DE1419780A1 - Process for the preparation of new dye derivatives - Google Patents

Description

documents

CLBA AKTIENaESELLSCHAr ι j, .u * „ _n ~

US. Z .: 20 499-BR / ro 1419780

Gases 4273/1 + 2 / E

Process for the preparation of new dye derivatives.

It has been found that new, valuable dye derivatives can be obtained by using organic substances in water sparingly to insoluble, at least one substituent which is reactive with optionally etherified alkylol groups

8 0 9819/1270 " _ΜΑ1

BATH ORIGINAL

containing dyestuffs with the BILdungegemieohen from gebananr-alls etherified Hai'Z-vorlto containing alkylol groups -densaten, especially £ iii.> \ clere the educational requirements of AmlnooJ.asten, implement »

The derivatives used for the manufacture of the dye are called the rare starting colors. ¹ have to be difficult to insoluble in water. They may, therefore, contain groups such as caffeine acid groups or sulphonic acid groups.

Furthermore, these starting dyes must at least one with alcylene groups or etherified alkyl groups have reactive substituents. As 3ubstuenten who have this quality, come at For example, the following can be considered:

N-Alkyloi, before2Ugsv / else N-MethyIo! Groups as well as the atomic groups convertible into H-Ailcylolgruppen, in particular H ^ H-Quirappen ^ }? N-methylolamide groups j

Of course, via an alkylamino radical a 1,3,5-triazine ring bound I ^ N-arupp ^ ri (Amides aar cyanuric acid), e.g. those of Formulas

N-C

(1) -C ^; N or

ΓΝΗ-AlkyLenV-. MR,

ⁿ " ^{l d} BAD ORSGINAL

(NB-Alkylenes _v IL

P ■ C.
(2) -C: j; K.

'N «C'

X

wherein X is a substituted amino or further Qxygruppe, a "Allcyl-, aryl or aralkyl group, or a halogen atom and RA and each η a whole count in width of at most 2 mean.

HgN-OG groups, where the carbonyl group, as in AcetamidabkÖminlingeß (HgN-OC-CH ₂ ), to an alkylenreat,

or never in urea derivatives, to an -NH group can be bound;

HgN-OgS groups

to allphatisehe hydrocarbon residues, to heterocyclic ones Hinge or preferably attached to aromatic hinge such as naphthalene or benzene rings HgN groups.

Further substituted amino groups bound to a triazine ring, e.g. -NH-alkyl or -NH-ary! Groups, which in turn may contain substituents, but not water-soluble groups. It can atapielsweiee atom groupings of the union HN-A

are considered in which A is a substituent, preferably an alkyl or aryl radical and B is an -HN-A group

BATH 809810/1270

(where A has the meaning given), a further · » substituted oxy group, e.g., an AXkoxy group or a halogenated in particular a chlorine atom »mean.

In addition, the starting dyes can be any dye class ^ e.g. those of the nitro dyes, the Oxazines, Acridone, the Kupfarphthalocjranine, the Polymethine and azomethines, the azoxy dyes or the anthraquinones belong. Anthraquinone and azo dyes are preferred into consideration, the monoazo dyes in particular being mentioned among the latter. The dyes can also be metals, in particular copper, chromium or cobalt, contained in a complex bond «,

For example, monoazo dyes can be used whose azo group on the one hand is attached to a benzene nucleus and on the other hand to a naphthalene nucleus or pyrazolone radical or those whose azo group is bonded to benzene nuclei on both sides is. These azo dyes contain, for example, aromatically bound BpN groups as reactive substituents or atom groupings of the formula (1).

Among the anthraquinone dyes, for example, there are two α-positions, that is to say anthraquinones substituted in the 1,8-, but especially 1,4- and preferably -1,5-position mention at which one of the substituents one over an -NH o group attached to the anthrachlnone nucleus of the above formulas (!) or (2) and * the other one

BATH ORIGINAL

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is the same group or an optionally further substituted benzoylamino group. Oute results are for example with the dyes of the formula

HN-

⁰ 1

- • VVN '

I, j I

UN-H VVN /!

ν; ' : c ~ nh

i?

^ό ι

HN-

.OC-R

H-N-B

.N-C.

-c;

.N;

achieved, wherein A and B have a substituent, for example an alkylresfc, or preferably a hydrogen atom> X and Y a -HN-A group, or a -HN-B group (where A and B have the meaning given), a Alley! Group, an alkoxy group or a halogen atom, especially a chlorine atom, R, an optionally further substituted benzene radical, -OC-R ^ -CO- the radical of a dicarboxylic acid of the formula HOOC-Rp-COOH and m and η each have an integer value of at most 2 mean.

Among the dyes of this type containing a single anthracnylrione nucleus and 1 to 2 triazine create are those of the formula

HN-C '
O'N

λ>
0

-C

-HN-OC-R

-η: ■ -

preferred, in which B ₁ and B _{2 are} a chlorine atom or an HUN group optionally bonded to the triazine ring via an alkylamino radical, R _{1 is} a Benaol radical and m, η, ρ and q are each an integer of at most 2.

More Änthraquinone derivatives are here to exhort those with acridone rings and dibenzanthrones.

For Orasets'Ling with the formation mixtures of the resin preconditioners, the starting dyes are usually processed into fine to dispersed dispersions, for example those with a part size of 1 to 10 μm. This can be done in the usual *. well-known knowledge with PIiIf s known devices, e.g. colloid mills and advantageously un-

1419760

ter addition of dispersants happen. It kifnnen the known non-lonogenen or anionakfciven dispersants are used. In some cases, condensation products of naphthalenesulfonic acid and formaldehyde are useful.

- ^. For the preparation of the dye derivatives «earth if necessary, the dyes with education mixtures athers Resin precondensates containing alkylol groups, in particular educational geniuses of aminoplasts implemented »Als Bildungsgemiaehe for the production of äsr Dyestuff derivatives are also to be considered such mixtures, the formation of the alkylol compound has already begun. Formulations of phenolic resins are Urethanharzsn, Sulfamidharsen, Dicyandiamidharzea, Tri » azone resins, but especially of melamine or urea resins, i.e. the formation mixtures resulting in such resins, consisting of phenolic or nitrogen compounds of the kind given, in particular melamine or urea * and formaldehyde or formaldehyde-releasing agents mention * also cyclic urea derivatives * such as acetylene » diurea, glyoxal monourel, oxypropylene urea, ethylene urea, Methylolarylamides can be used here.

• For example, there are dye derivatives based on urea-formaldehyde resin into consideration. These can consist of. ·, Methylolureas from 1 mole of urea and 2 to 4 moles of formaldehyde or the alkyl ethers of these methylol compounds

. _f . BAD ORIGINAL

': 809810/1270

niedlgmoleiiularon αοϊκ-η, like Meth & noA cü & r n-Eutanol., derive., whereby also ran * a part of the methylol groups present in the molecule can be etherified. As examples be hlsr far away © -! - * Methyl ether of methylol äthyienftö.rn ~ substances as well as MsUiylolacetiflenureas and their methyl " 'ether mentioned.

Furthermore, condensation compounds come from Formaldehyde with the dyes and such compounds Consider polygamy, such as dicyandiamide or melamine., at least once the atom grouping

* contain, or like cyanamides easily in such compounds pass over.

The formaldehyde condensation products to be used for the present purpose can be derived from a wide variety of compounds with the specified atom grouping, both cyclic and non-cyclic. Examples of non-cyclic compounds include dicyandiamide, dicyandiamidines, guanidine, acetoguanidine or biguanide mentioned. Suitable condensation products are, for example, those using more than 1 mole, such as _e of 2 to 4 moles or more of formaldehyde, based on 1 mol of the compound at least once

BATH

809810/1270.

the atora group Timg

- ν - c;

contains, can be produced apply, fiia in neutral, alkaline or acidic medium "

The condensate-ion products from Po: emai.d © hyd and cyclic Connections * which hurry at least once to Ätostigrupple- ·

■ - N - C.

Yo-y? -ug3weisö abstain from Äminotriaisinen. There are methyrolvic bonds of aminotriaciisn. or their Ästher or esters into consideration * Among the compounds were J.amino ~ l »3j5'-fc2'i & s especially Urasetisungsprodukts of formaldehyde and 2 _i 4 _i 6 ~ S: -in ₅ gewöhnlich- melamine mentioned above. Such condensation products can contain one to 6 methylol groups, usually they represent mixtures of different compounds. Furthermore, methyloliferous compounds of such derivatives of melamines which still contain at least one aromatic group, for example methylol compounds of melam, melamine, are possible. Ammelin ^ Ammelid or - of halogen-substituted aminotriazines, such as 2-chloro-4,6-diam3, no = _1,3> 5-tria5Slni also iVlethylolverbln-

BATH ORIGINAL 809810/1270

fertilize guanamines, like 2.B. of benzoguanamine, acetoguananrine or formoguanamln.

Such basic condensation products also occur into consideration that has been obtained by looking at the dye and in any order

a 5 methylol compounds of aminotriazines or their Ethers with low molecular weight alcohols,

b) aliphatic compounds that form a carbon chain of at least 7 carbon atoms and one reactive bonded to a heteroatom Contain hydrogen atom and

c) primary or secondary amines or tertiary amines Amines, which have a non-basic nitrogen atom in the molecule on an oxygen, a Sah, 3fel or other bound, reactive hydrogen ~ afcor / i, contain,

implemented with each other.

For the purposes of the present invention, formaldehyde condensation products of formaldehyde can also be used and Guany! melamin can be used. Such condensation products can be derived from mono-, di- or triguanyl meiasiin or their mixtures, which are available. " if you dicyandiamide in an inert solvent in the heat treated with gaseous hydrogen halides and the free amines from the resulting salts Adding strong alkalis separates. Also substituted ones

BATH ORiQINAL 809810/1270

Guanyimelamine grain; · -m -sur manufacture of Fc-rc « Condensation products are used.

The above statements relate to aminoplasts containing ol groups or v-etherified methyl groups. In some cases it is found to be advantageous to carry out the modification only after the methylolvex bonds have reacted with the dyes. For example, the dye can first be reacted with urea and formaldehyde and the methylol groups in the product thus obtained can be partially or completely etherified with a low molecular weight alcohol, for example /! Ethanol or, preferably, methanol.

It is known that the resin precondensates ^{which are available in this 1} _{MlBe 1} but are not etherified or etherified with alkanol or, in particular, methanol without the use of the water-insoluble dyes are generally water-soluble. The corresponding precondensates produced by the present process, on the other hand, are in most cases sparingly soluble in water «·

The property gets even more pronounced when the soluble dyes sparingly soluble in water with the formation of mixtures of limited water verStherte alkylol containing Harzvorkondensaten implements "The term ^lr in water sparingly soluble" importance

BAD OeKaiNAL

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tet that the Vorkc-Asnsat a certain, mostly pretty can dissolve a small amount of water, but in turn is sparingly to practically insoluble in water.

Among the educational mixtures that exist in water able to form slightly soluble precondensates are in particular those from (a) urea or elnera atninotriazine, preferably melamine, (b) formaldehyde and (c) preferably to mention aliphatic alcohols with 3 to 7 carbon atoms. These dye derivatives can can be conveniently prepared in the catfish that one finely dispersed starting dye in -aqueous medium and the urea, or the aminotriazine, reacts at the same time with formaldehyde and then in the methylol compounds formed in this way the methylol groups largely with aliphatic, Alcohol containing 5 to 7 carbon atoms oils such as n-propanol, isopropanol, isobutanol, n-pentanol or preferably etherified n-butanol? also come for consider the etherification of cyclohexanol and benzyl alcohol "

The quantitative ratio in which the reaction · » capable dye with the formation mixture of the aminoplast can be brought to a reaction within very wide limits vary. For example catfish can have 1 mole of dye

2 to 3 moles of aminoplast figurative device (e.g. 2 to

3 moles of urea and 4 to 6 moles of formaldehyde) permit. Above all, valuable products are preserved

80 98 10/1270 ^ßAD

Dec 18

if you use the dyes with a substantial excess at Amlnoplast-Bildungsgömlsoh. So you can, for example to 1 part of dye, about 5 to 100 parts of Aminoplast Forming Mixture use .

The reaction of the dyes with the formation mixtures of the aminoplasts generally poses no difficulty. You can follow the usual for such reactions per se known methods are carried out, preferably in aqueous medium. If, proceeding from the formation mixtures of the aminoplasts, an excess of this is used, so one can proceed in the same way as is done in the production of the aminoplasts without the dye.

The dye preparations obtained in the present process are particularly suitable for dyeing textiles. L> abei primarily those made of cellulose fiber !! into consideration. The dye derivatives should be in the finest possible dispersion are present. Under certain circumstances, for example if the dispersion has become coarser during the implementation it is appropriate to ensure that the derivatives are subsequently or subsequently returned to the areas that are advantageous for their use, be brought into a finely dispersed state.

It was found that textiles * can be colored in an advantageous manner, if

aan on these textiles dye derivatives, which are produced by the reaction of organic, sparingly to insoluble in water, Olndestena "Inen with sub-ethylol groups capable of reacting with optionally etherified alkylol groups containing dyes with mixtures of optionally etherified Hans precondensates containing alkylol groups, in particular Aminoplasts, are obtained, applied in the form of aqueous preparations and the textiles treated in this way are subjected to a heat treatment.

In the worst case, the textiles can be neutralized or soaped after the heat treatment. However, they generally have good wetness properties even without soaping, in particular good wetness, and They continue to draw through the evenness of the color tones and good rub fastness.

From Belgian patent 568 725 it is known to apply water-soluble dyes together with water-dispersible aminoplasts. This patent specification However, there is no indication of the inventive reaction of a water-insoluble color with a resin precondensate.

In the following examples, the parts mean unless otherwise noted. Parts by weight, the percentages by weight and the temperatures are in degrees Celsius specified.

ORIGINAL SKSPSCHFED

Example 1

7 * 0 parts of l ^ amino-S ^ fe ^ iiivoylaininoantln ^ acliinon are dissolved in 150 parts of nitrobenaol by heating. At 140 ° a solution ¥ is on 6 ₃ east Tei.len cyanuric chloride in 30 parts of nitrobenzene, after the time Kurser Monoiconäensationspi'odukt starts the formula

Cl

-IT - C.
HH - C '■ "N

0 '; -η * C--. (6) - / VyN ^G1

, "■ ·%. Co -im

see to deposit in small yellow crystals ”, One stirs still for 5 hours at 140 "to 145 ° and filtered the Product after the Geiaisch has cooled down *

24.5 parts of the product thus obtained ■ sfsi'dsn with 500 parts of nitrobenzene mixed in an autoclave, Dana'rird dry ammonia gas pressed on until the pressure is about 6 atu amounts to. The device is heated to 140 to 150 ° and is kept at this temperature for 12 hours. After the Erkal = th is filtered off, washed with benzene, alcohol and water and dried in vacuo at 90 -bit 100 °. That so

8098 10/1270,

* 16 -

holding pigment of the formula

., N HN - C *
O 1 "N =

⁽⁷⁾ -κ ι NH ₂

/ 'N-CO-NH

forms an orange powder. It is common in in a known manner with the help of a condensation product from naphthalenesulfonic acid and formaldehyde to a microdisperse aqueous dough with 15 # pigment content processed.

In a reaction vessel with a stirrer and reflux condenser and thermometer become 148.5 parts of 37 # aqueous formaldehyde solution and 0.7 parts by volume of 30 # strength sodium hydroxide solution heated to 60 ° and mixed with 31.5 parts of melamine. After dissolving the melamine, 56 parts of the above-described, 15 # of the pigment of the formula (7) containing, microdisperse dough and then 200 parts of dist. water added. During the following condensation should be in regular Distances of the p "- Fourth determined by electrometry and if necessary with additional sodium hydroxide solution. p "value 7.5 to 9 can be set. The mixture

is heated to 90 °. Two parts by volume of 30 # Lge sodium hydroxide solution are added within 35 minutes, NaOH for 40 minutes is cooled to 60 ° and the mixture is mixed with 110 parts of methanol and then with 1.5 parts of conc. Hydrochloric acid »diluted with 2 parts of water. After 15 minutes, the etherification is terminated by adding 3.5 parts by volume of 30 # strength sodium hydroxide solution (p "control). The mixture is cooled and concentrated in vacuo at a bath temperature of 50 °. About 225 parts of a finely dispersed suspension with about 4l dry content of derivative I are obtained.

Example 2

Dlazoped 1-amino-4-metho ^ ybenzene is used in Sodium carbonate alkaline medium with 1-acetylamino-4-oxybenzene coupled. Then the Acetyiamine group saponified and the aminoazo dye frait cyanuric chloride condensed and then one by reaction with ammonia de * both Chloratorae bound to the Trtazinrlng exchanged for an HgN group. The color thus obtained stofi the formula

HO

(8) HC - O - V - \ N * N - .., ^; ~~% Cl

{, N ~ C HK-C N 'N »C

is dried at e Vm 40 ° in a vacuum.

In a reaction vessel with a stirrer, reflux cooler and thermometer, 690 parts of 37% aqueous formaldehyde hydration and 21.4 parts of conc. aqueous Ammoniaklöaunfy heated to βθ ^7. After 151 parts of Hilamine had been added and dissolved, 400 parts of water and 40 parts of dye of Όπηβΐ (8) were added.

During the subsequent condensation it rumbles I -, - regular intervals checked electrometrically and If necessary, with the above sodium hydroxide solution

BATH ORIGINAL

set to 8 to 8.5. The mixture is heated to 85 ° for about 15 minutes while stirring. At 80 °, 220 to 250 parts by volume are distilled off in vacuo. After Enter H of 730 Vclumteilen butanol Distillation is continued in vacuo until a distillate about 400 parts by volume of water and 520 parts by volume of butanol receives _o The separated butanol together sit 3 * 5 parts conc. Formic acid was added to the reaction mixture. The distillation continues. After adding 350 parts by volume of butanol, the solution is concentrated in vacuo until about 430 parts of a viscous clear resin solution with about 77 # dry content are obtained.

320 parts of this yellow-colored resin solution are stirred with 70 parts of a 50% aqueous solution of a reaction product of 1% hydroabietyl alcohol and 200 parts of ethylene oxide, crosslinked with about 1% hexaraethylene diisocyanate. While stirring vigorously, the resin is distilled by gradually adding 315 parts. Water dispersed. About 700 parts of a stable, yellow-colored resin dispersion with about 40 μl of dry content derivative II are obtained.

"" 'BAD ORIGINAL

■ .-. Ι ι - *. "I." £ if;

Example 3

Open the apparatus described in Example 1. 72 parts of 37% aqueous formaldehyde solution and 0.2 parts by volume of 30% sodium hydroxide solution were mixed with 15.7 parts of melamine at 60 °. After dissolving the melamine, 55 parts of a microdispersan dough, the 15 # pigment of the formula

HK-C N

9 ^K " ^c (made from 1-amino« ^ "'KH ₀ anthraquinone and cyanur- '" ■ * ' <"ν ν« 2 chloride, analogous to example 1)

w = t r "

contains, and then 150 parts the more water is added. Dial, At the end of the subsequent condensation, the p "value becomes electrometric checked and, if necessary, adjusted to 8 to 8.5 with additional sodium hydroxide solution. The mixture is heated to 87 °. After 40 minutes, the mixture is cooled to 60 ° and 60 parts of methanol are added to the mixture and then with so much '2n' hydrochloric acid that one powers off 4.5 to 5 is reached. After 15 minutes there will be a recovery by adding 30 # sodium hydroxide solution to

BAD ORlQlNAk 809810/1270

to the p "-tfert 8.5 to 9 canceled. The mixture is cooled down and concentrated in vacuo at a bath temperature of 50 °. About 105 parts of a hostile spersen are obtained. Orange-colored suspension with a dry content of about 43 %. Derivative III

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In the example J. beoohr! .Ob ;; turn the apparatus } .5b Ίιΐϋβ;> 7 <" ^: -B, t older .ig * Fot" Ha.l <ielrytnöri.ung and '

3 ^, 4 ropes kous, wH.iS-irig.! Ammonia solution b ::,!. 60 ° with 31 * 5 parts of melamine vis ^ tst. After dissolving the melamine 17 Tellft Pavbütoff etc. Formal OCH.

Cl ■.

and 100 parts u * & t, Vtersüör aup: öfUgfc. The garnish is stalled with koria, wäjjserigei 'ammonia solution on the p "- fourfc 7.5 and heated to 80 ° with a stirrer. In the Vatcuuiii, 100 to 120 volumes of volume are removed so that the internal temperature does not fall below 70 ° C. After adding 166 parts by volume of butanol, the distillation is continued in vacuo until 70 parts by volume of 'iasam' are obtained as distillation, about 110 parts by volume of butanol. The separated butanol is together with 1.5 parts of lconz. Formic acid added to the Röalctionßgomijjah. The distillation was continued under the same conditions until no more water can be distilled off. After adding 100 parts by volume of butanol, the

BATH ORIGINAL

80 9810/127 0

Solution in vacuum at $ 0 "' bath temperature koazfciit'r: k? Rt, until you get about 105!' Hurry of a yellow resin solution with about Styg dry content; ,,

104 parts of this resin solution were mixed well with 26.3 'parts of a 50% aqueous solution of a decomposition product of 1 mol of hydration alcohol and 200 mol of ethylene oxide, crosslinked with about 1 hexa-meth; Input of 85 parts CQBt ,. What sw -®inulgi & x * t * You get about SIi T ^ iJe a yellow-colored resin dispersion with etiva Hstf Trookengehaits derivative IV ..

If , according to the instructions given above, a Koridensci * is prepared with 16 "5 parts of dye of the formula

OCH,
j

αχ) ei. * · - ν

this gives about 124 parts of an orange-colored resin solution with about $ 75 Troekengehalfc. "

80 parts of this resin solution are emulsified with parts of the abovementioned emulsifier in 72 parts of distilled water. Water, bo one obtains about 1.68 parts of a resin dispersion with about 36% dry matter content: derivative V.

BATHROOM OFFICIAL

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Example 5

In the apparatus described in example i 72 parts of 37% aqueous formaldehyde solution are used 0.2 Volumfceile 30 # strength sodium hydroxide solution at 60 ° with 15.7 parts of melamine were added. After dissolving the melamine 11.4 parts of dye of the formula

HN ~ C ^: N

0 I ^V N * C- ' UL ¹

(made from 1, ^ - diamino-

/ f "anthraquinone üttd CyanurcKlo-

0 ί rid, analogous to example 1)

NIi

and added 100 parts of water; During the subsequent condensation, the p ^ value is checked eleittrometrically and, if necessary, adjusted to 8.5 with sodium hydroxide solution. The mixture is heated to 87 °. After ho minutes it is cooled to 60 ° and the mixture is mixed with 60 parts of methanol and then with enough hydrochloric acid

that the pjj value % »5 to 5 is reached. After 15 minutes

BATH ORIGINAL

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etherification is achieved by adding 505 sodium hydroxide solution aborted until p ^ -Wsrt 8.5 to 8. The mixture is concentrated in vacuo at a bath temperature of 50 °.

Pie suspension is more commonly known per se Catfish with the help of a condensate product made from naphthalenesulfonic acid and formaldehyde (up to about 50 #, sourced on pigment) to a microdisperse, violet-colored, watery dough with about $ 37 trooken content processed: Derivative VI. -

In the table below, further dye derivatives are listed, which are after. given above Regulation from the dyes of column II can be prepared, the amount of dye specified in column III being used in each case. Column IV there Information about the color and column V about the dry content

derivative

: No.

VII

II
Output dye

-. V.o

.N-C .NH-C 'N

Table A.

XII quantity

Hue ; TrocfcengehaXt % black

Λ> ο "(13)

VIII

N-C 0 NK-C M

H ₂ N

,O-"-. i 'ί ^v

N C-HN 0

^ C-N *

M = C NK

11, *

Red orange

38

! IX H ₂ N I. 2 ^ i
i
I. NHg NH ₂ i Red Yellow S. orange \ 38 r I.
Ϊ N-C. , .N-C ,. ϊ
ί ι
i "V.NH-C" 'K "V-NH-c; n N »C - ^ NC " I. t I ■ ί Cl ! ί 9.2 NH ₂ 1
ΐ
ί * ~~ V -N »N - ./-* "-" Ί 8.7 ί ^; 35 X ί
; (15) . ■ ;
■ (16)

BATH

■ mgyeu

~ 27 -

; ■ I derivative;

II Äusganffsfarbenätbff III

■ I ¥; V

Color shade of dripping

JiH-I

N-C.

Mi. ,, - " ^c _r NH-C K

'N = C'

(1?) NH- <

ρ fm-c

ti

O NH S ~% (18)

O NK-C

NH ₂

xiii \ "■ '·. /,

(T)

° CO

N-C;

■ i

ι ι. ^ v A - '

j O NE I OO

NH ₂ (19) 13.8

13, δ 'WMx j

; orange

j rubih

18th

19th

37

'35

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I I XVI f II t
] III IV ; stole j V 32 \ i • ι ^ derivative ■ - - · ■ ■. Initial dye ^{g 0G} * ^H 5 lot hue 1 ! Trookengehalfc ί ; NO O
t- XVIII i I % i ■ ^m 2 V ^ / ^ C0-NH -_ ^^ .- NH-C N j U-C, - j XVII 0 NH-C "N (23) ^ j ₅ ΐ purple ί ^; . j '' NC * I XY Γυ'τΛ ^nh 2 ^ ²⁰ ) 11.4 33 \ ; 0 ^ 2 ! .N-C. ir * nh-c "; n I.
f ; ■ 'N-C' Ϊ
" Ji-C. ; orange • : o NH-C ^V N ! _β j I ' ^S -NC- (21)
; fY'O NH ₉ 8.3 36 y j ό - ^{1 H} 2f Cl S3 . N ^ ^"Nii c-HN ^Λ ^ ⁰ VJ, ^M * y - ⁰⁰ S 'c «r. IJ. ^ Jj 1, _m ,
KgN ^h 5 ^C 2 ° ^N ^ ^{0 D} Ji-C.
- C ">
N = C
ι gray j (22) i 14.3 OCgH ₅ 17.4

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In the following Table B, further dye derivative θ are listed, which are represented according to the above specification, with the difference that they are made with the aid of an urase product of 1 mol of hydroabietyl crosslinked with about 1% hexamefesrene diisocyanate. alcohol and 200 moles of ethylene oxide (up to $ 50, based on pigment) have been processed into a microdisperse dough,

Table B.

j derivative _; I Nov =

II starting dye

NH-C

NH ₂ {20) NH ₂

ΝΗ

HI \ IV j V

Amount of color dry content %

11.4 j purple

37

- "50 -

[II II \ III
Derivative! Starting dye s amount
No. j. ! " IV
hue V
Dry-
held % ! I.
)!
Ί ν ..... <· " ¹ V- NH-CO ...; ■>.!
XXI j ^{w d J} I ^if *
j. _v i .0H NH ₂ 'j
j I CO-MH-; ^, NH-C _v ^ _c N j
i I ^!
= (23) - NH _p *
I ^! · '" stole
- 23

BATHROOM QRiGlNAL

U1B780

Belsiplei. 6th

In the apparatus described in Example I, 15.7 parts of melamine are added to 72 parts of 37% aqueous formaldehyde solution and 0.2 parts by volume of 3QJ6ige halide solution at 60 °; 37 parts of a microdisperse dough containing 2.01% pigment are added to the melamine solution the formula

(24) Cl

contains, and 35 parts dist. Water added. During the subsequent condensation, the p "value is adjusted to δ to 8.5 by adding sodium hydroxide solution. Paa Geroisch is heated to 87 ° for 40 minutes, it is cooled to 50 ° bath temperature and the mixture is concentrated in vacuo. About 580 parts of a yellow-colored suspension with a dry content of about 19% are obtained: derivative XXII.

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Example 7

In the apparatus described in Example 1, the 72 parts "57 # lee wüÄe & rlge Formrnldetoyäl $" ufcg utid O, £ Üfeile 5ö # ige l ^ triiinihfdrostyälöaimg feel 3Ö ⁰ tiiit 12 »£ files urea. After dissolving the urea

I im

^ ν ■ -% Τ «

and 35 parts dist. Water added. During the subsequent condensation, the _pH value by Zugmbe of. Katriumhy <5rοxydlösung divided into 8.5. The Oemieoh is heated to 90 ° »» after 75 minutes, it is cooled to 5o ⁶ bath temperature and about 50 parts by volume are distilled off in a vacuum. NaOH cooling to 30 ° "ground 60 hawks" methyl alcohol, after further cooling to 20 ° as much Sn ealaeaure added "to a _pH value of 4 is reached to -5. 5 After 15 minutes, the etherification is terminated by adding sodium hydroxide solution up to a pg value of 8.5. The mixture is concentrated in vacuo at 50 °.

The suspension will help in the usual manner

• A condensation product of naphthalenesulfonic acid and formaldehyde processed into a mlkrodispereen, yellow-colored aqueous dough with approx. 30 # Trooken content : Derivative XXIII.

If the condensation and etherification are carried out according to the instructions given above, using 48 parts of a granulated dough, the 20 # pigment of the formula

* «■ -ν

N - C

O NH - C N

N * C

1 V 'r V

HH 0
, CO

contains, dui »oh, oo you get a microdisperse orange-colored wäaserigon dough with about 3 ^ dry content Derivative XXIV.

BAD OHiGlNAL

Example 8

In the apparatus used in Example 1 get 100 Telia 37 # lge wliasarige formaldehyde solution, 80 Telia butyl alcohol and 4.2 parts of conc. aqueous ammonia solution at 30 ° with 30 parts of urea and 18 parts Parbßfcoff the formula

Cl ^H0

C - N., '·· .. NH ₀ (26) · \ N «· N - C ■ ·" ■ · ■ ^d

^C1 H., C

varseczt. The Oemlach is heated to 90 °. At this temperature, about 33 parts by volume are abdeafcilllurt at Norraaldruok. The mixture is adjusted to p "5 by adding 75% phosphoric acid, dissolved in ten times the amount of butyl alcohol. About 17 Volunitoile are distilled off in vacuo at 80 °, and parts of butanol are added to the resin solution. This operation is repeated about 7 times. The resin solution was concentrated to about 100 parts by volume by further distillation in vacuo, 0.2 part of diethylamine in 2 parts of butyl alcohol was added and the mixture was stirred while cold.

100 parts of this resin solution become 100 parts Mix well the aqueous polyvinyl alcohol solution and stir

BATH

by gradually adding 208 parts of dtat. Water emigrates. About 400 parts of a yellow-colored resin dispersion are rolled with about 21Ji alcohol content: derivative XXV.

If one leads the condensation and etherification naoh the above regulation with 17.6 parts of the dye Ponwl

through, eo receives "am" ine clear, orange-colored resin solution. 50 parts of this resin solution are mixed with 15 parts of a 50 # strength aqueous solution of a lubricant crosslinked with about 1% HoxamethyleneüiJRooyaQat of 1 mol hydroabietyl alcohol and 200 mol of ethylene oxide and duroh aLiin & hltetie- addition of% 5 parts of est. Water eiaulgiex't. About 105 parts of a resin die perfume are obtained with about 2 % TiCkenhaltt ί derivative XXVI.

BAD ORSGiNAL

1 η / 1 97n

- 36 - Example 9

65.6 parts of 4,4 *, * ^M , 4 ^lf '-tetramino-copper phthaioeyanine and 200 parts of nitrobenzene are ground for several hours in a "Kleen roll mill" then poured into a suitable reaction vessel with further 1030 parts of nitrobenzene. After adding 110 parts of cyanuric chloride, 1 part of pyridine and 1 part of dimethylformamide, the reaction mixture is kept at a temperature of 200 to 205 ° for 50 hours. After cooling, it is filtered off on a suction filter and the residue is washed thoroughly with acetone and then dried. About 86 parts of a greenish-blue powder with a chlorine content of 12 liters are obtained.

63 parts of the condensation pro duietea thus obtained are finely powdered in an autoclave with a capacity of 2000 broaching parts in 1200 Share nitrobenzene supendlert. Be in cold condition about θ atmospheres of ammonia gas pressed from a bomb, then the closed autoclave is heated to 1 * 0 bit 150 ° for 15 hours, the pressure being a maximum of 37 atmospheres achieved. After cooling, the contents of the autoclave are placed on a. Nutsche filtered and successively with Nitrobensol, Alcohol and Watstr washed. Obtained after drying

809810/1270

an ollvogrUnea powder with a nitrogen content of 25 »5 # and a chlorine content of 4.1 #"

In the catfish indicated in Example 5, 15 parts of the product thus obtained are then mixed with 72 parts of 37 # aqueous formaldehyde solution and ^? f5 "j7 parts of melamine are reacted, the methylene compound is etherified with methanol and the methyl ether is processed into a microdisperse dough with a dry content of about 39.6% with the aid of a condensation product of naphthalene sulfonic acid and formaldehyde: derivative XXVII.

Claims (1)

. ' Claim 1. A method of Kai * "distribution ne ^ he dye derivatives, characterized geksrmzelcmiet that one organic öehiifer- in water to ukLösIlohe, at least one ätherten VSR with optionally Alkyiolgruppen dyes containing reactive Sub3tifcuenten with the formation of mixtures of optionally v-isräfcherte Älkylolgruppsn containing Har - precondensates, in particular the formation of aminoplasts, iuasafcst> 2. The method according to claim 1, characterized in that nsan uses raw materials which contain HgN-öruppsn as reactive substances. 3. The method according to claim 2, characterized in that one uses DAS3 Aasgangsfarbstoffe that a Remainder of the formula (HN- alkylene} ^ - NH ₂ .N - t, - G &quot; N cm, in which X a further substituted anno- "^ or oxy group, an alkyl, aryl or aralkyl group, φ a halogen atom or a C-HN-alkylene> —- γ — NH ^ group σ * ' ο means, where m and η are each an integer of the value of co represent at most 2 . _BÄD of |, _Q , _NAL NftUO 1413780 4. Proceed. ϊ \ &<ύι claim 3 * thereby gefeennzeioh * net that starting materials i'erwendet that the remainder of the formula ., HC-
- C "N ' -: "if = 0 contain., 5 · The method according to claim 2, characterized in that one uses starting Farbbsfcoffö as reactive Substituents !! on benzene or naphthalene residues contain bound iUN groups » 6 ο lapse according to one of claims 3 and 4, since te * characterized by., Äass raan as starting materials used in 1,4- or preferably!, S-position substituted anthraquinones, in which one of the substituents is an atomic grouping bonded to the anthraquinone nucleus via an -NH group of the one of claims 3 ϊϊπο 4 indicated composition and aev others an identical grouping or an aylaraino group, preferably an optionally further substituted aroylaraino group. 7. The method according to any one of claims 3 ^and d ^ *, characterized in that further substituted dibenzanthrones are used as starting dyes in the specified catfish. BATH 809810/1270 8. Proceed. h one of the claims j! /. "S to 5, through characterized in that the starting dyes in further substituted azo dyes are used in the manner indicated. 9. The method according to any one of claims 3 and h, characterized in that further substituted oxazines are used as starting dyes in the manner entered. 10 p method according to any one of claims 1 to 9, characterized characterized in that the dyes are reacted with urea and formaldehyde. 11. Process according to one of claims 1 to %, characterized in that the dyes are reacted with amitiotriazines, preferably melamine and formaldehyde " Iß, method according to any one of claims 1 to 11, characterized marked that the dyes with «inta Substantial excesses of aminoplast formers, Ü5. Method according to claims 10 to 12, characterized characterized by the fact that the starting material is »in the quantity ratio from 1 molecule of dye to about 5 to to molecules nitrogen-containing aminoplast former and about 10 to XiO 'Molecules formaldehyde umsitat'. "■■ · '..- ■■' BAD ORIGINAL '■ & 09810 / 127Ü' Ι4α method according to one of claims I to 13, characterized in that the reaction products au »dyes and aminoplast formers; with nteärlgmolekulartn Alcohols, preferably methanol, are compared. " Process according to one of Claims 1 to IJ, characterized in that the reaction products of dye and thermoplastic compounds are etherified with alcohols containing 3 to 7 carbon atoms, preferably n-butan-nol. 16. The method according to any one of claims 1 to 15, . characterized by the fact that the starting dyes are used in finely dispersed form with the formation of the Harxvorkondensatö implements. BATH 809810/1270