DE2140444A1 - - Google Patents

Description

dr. W. Schalk- dipl.-ing. P.Wirth dipl.-ing. G. Dannenberg DR. V. SCHMIED-KOWARZIK. · DR. P.WEINHOLD · DR. D. GUDEL

. 6 FRANKFURTAM MAIN

GR. TSCHENHElMER STRASSE 39

FP / M-7-87 Mitsubishi Chemical Industries, Limited '.

2-3-1, Marunouchi, Chiyoda-ku, Tokyo, Japan

Dxyquinophthalone dyes and their method of use

The present invention relates to water-insoluble yellow dyes and to a method for their use in coloring thermoplastic molded articles.

There are already various yellow dyes for coloring more synthetic polymeric materials have been proposed. They have oxyquinophthalone dyes Because of their good lightfastness and luminous tint, "found wide use", however, their disadvantage is poor resistance against sublimation.

It is therefore an object of the present invention to provide a dye with good authenticity, especially against sublimation.

Another object of the present invention is to provide a method for coloring thermoplastic materials such as polyesters, polyamides, polyacrylic and cellulose ester fibers, and molded articles made of thermoplastic Resins.

209850/1186

- 2 - 2UO4U

The dyes of the present invention are oxyquinophthalone derivatives of the following general formula (i)

12 3 in which X represents a hydrogen or halogen atom; Y, Y and Y stand

each for a hydrogen or halogen atom or a lower alkylol or lower alkoxy group; and at least two of the substituents X, Y, and

2 3

Y and Y have a different meaning than hydrogen; if still two

12 3

of the substituents X, Y, Y and Y are hydrogen, then they have two other substituents have a meaning other than hydrogen.

In the above formula (i), X can, for example, represent a hydrogen atom or a halogen

12 3

atom, such as chlorine and bromine, stand; Y, Y and Y include, for example, a hydrogen atom, a halogen atom such as chlorine and bromine; a lower alkyl group such as Methyl and ethyl, and a lower alkoxy group such as methoxy or ethoxy.

The dyes of general formula (i) include e.g. 3-Hydroxy-6-methyl-5- (or -7) -chlorquinophthalone, 3-Hydroxy-6-methoxy-5- (or -?} - chloroquinophthalone, 3-Hydroxy-6-methyl-5- (or -7) -bromoquinophthalone S-hydroxy-ö-methoxy-S- (or -7) -bromoquinophthalone, S-Hydroxy-G-methyl-B-chloroquinupthalone, 3-hydroxy-4-bromo-6-methoxy-5- (or -7) -chloroquinophthalone, 3-Hydroxy-4-bram-6-methyl-5- (or -7} -bromoquinophthalone, 3-Hydroxy-4-chloro-6-methoxy-5- (or -7) -chlorquinophthalone,

209850/1166

2U0444

™ * j "·

S-hydroxy- ^ brorri-e-athoxy-B- (or -7) -chlorquinophthalone, S-hydroxy- ^ bromo-β-ethyl-? - (or -B) -bromo-ghinophthalone, S-hydroxy- ^ B-dibromo -Ö-methylquinophthalone, 3-hydroxy-4-bromo-6,8-dimethylchinophthaion _t 3-hydroxy-4, S-dibromo-ö-ethylquinophthalone, 3-hydroxy-4,5- (or -Q ^ -dichlor -e-methoxychinophthalori, 3-hydroxy-4,5- (or -4,?) - dichloro-ß-ethoxyquinophthalone,

l-S (or -7) bromoquinophthalone and (or -6.7- or -6.8-) - chloroquinophthalone.

The dyes of the formula (i) are prepared by reacting phthalic acid, Phthalic anhydride or a derivative thereof with a quinaldine compound of the general formula (ll):

X ¹

in which X stands for a hydrogen or halogen atom or a carboxyl group stands; the nucleus A stands for a benzene nucleus with up to 3 substituents, one or two of which represent a halogen atom or a lower alkyl or lower alkoxy group; the material can continue to undergo halogenation be subjected.

Typical examples of the quinaldine compounds represented by the general formula (II) are e.g .:

209850/1166

2UÜ4U

S-hydroxy-S-methoxyquinaldine-A-carboxylic acid, S-Hydroxy-EJ-methylquinaldine-A-carboxylic acid, 3-Hydroxy-5- (or -Vj-methylquinaldine-A-carboxylic acid ,. CJ-Hydroxy-ö-chloroquinaldine-A-carboxylic acid, 3-hydroxy-6-ethoxyquinaldine-4-carboxylic acid, 3-hydroxy-6,7- (or -5,6) -dichloroquinaldine-4-carboxylic acid, 3-hydroxy-6, ß-dimethylquinaldine-A-carboxylic acid, S-Hydroxy-eiß-dimethoxyquinaldine-A-carboxylic acid, S-Hydroxy-G-methoxy-5- (or -7) -chloroquinaldine-4-carboxylic acid, S-Hydroxy-G-methoxy-S- (or -7) -bromquininaldine-4-carboxylic acid, S-Hydroxy-S-methyl-B-chloroquinaldine-A-carboxylic acid, 3-Hydroxy-6-methyl-S-bromoquinaldine - ^ - carboxylic acid, S-Hydroxy-S-methoxy-B-chloroquinaldine - ^ - carboxylic acid, S-Hydroxy-ö-methoxy-B-bromochinaldine ^ -carboxylic acid, 3-hydroxy-ß-methylquinaldine, S-hydroxy-A-chloro-G-methylquinaldine and S-hydroxy- ^ bromo-S-methylquinaldine.

The reaction of the quinaldine compound with phthalic acid, phthalic anhydride or phthalimide takes place in the presence or absence of an inert organic Medium at elevated temperature. The media used in the present invention include, for example, o-dichlorobenzene, trichlorobenzene, o-nitrotoluene and Nitrene benzene. The solvent is used in an amount of 3 to 10 times Weight of. Quinaldine compound used; in this reaction, the phthalic compound is used in an amount of 1.0-1.5 moles per mole of quinaldine compound used. If the reaction takes place in the absence of a solvent, will preferably a molar excess of the phthalic compound is used.

209850/1166

. ^] 2U0444

"™ * w ■"

The temperature for carrying out the reaction is between 120-260 C ₁ , preferably between 170-230 C; at a temperature below 120 ° C. the reaction speed is slow and a long reaction time is required.

After the completion of the reaction, the reaction system is allowed to cool and the precipitate thus formed is filtered off. The system is preferably diluted with a diluent such as methanol, ethanol or propanol. The precipitate is then filtered off to obtain the desired product. The excess solvent can also be removed from the reaction system by steam distillation and the precipitate formed can be recovered.

If a quinaldine compound in which X stands for hydrogen or a carboxyl group is used as the starting material, then one chooses a dye in which X stands for a hydrogen atom; if X in the starting material is a halogen atom, then X in the dye stands for a halogen atom.

The amino phthalone compound thus obtained can be halogenated. It will the reaction mass containing the quinophthalone compound or a slurry the quinophthalone compound is subjected to an ordinary halogenation treatment in an inert medium.

The inert media which can be used in the halogenation include aromatic liquids, such as chlorobenzene, o-dichlorobenzene, trichlorobenzene, nitrobenzene and o-nitrotoluene, and acids, such as mineral acids, for example sulfuric acid, or organic acids, such as acetic acid. The amount of the medium is 3 to 10 times the weight of the quinophthalane compound to be halogenated. The halogenating agents include, for example, halogens such as chlorine or bromine, halides such as phosphotrichloride, and thio compounds of the halogens such as thionyl

2098S0 / 1166

Chloride and sulfuryl chloride; the preferred halogenating agent is chlorine or bromine, the halogenation takes place at a temperature of 40-180 C,

preferably 60-160 ° C. In the halogenation of the oxyquinophthalone compounds, where X in the general formula (il} stands for a hydrogen atom, a halogen atom is preferably in the 4-position of the quinaldine nucleus before it is introduced into the 5-, 6-, 7th-position - introduced or 8-r-5tellung; is the 5-, 6-, 7- or 8-position, however, already substituted by a halogen atom, then no further halogenation, but when the ¹ 5-, 6-, 7- or B Position is substituted by an alkyl or alkoxy group, then a halogen atom is easily introduced into the nucleus.

The quinophthalone compound of the general formula (i) thus obtained is suitable for coloring various synthetic polymeric materials, in particular Polyester fibers, cellulose ester fibers and molded articles made of thermoplastic resins, in a yellow shade with good fastness, especially to light and sublimation. The dye can withstand the high temperatures, at which the molded articles are made endure; therefore, discoloration does not occur.

The polymeric materials to be colored with the dyes of the invention For example, molded articles and fiber mice include polyesters such as polyethylene glycol terephthalate, cellulose esters such as cellulose acetate and cellulose triacetate; Polyamide and polyacrylic resins; and molded articles made of thermoplastic resins such as polyvinyl chloride, polystyrene, acrylonitrile / styrene copolymers and acrylonitrile / butadiene / styrene polymerizate

20 9850/1166

_ 7. 2U0444

The dyes according to the invention can be used alone or in the form of a mixture of two or more dyes can be used. Furthermore, uer Dye in a mixture of 3-hydroxyquinophthalone or its 4- and / or its β-halogen, -alkyl or -alkoxy derivatives can be used. The ones with these 3-Hydroxychinapl "itl ~ alon ~ to be used together with dyes according to the invention

derivatives include, for example:

S-hydroxy - ^ - bromoquinophthalone, 3 "hydroxy-6-bromoquinaphthalone, 3-hydroxy-4,6-dibrofrichinophthalone, S-hydroxy-G-methylquinophthalone and S-iMydroxy-G-methoxyquinophthalone.

The inventive dye is used to make a dye bath or a printing paste dispersed in an aqueous medium. These can be used for Dyeing or · printing of synthetic fibers by conventional methods used will.

Hei manufacturing cinss dyeing bath or a printing paste, a Dispcr- gjerungs'fiittelj as a condensate of naphthalenesulfonic acid and formaldehyde, condensate of ciin Kophthalsulfansäure, cresol and formaldehyde _f l.igninsulfonat, a Schwofölsäureester of higher alcohols or higher uin Allcylbenznliiuli'onet, zugr-: nöbsn. If necessary, a cloud, ie a phenolic compound, a chlorobenzene, exn-j DxybKn; 'oo, can be added to the dye bath or the printing paste. ^t cäiu-'e _i an AUcylnaphthalin ader an ester of an aromatic carbon ™ jb'L v.; -: rdfjn

209850/1166

BATH ORIGINAL

The dye bath is produced in the appropriate dye concentration by dispersing the dye in an aqueous medium. The dyeing of synthetic fibers takes place at a temperature of 120 ~ 130 ^D C. for 60-120 minutes, then the dyed material is soaped in the usual way. When incorporating a carrier, the dyeing takes place at 80-100 ° C. for 60-120 minutes.

Dyeing of a molded article made of a synthetic resin is carried out according to different procedures.

The dyestuff of the general formula (i) is mixed in finely divided form with tablets or beads of a thermoplastic resin and optionally with additives such as heat and light stabilizers and lubricants in a suitable mixer. The mixture is then shaped, for example by injection molding, extrusion or blow molding. The deformation temperature varies according to the resin and the applied deformation process and is usually between 150-300 ⁰ C. The dye may be added to a Polymerisatianssystem containing one or more monomers and initiators or catalysts for the polymerization; After the polymerization has ended, the plasticized or melted material is then subjected to a deformation process. Or the dye can be mixed with a small amount of the synthetic resin to form a base dye batch.

The synthetic fibers or molded resin articles dyed according to the invention are resistant to light and sublimation; they are superior to articles or fibers made with known dyes, as shown in the following table. In addition, when using the invention-based dyes to mold synthetic resins, little or no dye flakes are left on the inner wall of the device.

209850/1166

_ ₉ . 2UÜ444

The following table shows the results of the inventive dyeing of Polyester fibers compared to similar known dyes. From the Tahelle it can be clearly seen that the dye according to the invention in his Authenticity is superior to known materials against sublimation. That The dyeing procedure was carried out in the manner given in Example 1 using

based on the fiber weight * of a dye concentration of 2 wt. p / o, / The light fastness was determined in accordance with JIS L-1044 (1959) measured using a Fade-O-Meter. The resistance to sublimation was determined for 3D seconds at 180 ° C. in an iron tester.

In the following table, samples 1 to 4 are known dyes, while Samples 5 through 7 are dyes of the invention.

209850/1166

2U0U4

sample

Structure '

Fastness to sublimation light

- • r

OH

cn

^N co>

OH

Br

OH

cn

^0H

CH (- Jf

^v co ^

OH.

CH (Ti J ^X co ^^

Br

cn (

2 ^ 3

3 *

Br

-4

209850/1166

The following examples illustrate the present invention without it to restrict. Unless otherwise stated, all parts are parts by weight. In the examples, "A max" means the wavelength of the maximum in one Acetone solution measured absorption. The light fastness was measured according to JIS L-1044 (1959) using a fade meter; the sublimation fastness was determined for 30 seconds at 180 C. in an iron tester for polyester fibers, 5 hours at 120 C. for acetate fibers and 3 minutes at 150 C. for polyamide fibers measured.

example 1

A three-necked flask equipped with a stirrer and reflux condenser was filled with 25 Parts of trichlorobenzene, 5.0 parts of a mixture of 3-hydroxy-6-methoxy-5-chloroquinaldine-4-carboxylic acid and S-hydroxy-G-methoxy ^ -chlorquinaldine - ^ - carboxylic acid and 4.2 parts of phthalic anhydride charged; the mixture was then heated to 200 ° C. with stirring and reflux for 3 hours.

After the reaction had ended, the reaction mass was allowed to cool while stirring, the solid thus formed was filtered off, washed with 50 parts of methanol and then with 500 parts of water and dried; thus obtained 5.0 Parts of a dark orange dye with λ max = 455 rri / U and the following elemental analysis:

calc .: C 64.53 H 3.40 N 3.96 ° / »found: C 64.00 H 3.70 N 4.25 ° p

These values correspond to those of a compound of the following structure:

egg

209850/1 1G6

- 12 - 2U0444

It became a. Dyebath prepared by adding 1 part of the dye thus obtained, 3 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 4 parts of the sulfuric acid ester of a higher alcohol to 3000 parts of water. 100 parts of polyester fibers were then dyed in a dyebath at 130 ° C. for 60 minutes, washed with water and soaped for 15 minutes at 90 ° C. with 3000 parts of water containing 4 parts of sulfuric acid ester of a higher alcohol. The dyed fibers were bright yellow with a lightfastness of 6 and a sublimation fastness of 4.
Example 2 '

According to Example 1, 12 parts of a mixture of 3-hydroxy-6-methoxy-5-chloroquinophthalone were used and S-hydroxy-S-methoxy ^ -chlorquinophthalone in 100 parts o-Dichlorobenzene with 5.3 parts of bromine at a temperature of 150-160 C. brominated; in this way a mixture (Λ max. = 447 rri / u) was obtained

Cl Br H5CO,

and

HjCO ^

209850 / 116G

- ₁₃ - 2U0444

1 part of the dye thus obtained was in 3000 parts of water, the 2 parts of the condensate of naphthalenesulfonic acid and formaldehyde and 4 parts of sulfuric acid ester a higher alcohol contained, dispersed to make a dyebath.

In the dye bath, 100 parts of polyester fibers were stained for 60 minutes at 130 C., washed with water and contained a higher alcohol with 3000 parts of water, the 4.Teile Schwefelsäureester, ⁰ C. soaped at SO 20 minutes. The dyed fibers were bright yellow and had a lightfastness of 6 and a sublimation fastness of 4-5.

Example 3

0.2 parts of the finely divided dye prepared in Example 2 and 100 parts of polystyrene tablets were placed in a closed rotating jar and mixed together at room temperature by rotating the vessel to distribute the dye particles on the tablet surface. the Tablets were in a screw extruder, the outlet with a rotating Cutting device was treated at a drum temperature of 200 C. to form colored grains. These were made in an injection molding machine melted at 245-250 C. and formed into 5 cm discs Diameter and 0.3 cm thick injected into a mold held at 70 g.

There was no discoloration of the dye when deformed, and on the inner wall No staining of the dye was observed on the device. the The panes produced had good light and heat fastness.

209850/1166

- 14 - 2H0444

Example jl

According to Example 1, 50 parts of trichlorobenzene, 10 parts of S-hydroxy-ö-methoxy-8-chloroquinaldine-4-carbansäure and 8.4 parts of phthalic anhydride was heated for 3 hours at 200 C. ^D. When the reaction had ended, the mass was allowed to cool while stirring and the solid formed was filtered off, washed with 50 parts of methanol and then with 500 parts of water and dried; 10.2 parts of a dark orange product were obtained in this way.

10 parts of the product were mixed with 50 parts of 0-dichlorobenzene and

heated to 150 ° C., 4.5 parts of bromine being added dropwise to the mixture; the Bromination continued for an additional hour. The reaction mass was Allowed to cool to room temperature and the precipitate filtered off, with Washed methanol and water and dried. This gave 11 parts of yellow Crystals with a F. of 311-313 C, Λ max. = 44? m, u and the following Elemental analysis:

calc .: C 52.80 H 2.54 N 3.23% found: C 52.41 H 2.3? N 3.01 * /,

These values correspond to those of a compound of the following structure:

Br

Cl

The product thus obtained was finely divided and, as in Example 2, for coloring used by polyester fibers. The stained material was bright yellow with a light fastness of 6 and a sublimation fastness of 4-5.

209850/1186

- β - 2U0U4

According to Example 3, using 0.2 parts of dye and 100 Split polystyrene tablets made of colored polystyrene discs that were clear and bright yellow with good light and weather fastness. No discoloration of the dye was found during the deformation process.

Example __5

5 parts of S-Hydro ^ -S-methyl-S-chloroquinaldine- ^ l-carboxylic acid and 4.0 parts of phthalic anhydride were dispersed in 15 parts of trichlorobenzene and the mixture was heated to 190-200.degree. The reaction took place for 3 hours at this temperature range. The reaction mass was then allowed to cool while stirring and the precipitate was filtered off, washed with methanol and water and dried; this gave 4.2 parts of a yellowish brown dye with an F. of 269-273 C ₁ Λ max. = 450 m, u and the following elemental analysis:

calc .: C 67.70 H 3.56 N 4.15 ° / o found: C 66.90 H 3.85 N 4.01 ° / o -

These values correspond to those of a compound of the following structure:

The product was finely divided and according to Example 1 for dyeing cellulose acetate fibers used; the dyed material was bright yellow with a lightfastness of 6 and a sublimation fastness of 5.

209850/1166

■ - 16 example 6

2HO444

12 parts of S-hydroxy-e-methylquinophthalone in 100 parts of D-dichlorobenzene were with 10.0 parts of bromine at a temperature of 150-160 C. to form a Connection with a value of A max. = 452 m, u and the following structure implemented::

1 part of the dye thus obtained was dissolved in 3,000 parts of water with 3 parts of the condensate of naphthalenesulfonic acid and formaldehyde and 5 parts Marseille soap dispersed to make a dye bath. In this were 100 parts of cellulose acetate fibers dyed at 80 ° C. for 60 minutes, with water washed with 3000 parts of water containing 5 parts of Marseille soap, soaped and dried; so one obtained bright yellow fibers with a light— fastness of 6 and a fastness of sublimation of 4-5.

This dye was used for dyeing polyester fibers according to Example 1. Bright yellow fibers with a light fastness of 6 and a sublimation fastness of 4-5 were obtained.

Example 7

Polymethyl methacrylate tablets and 1 p / o by weight of the dye from Example 6 were at room temperature for 60 minutes as in Example 2 in a rotating vessel mixed. The tablets treated in this way were melted by an extruder with a drum temperature of 200 ° C. to form a base color extruded.

209850/1166

^ M 2U0U4

10 parts of the base color and 100 parts of polymethyl methacrylate were melted at a temperature of 180-200 ° C. in a screw extruder which was provided with a rotating cutter at its outlet; this is how one fills colored grains. As in Example 2, these were injection-molded into a Maren, yellow molding with excellent light and heat fastness; No dye stains due to sublimation were found on the inside of the deforming device during or after the deformation. Example B.

An intimate mixture of 15 parts of a-hydroxy-GJB-dimethylchinaldin-fl-carboxylic acid and .15 parts of phthalic anhydride was längsam to 240 ^D C. heated; then the reaction was continued at that temperature for 4 hours. The reaction mass was allowed to cool to room temperature and ground into finely divided particles, which were then extracted with 1000 parts of 50% aqueous sodium hydroxide solution. The extract was made by adding conc. Acidified hydrochloric acid; the desired product was precipitated, filtered off and dried. 14.2 parts of yellow crystals were obtained having a melting point of 278-280 ⁰ C., identified as S-hydroxy-öjB-dimethylchinophthalan.

10 parts of the product were added to 30 parts of trichlorobenzene and the Mixture heated to 150-160 C.; at this temperature there were 2.5 parts of chlorine initiated within 2 hours, then the chlorination was carried out for a further 2 hours. The reaction mass was allowed to cool and the formed The precipitate is filtered off, washed with methanol and water and dried; this gave 10.5 parts of yellow product with A max. = 446 m, u and the following elemental analysis:

209850/1166

-1B-

calc .: C 68.25 H 4.00 N 4.00 Cl 10.01% found: C 68.43 H 4.14 N 3.88 Cl 9.53%

These values correspond to a compound of the following structure:

Cl

OH

The product was ground into finely divided particles and as in Example 1 used to dye polyester fibers; bright yellow fibers with a light fastness of 6 and a sublimation fastness of

Example 9

The dye used in this example had a value of Λ max. ^C /> m, / U and the following structure:

Br

OH '

It was prepared by reacting 5 parts of 3-hydroxy-6,8-dimethylquinaldine-4-carboxylic acid with 4.5 parts of phthalic anhydride in trichlorobenzene and subsequent bromination with bromine.

According to Example 1, 100 parts of polyester fibers were obtained using 1 part stained with the above dye. The dyed material was bright yellow with a lightfastness of 6 and a sublimation fastness of

- 18a -

2098 50/1166

Example 10

Using the dye of Example 9 and following the procedures of Example 7, polymethyl methacrylate was dyed and used to produce a injection-molded clear, bright yellow disc. During the deformation there was no discoloration and that formed on the inner wall of the device Number of stains was lower than when using 3-hydroxy-4-bromoquinophthalone, which is similar to the dye of the invention.

. - 19 -

209850/1166

B is ρ iel

2.5 parts of 3-hydroxy-4-bromo-B, 8-dimethylquinophthalone were in 10 parts Dissolved α-dichlorobenzene at 150 C. At this temperature it was 1.3 parts Bromine was added dropwise to the solution within an hour; then the bromination takes place 30 minutes with stirring. The reaction mass was allowed to cool to room temperature left, the formed precipitate was filtered off, washed with methanol and then with water and dried. Yellow crystals (2, B parts) were obtained with an F. of 281-285 G., Λ max. = 455 m / rev and the following elemental analysis: ...

Calcd .: C 50.55 H 2.76 N 2.95 Br 33.65% found: C 49.61 H 2.2 N 2.4 Br 34, B4 ⁰ ^

These values correspond to those of a compound with the following structure:.

Br, OH

(in which one of the bromine atoms was substituted in the 4-position; the substituents the other's position was not identified.)

The dye thus produced was used for dyeing polyester fibers according to Example 1 used; bright yellow fibers with a light fastness of 6 and a sublimation fastness of 4-5 were obtained.

B e i s ρ iel 1_2 up to 16

Various dyes listed in the following table were used for coloring various synthetic fibers and synthetic resins are used .; the results are also given in the table.

2 0 9850/1166

example

structure

απ *

Br

HcC

H ₅ CO

max. to be dyed, color (iTi / u) Material clay

Polyester fibers

Polyester fiber & ABS resin

Cellulosic

el C S "CcLu" ·

fibers

Polyester fibers

yellow

Authenticity to light sublimation

2U0U4

Example 17 to 26

Various quinaldine compounds listed in the following table

were with phthalimide (Example 17, 18, 20 to 26) and phthalic anhydride

(Example 19) implemented; then the product was optionally halogenated. So FarDstoffe Brhalteny were used "for" dyeing polyester fibers,

Structure and properties of the dyes and properties of the dyed Polyester fibers are also given in the table.

209850 / T166

inn

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Πί QJ P. St. Xl ·> Η "c η G) υ Tuesday
approx 'Yy D) • μ • Η -P ω χ: Ö ω -P • Η χ:
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to

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tn in st

BATH

entered üm..3u, .sß 2U0U4

SL • Ρ SZ U UJ

TD O U Q.

s: -η α χι

D. U] • rl Q]

in

CO

XI H

ω cn

CO co

in

■ / w

O O Q

ο ο

ο ο

O

t-l O

I cn
ω c I. cn D • Η ■ D U E cn H Ql (Ö · Η r ^ -j X C ω.u

CO

co

approx

ό a

ο ρ

(M CM

CD CM CO CM

received on.

209850/1166

Claims (1)

Claims I.-Oxychinophthalonfarbstoffe of the general formula 12 3 in which X stands for a hydrogen or halogen atom; Y, Y and Y each represent a hydrogen or halogen atom or a lower alkyl or lower alkoxy group, where at least two of the substituents X, Y, 2 3
Y and Y have a meaning other than hydrogen and - if two of the 12 3 Substituents X ₁ Y ₁ Y and Y represent hydrogen - the other substituents have a meaning other than hydrogen. 2, - dyes according to claim 1, characterized in that X is a water 12 3 is a material, chlorine or bromine atom and Y, Y and Y are hydrogen, Chlorine or bromine or a methyl, ethyl, methoxy or ethoxy group stand. 3. Dyestuffs according to Claim 1, characterized in that X stands for a bromine atom 1 2 3
and Y, Y and Y represent a hydrogen or bromine atom or a methyl standing group. 209850/1166 2nd U 04 4th 4.- dye of the formula} Sb OH CH " -CO CO 5, - dye of the formula: Br 6, - dye of the formula: CO co 7, - dye of the formula: OH CH CO co 8, - process for dyeing thermoplastic fibers and molded objects, characterized in that dyes are used in orphan known per se according to claim 1 to 7 used. The patent attorney: ¹ / 209850/1166