdl and it stains after the procedures of Examples 2, &, 6.8 or 10 Polysster in purple:

At Bplel 52

4.7 TIe. 1,4-Dimesidinoanthraquinone become ⁰ A TIn. Glacial acetic acid. There will be 1.5 tie. Boron trifluoride etherate added here. 6.6 tIe. N-methylol-trimellitimide are still included. The mixture is stirred for 20 h at 50 to 55 ⁰ O and then in 600 TIe. poured cold water. The crystals produced are filtered off, washed with water until neutral and dried. The yield is 10.3 TIe.

This dye has the formula below, and when polyesters are dyed with it according to the procedures outlined in Examples 2, 4, 6, 8 or 10, the result is a blue color:

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CHo - K

CO ₂ H

Example 55

4.2 tie. 1 _{l of} 4 ~ di (4-tol \ adino) anthraquinone are dissolved in 63 90% strength sulfuric acid. H-methylol-4-ureidobenzoic acid was added to the solution in small amounts. If the solution was stirred at ZiBMertemperatur 24 h, 8.5 TIe. 1,4-D1-phenylcarbamidomethyl-4-toluidino) anthraquinone obtained from Porael listed below. When pairing polyester with this dye according to the procedures shown in Examples 2, 4, 8, or 10, these are dyed green.

-GO ₂ H

CH ₂ NHCOHH - / ^ -CO ₂ H

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009838/2117

ti

Example 54

4.2 tie. 1,5-Di (4-toluidino) anthraquinone are used in 63 Tie. dissolved in 95% sulfuric acid. Ea will be 5 »4 tie. 3-ureidobenzoic acid added to this solution. 0.9 Tie .. Paraformaldehyde are incorporated into the solution in small amounts. The solution is at room temperature for 24 h stirred, with 9 »3 teas. 1,5-Di / ~ (3-carbo3cyph .enyl-carbamidomethyl) -4 ~ toluidinoj ' anthraquinone represented by the following formula. This dye dyes Po3.yester purple.

O-

NHCONHCH ₂

In Table II below, the picks are those synthesized by the same procedures as in Example 52 or 53 Dyes / listed in the second column and those with these according to the procedures of Examples 2, 4, 6, 8 or 10 colored polyesters are listed in the third column.

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Table II example

• 55 56 57 58 59 60 61

62

dye

hue

65

-Di jf {4 ~ carboxyphenylcarbamidohyl ') ^ me "bho3q7phenylthio" J antbra

chinone

1,4-Di / (3-carbo3cyphenylcarbamidomethyl} ~ 3 ~ culorphenyltnioJ7 anthraquinone

1,5-di / "i3 ~ carboxyphenylcarbamido-

iaethyl ^ i-ehloranij.inojy anthraquinone

1,5-Γα £ (4-c & rboxyplienylcarbamidomethyl} -vic-m-xylidi.no_7 anthraquinone

1,4-DiZ "(4-carboxy-3-methylphenylcarbainidomethyl ) -2,6-dimethyl-4-t-butylaniline qj anthraquinone

carbamidomethyl) -2.3.5 % 6-tetramethylanilino_7 anthraquinone

1-Amino-2- C (4-carboethoxyphenylcarbamidomethyDphenylthioJ -4- C (4-carboxyphenylcarbamidomethyl) -4-toluidinojf anthraquinone

1,4,5,8 ~ a? Etraf (3-carboxy-4-chlorophenylcarbamidomethyl) phenylthioj anthraquinone.

1,4-Di C C3-carbox7-4-chlorophenylcarbamidomethyl) anilino_7 -5,8-aihydi anthraquinone

I-Cyclohexylamino ^ - / (3-Oarboxy-

phenylcarbamidoniethyl) -4-anisidino] 7

anthraquinone

1-hydroxy-4- L (4-car ^D o ^ -3-methoxy-

phenylcarbamidomethyl) mesidino7

anthraquinone

yellow

purpxir

reddish purple

blue

bluish purple

Red

green

blue

bluish red

009838/2117

Example 66

4.5 tie. 6-anilino-3 ·, 4'-phthaloylacridone become complete in 63 TIn. Dissolved 95% sulfuric acid. There will be 3.3 TIe. N-methyloltriraellitimide in small proportions added to the solution. If the solution is then stirred for 20 h at room temperature, 7.0 TIe. dye obtain"

This dye has the following structure and it colors according to the procedures of Examples 2,4,6,3 or 10 polyester green.

Example 67

3.5 tie. 6-anilino-3-methyl-l '(N), 9-anthrapyridone vierden in 50 TXn .. 95% sulfuric acid dissolved. Ss will be 3.3 TIe. N ^ '- methylene-bisCcarboxyacstamide) gradually into solution given. If the solution is then stirred for 20 hours at room temperature, 4.2 TIe. of a red dye obtained.

This dye has that represented by the following formula Structure and colors polyester red.

- 26 -

009838/2117

- CH,

CH ₂ NHCOCH ₂ CO ₂ H

In the following Table III the names of the after same procedure as in Example 65 or 66 synthesized dyes indicated in the second column and the color shades of the polyester dyed by the same method as in Example 2, 4, 6, 8 or 10 in the third column. ~

Table III

Example 68

69 70 71 72 73 74

dye

hue

4 - / ^ (H-methyl-4 ~ earboxybenaamido-. Red "Ethyl) anilinoj 2-methyl1" (N), 9'anthrapyridine

6 - / "(4-Carbo3cybenzamidomethyl) - purple anilinqj -1 ', 9'-anthrapyrimidone

e-CTriiiellitimidomethylanilino) - red 3-methyl-1 '(R), 9' -anthrapyridone

5- (Triaellitimidomethylanilino) -1 9 ¹ (H) -ieothiazolanthrone

yellow

6- (Trimellitimidomethylphenylthio) - blue J ', 4 · -phthaloylacridone

6-! ('V-Carboxyphenylcarbemidomethyl) green anilinoj -5 ', 4' -phthaloylacridone

6- £ (j-Carboxyphenylcarbamidomethyl) - ^w 4-toluidinoJ -3 ', 4'-phthaloylacridone

- 27 -

it

Ib 6 - / ^ 4-Carboxyphenylcarbainidomethyl) - blue

phenylthio ^ -J ¹ , ^ '- phtha ^ oylacridon

4 ~ £ p ~ carboxyphenylarbamidomethyl) ~ red aniline, J -2 ™ 3-methyl-1 ', (N), 9'-anthrapyridine

6 ~ £ O ^ -Car-boxyphenylcarbamidomethyl) - purple anilineJ Ά ', 9' ~ anthrapyrimidone

5 - ^ "(4 ~ carboxypb.enylcarbamidomethyl) - yellow anilino J -1 ^f , 9 '(N) ~ isothia.zol-anthron 4', 5 '-Di Γ (4-carbo3qyphenylcarbaniidomethyl) - 4-methylphenylthioJ -1 · _S 8'-naphthoylenebenzimidazole

- patent claims -

- 28 -

_BAD 009838/2117

Claims (1)

Patent awards 1. Dye of the following general formula: R ₁
CH ₂ -IiOOR ₂ where D is a dye residue with 3 to 8 fused rings, none of which has a sulfonic acid group and each with a hydroxyl, amino, nitro, halogen, alkyl, alkoxy, N-alkylamino, arylamino, cyclohexylamine or carboxyl radical can be substituted, A represents an imino radical ¹ or a sulfur atom, Z represents a hydrogen atom, an alkyl radical, an alkoxy radical or a halogen atom, R ^ represents a hydrogen atom, an alkyl radical or the radical -CO-R _x and when R- is Hydrogen atom or an alkyl radical, Rg is a saturated or unsaturated alkyl radical substituted with a carboxyl group, a carboxyary group or its ester, an aromatic alkyl radical with a? Represents a carboxyl group, a carboxyalkyl group or its ester-substituted radical or an aniline radical which is substituted by a carboxyl group and which can furthermore be substituted with an alkyl radical, an alkoxy radical or a halogen atom, and when R ^ represents the radical -CO-R, Ro and R ,, which are connected to each other, represent R ₁ ^, where R ^ has the following meaning: - C »C - or -OH - OEU-R ₅ R ₆ - ■ 29 "- 00983872117 and R ₁ - and Hg, which are connected to each other, represent a radical _{forming a benzene ring substituted with a carboxyl group Λ} or its ester, and m and η each represent an integer from 1 to 4 and when η is> 2 , A can be the same or different. Dye of the formula N-CH CH ₂ -N, Dye of the formula / Vnh HO ₂ CCh ₂ GONHCH ₂ ti Il CH ₂ KHGOCH ₂ CO ₂ H QQ9838 / 2117 Par ¹ formula Dye of the formula Dye of the formula Il 11 Il CH ₂ N CH ₅ π HII - <f <> - CH Il I ₂ N Il - 31 -009838/2117 Dye of the formula CH ₅ OH ₂ NHCOCH ₂ CO ₂ H CH ₅ 'CH ₂ NHCOCH ₂ CO ₂ H Dye of the formula GH ₂ NHCO- 0 HN- • -CO ₂ H CH ₂ NHCO- (J -CO ₂ H Dye of the formula > -NH -CONHCH, CO ₂ H CH ₂ NHCO- 009838/2117 Dye of the formula CH ₂ NHCO- CO ₂ H CH ₉ H CH ₂ NHCO- Dye of the formula GO ₂ H Dye of the formula CH ₂ NHCONH- CH ₂ NHCONH- -CO ₂ H -CO ₂ H 0 09838/2117 13 · Jf Dye of the formula 14th Dye of the formula CH ₂ Ii CO ₂ H 15th Dye of the formula HO ₂ C Ü09838 / 21 1 ORIGINAL INSPECTED Jf 16. A method for producing a dye according to claim 1, characterized in that g e kenn ζ e ic h η et that A compound represented by the following formula :. wherein A, Z, m and η are as defined in claim 1, having one by the following formula reproduced connection: T - GH ₂ - H - GOR ₂ wherein H- and H _{2 have} the meaning given in claim 1 and T is hydroxyl, a halogen, alkoxy or alkylamino, in a solvent, optionally in the presence of a catalyst, or with a compound represented by the following formula: HH - COH ₂ wherein S- and H _{2 have} the meaning given in claim 1, in the presence of formaldehyde, paraformaldehyde or di (halomethyl) ether, or with a compound represented by the following formula: HC-Ro η *, A, «t«% Λ / 4 »4« «■ where Hr, a saturated or unsaturated _{alkyl radical substituted with carboxyl T} carboxyaryl or its ester, or an aromatic radical substituted with carboxyl, carboxyalkyl or their ester, is reacted in the presence of formaldehyde, paraformaldehyde or di (halomethyl) ether. 17 · Use of the dyes according to one of Claims 1 to 1 $, for coloring synthetic polyesters, characterized in that one or more of the Dye (s) is / are added to the polyester, the mixture is melted and the melt is used to form molded articles or by forming the polyesters in the presence of one or more of the dyes to obtain a colored polyester, which is then molded into molded articles.