DE3000569A1 - DYE PREPARATIONS AND THEIR USE - Google Patents

Description

^Case

Dye preparations and their use

The present application relates to new and advantageous dispersion Dye or optical brightener preparations, in particular those of disperse dyes, containing alkoxylated Formaldehyde condensation products of mixtures of alkylphenols and (higher-alkyl) -aminoalkylene-polyamines, optionally mixed with unsubstituted alkylene polyamine or alkyl phenols themselves or mainly containing mixtures of both formaldehyde condensation products, all of which have between 30 and 450 (lower alkylene) oxide units per molecule (based on the total number of phenolic and amino groups) contain »

In particular, the present invention relates to such preparations containing as a dispersing agent, formaldehyde condensation products or more mono- or di-C-C-alkyl phenols, preferably in Mixture of N-C -C -alkyl-aminoalkylene-polyamines, or a mixture thereof with unsubstituted alkylene polyamines, in which between 30 and 450 (lower alkylene) oxide units per molecule (based on phenol and Amine component) are present.

The present invention accordingly covers such preparations which contain formaldehyde condensation products of mixtures of alkoxylated C -C -alkylphenols of the following formulas I and II as dispersing aids

II R

wherein the phenolic groups with the same or different - (alk-O) -H Residues in which alk = C “H. or CH and η = 30-450,

2 4 3d

Mthert are, the ratio of I: II between 1: 1 and 1: 3 and in which R stands for the same or different C ^ -C. " Alkyl radicals.

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The present invention primarily relates to such preparations which, as dispersing agents, are reaction products of C -C -alkylphenols and N-C 1 -C 4 -alkyl-aminoalkylene-polyamines (2N-6N) or their Mixture with unsubstituted alkylene polyamines (2N-6N) with formaldehyde, further alkoxylated with 40-300 times the amount of a lower alkylene oxide, in which the ratio in the phenol / amine mixture between 2: 1 and 1: 2, especially 1.5: 1 to 1: 1.5, especially 1: 1 is included.

In a specific embodiment, the present invention relates finally those preparations in which the aforementioned two Basic components are present together · Such mixtures contain these components in any proportions, but preferably between 1: 5 and 5: 1.

The present invention further relates to the production of such preparations as aqueous concentrates or pastes, their use for treating, especially for dyeing, textiles and the treated bezw. dyed textiles themselves.

The inventive auxiliaries of the mono- and disubstituted phenol type (a), in which R a ^c -, ~ ^c - _,? > Particularly a C-C alkyl group, and specifically the nonyl radical is known to be prepared by the reaction of 0.5-1 mol of formaldehyde per mole of phenol under acidic conditions (zBbei 50-65 ⁰ C, H SO, several hours). The further reaction with 30-450 mol, preferably 40-150 mol, of a lower alkylene oxide, especially ethylene or propylene oxide or mixtures of both, preferably ethylene oxide, proceeds under alkaline conditions (eg at_140-180 ° C; NaOH; several hours).

In the auxiliary type (b) according to the invention, the one which is mono- or dialkyl-substituted Phenol is again preferably a C -C -alkyl substituted phenol with the substituents in the 2 or 2,4 position. The polyamines contain up to 6, first up to 4 N atoms as primary or secondary amino groups and accordingly up to 5, preferably up to 3, alkylene groups (preferably ethylene or propylene).

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In the case of an alkyl substitution, a ^C ₁₉ "" C, preferably C -C "-alkyl radical is present on an N atom. Preference is given to N-alkyl-substituted propylenediamines such as stearyl- or behenyl-propylenediamine or the known aminopropyl tallowamine (a C - C - alkyl group-containing compound) .Unsubstituted ethylene polyamines can be condensed in up to about 30% (by weight); DMthylenetriamine is preferred here.

The mixtures contain a ratio of phenol and amine components 2: 1 to 1: 2, preferably 1.5: 1 and 1: 1.5, especially about 1: 1. The condensation with formaldehyde, under basic conditions, happens with up to to 1 mole of formaldehyde per total mole of phenol and amine. The condensation with 30-450, especially 40-200 and especially 40-150 mol of a lower one Alkylene oxide also happens [as under a)] under basic conditions, preferred alkylene oxides being the same as set out in (a) above.

An auxiliary (c) preferred according to the invention is one of (a) and (b) where the ratios of (a) to (b) in this mixture are preferably between 1: 5 and 5: 1. The preparation of (c) can be both by simply mixing (a) and (b), as well as by alkoxylation together of the two preliminary products.

All connections are neutralized in a final stage, e.g. with Vinegar — or formic acid.

Suitable dyes for the production of the preparations according to the invention are above all the disperse dyes of the most diverse dye classes known from the Color Index, as well as brighteners. Most of all are these are compounds of the azo and anthraquinone series.

For example, without wishing to limit the invention, the following are Dyes called:

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C.I Disperse Yellow 60, C.I. Disperse Yellow 3, C.I. Disperse Orange 30, C.I. Disperse Red 5, C.I. Disperse Red 13, C.I. Disperse Red4, CI. Disperse Red 167, C.I. Disperse Violet 1, C.I. Disperse Blue 19, C.I. Disperse Blue 14, C.I. Disperse Blue 3, C.I. Disperse Blue 26, C.I. Disperse Blue 73, C.I. Disperse Blue 79.

The preferred optical brighteners are those of the Thermosol series.

The usual additives can be used as additives in the preparations according to the invention Auxiliaries such as antifoam agents, anionic or non-ionic surfactants or preservatives may be present. Also suitable water retention agents such as alkylamino higher alkyl amines, glycol, glycerine, Diglycol, urea or formamide can be used in the preparations according to the invention be included.

The dye preparations according to the invention are produced in Usually, in conventional wet grinding apparatus, such as kneaders, ball or vibrating mills, high-speed agitator ball mills and similar aggregates, whereby a comminution of the dye particles down to "* - 2 / µm is sought.

The amount of dispersing aid in the finished preparation is approximately 10 to 100% of the dye or brightener, preferably 30 to 60%.

Adjustment to the desired dye concentration of the liquid preparations takes place after grinding. 15-25% settings are preferred, but higher concentrates up to e.g. 50% (usually these are Pastes).

The new preparations are particularly suitable for the production of dye liquors and printing ink preparations which contain a cellulose ether as a binder, saponified natural resins or water-soluble synthetic resins or also Po-

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lyacrylate binders as well as synthetic or natural commercially available thickeners contain.

The dye preparations according to the invention are distinguished from known ones Dye dispersions mainly due to a high dye concentration and good compatibility with binders. The dyeings or prints produced therewith show an excellent print yield.

The following examples serve to illustrate the invention. Parts are parts by weight or volume and percentages are percentages by weight, temperatures are given in Celsuisgraden.

example 1

A) 283 parts (1 mol) of a 50:50 nonyl / dinonylphenol mixture are reacted with 24 parts (0.8 mol) of formaldehyde at 50 to 65 ° in the presence of 3% H SO within 3-4 hours. This is followed by washing out the H ^so and draining in vacuo. Subsequently, ethoxylation is carried out at 140-160 ° with 1980 parts (45 mol) of ethylene oxide with the addition of 2.5% NaOH as a catalyst. After the reaction has ended, the reaction product is neutralized with formic acid.

B) 24 parts of the dye CI. Disperse Orange 30 10 parts of the above reaction product

24 parts of glycerin and

42 parts of water are mixed with one another and then in a ball mill up to an average particle size of ~ 2 / ** grind.

The above formulation shows none with synthetic thickeners Viscosity drop. The pressure yield is excellent, the dispersant shows no retarding effect.

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Example 2

A) 110 parts (0.5 mole) of p-nonylphenol and 163 parts (0.5 mole) of stearylpropylenediamine are allowed to react with 30 parts (1 mol) of paraformaldehyde for 6 hours at 80-100 °. After removing the water in the In vacuo and adding 1% NaOH, 3580 parts (80 mol) of ethylene oxide are added in portions at 160-180 ° and until the end of the Reaction heated further. The reaction product is neutralized with formic acid and can be used as such.

B) 15 parts of the dye CI. Diäperse Blue 79

5 parts of the above reaction product
IS parts of glycerin and

65 parts of water are mixed together and then ground in a ball mill to an average particle size of ^ - 2 μ .

The concentrate obtained can be stored as such. The formulation does not cause a drop in viscosity with synthetic thickeners. The pressure yield is excellent, the disperser does not show any retarding effects Effect.

Example 3

A) 620 parts of 2,4-dinonylphenol (technical), 218 parts of 4-isooctylphenol and 214 parts of 2,4-di-terr. Butylphenol are mixed with 202 parts of an aqueous 30% CHO solution. 0.4 mol per phenol component) in the presence of 31.6 parts of H _? ^S0 /, (monohydrate) implemented. The CH 0 solution is added in 2 portions within 60 minutes (20 minutes each) at 50-65 °. The reaction product obtained was neutralized with 250 parts of 15% NaOH (temp. -70 °). The water is distilled off in vacuo. The MW of the reaction products is 274-277.

B) 310 parts of dinonylphenol (technical), 108.9 parts of 4-isooctylphenol and

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63.5 parts of xylenol (technical) are added to 415 parts of stearylpropylenediarain and 129 parts of diethylenetriamine mixed. 6 hours long condensed with 150 parts of paraformaldehyde at 50-65 °. The distance the water takes place in a vacuum at 90-100 °; the reaction product obtained has a MW of 473-477.

C) 274 parts of A) and 473 parts of B) are in the presence of 18.7 Parts of NaOH reacted at 160-180 ° with 1320 parts (30 mol) of ethylene oxide. When the reaction has ended, it is neutralized with formic acid. The reaction product is a completely water-miscible liquid and can as such, as indicated in Examples 1 and 2, be used.

With 2640 Teil.n (60 mol) of ethylene oxide a soap-like dark brown A crude product is obtained which can also be used as such · with 3960 parts (90 mol) of ethylene oxide it becomes a paste-like product Get a product that can be used directly.

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Claims (9)

30Q0569 SANDOZ-PATENT-GMBH 7850 Lörrach Dye preparations and their use 1. Dispersion dye or optical brightener preparations, containing as dispersing agent formaldehyde condensation products of one or more mono- or di- C 1-4 alkyl phenols, preferably in a mixture with N- C 1-4 alkylaminoalkylene polyamines, or their mixture with unsubstituted alkylene polyaraines, in which between 30 and 450 (lower alkylene) oxide units (based on phenol and amine components) are present per molecule. 2. Preparations according to claim 1, containing as dispersing agents Formaldehyde condensation products of mixtures alkoxylioiter C.-C.-alkyl phenols of the following formulas OH R wherein the phenolic groups with the same or different - (alk-0) -H radicals, in which alk ■ C ₀ H, or C ₀ H, and ο 2 4 3 6 η ■ 30-450, are etherified, the ratio of I: II is between 1: 1 and 1: 3, and in which R stands for identical or different C -C alkyl radicals. 3. Preparations according to Claim 2 containing such as dispersing agents 030031/0629 - 2 - Case 150-4261 Compounds in which a derivative of a C ~ C mono- and dialkylphenol-7 especially a nonyl / dinonylphenol mixture, ethoxylated with 30-450, especially 40-150 ethoxy units, is present. 4. Preparations according to claim 1, containing as dispersing aid, Reaction products of C -C -alkylphenols and N-C -C -alkyl-aminoalkylenes , polyamines (2N-6N) or their mixture with unsubstituted alkylene ■ ·. -polyamines (2N-6N) with formaldehyde, further alkoxylated with 40-300 times the amount of a lower alkylene oxide, in which the ratio in the phenol / amine mixture is between 2: 1 to 1: 2, especially 1.5: 1 to 1: 1.5, especially 1: 1. 5. Preparations according to claim 4, containing as dispersing aid the reaction products mentioned there, alkoxylated by 50-200 times molar amount of a lower alkylene oxide, especially des Ethylene oxide. 6. Preparations according to Claims 1 to 5, containing the components of claims 2 or 3 and 4 or 5 mixed with one another in a ratio between 1: 5 and 5: 1. 7. Preparations according to claims 1 to 6 as aqueous concentrates or pastes. 8. Use of the preparations according to Claims 1 to 6 for dyeing Textiles. 9. The textiles obtainable according to claim 8. 030031/0129 BATH