DE102007051279A1 - Colorant preparation, useful for tinting a cleanser, preferably softener or detergents, inks, crayons and markers, comprises coloring agent from acid-, polymer-, reactive- or solvent-dye, and oligo- or polyester-compounds - Google Patents

Abstract

Washable colorant preparation comprises: a coloring agent from acid dye, polymer dye, reactive dye or solvent dye; and oligo- or polyester-compounds (I). Washable colorant preparation comprises: a coloring agent from acid dye, polymer dye, reactive dye or solvent dye, and oligo- or polyester-compounds of formula (R 1>-(O-R 2>) a-[O-C(=O)-R 3>-C(=O)-(O-R 4>) b] c-O-C(=O)-R 5>-C(=O)-O-(R 6>-O) d-R 7>) (I). R 1>, R 7>1-18C-alkyl; R 2>, R 4>, R 6>1-8C-alkylene; R 3>, R 5>arylene or alkarylene; a, d : 1-500; b : 1-200; and c : 1-20. Where the sum of a, b and d is at least 5. An independent claim is included for preparing the washable colorant preparation, comprising dissolving, milling or melting (I) and the coloring agent.

Description

These Invention includes washable color mixtures with specific oligo- and polyesters. The blends are made by mixing colorant or ink made with the polymer. These mixtures show excellent coloring, but low staining behavior, especially in polar preparations, such as. In dishwashing detergents, Inks, colors and marker colors.

The Designation "washable color mixture" within this Invention includes paint formulations for detergents, inks and other colored preparations made by water and / or Detergents can be washed off fibers or skin.

Although water-soluble polymer dyes are preferred, acid dyes are often used as a coloring ingredient for fabric softeners and detergents. The leachability of such formulations depends on the colorant or dye used, but this property can be improved substantially by laxability improving additives within the preparation. These additives belong to a class of substances (including polymers) that facilitate leachability and removal of colorants from unwanted surfaces. Without reference to a scientific theory, it is believed that these additives either interact with the potential "docking sites" in front of the colorant or ink, or block the reactive groups of the colorants, thereby preventing attachment or reaction with the substrate such dye-blocking preparations are prepared with polyaromatic sulfonates and their salts, as in US 5,116,410 . EP-A-0 557 115 A1 , and WO 98/36032 A1 described. Such specific dye blockers are used to prevent permanent staining of certain substrates; however, many of these preparations are highly colored and often have a negative effect on the hue's hue. This is especially true for lighter colors.

WO 01/88043 describes washable color preparations of mixtures with specific low molecular weight carboxylic acids / carboxylates with colorants, dyes, inks and the like. However, the carboxylic acids must first be neutralized with caustic prior to use, which means an additional operation. Furthermore, the use is set to a neutral pH range.

It So there is still a need for the industry to be environmentally friendly, easy and inexpensive to produce, washable Color preparations with low staining potential and great color strength.

aim the invention is the development of washable color preparations, the high solubility, excellent dyeing properties and low staining potential for skin and Have clothes.

One Another object of the invention is the preparation of a preparation, which is easy with water or polar solvents from surfaces how clothes and skin can be removed.

A Another object is the provision of a washable paint preparation, in sufficient quantities in fabric softeners, detergents, Inks, marker compositions and the like can be used can. Furthermore, the preparations should be in a wide pH range used and mixed with perfumes and preservatives without destabilizing the resulting mixture or complexed.

worin
R¹ und R⁷ ein linearer oder verzweigter C₁-C₁₈-Alkylrest bedeutet,
R², R⁴, R⁶ unabhängig voneinander C₁-C₈-Alkylen-, z. B. Ethylen-, Propylen-, Butylen- und/oder Cycloalkylenreste, z. B. 1,4-Cyclohexylen- oder 1,4-Dimethylencyclohexylenreste sowie deren Gemische, bedeuten,
R³ und R⁵ Arylen- oder Alkarylen-, wie z. B. 1,4-Phenylen, 1,3-Phenylen, 1,2-Phenylen, 1,8-Naphthylen, 1,4-Naphthylen, 2,2'-Biphenylen, 4,4'-Biphenylen und deren Mischungen bedeuten,
a und d jeweils eine Zahl zwischen 1 und 500 bedeuten,
b eine Zahl zwischen 1 und 200,
wobei die Summe von a, b und d mindestens 5 ist;
c eine Zahl zwischen 1 und 20 ist.The invention relates to a washable colorant preparation containing a colorant from the group of acid dyes, polymer dyes, reactive dyes and solvent dyes, and oligo- and polyesters of the formula (1)

wherein
R ¹ and R ^{7 is} a linear or branched C ₁ -C ₁₈ -alkyl radical,
R ² , R ⁴ , R ^{6 are} independently C ₁ -C ₈ alkylene, z. For example, ethylene, propylene, butylene and / or cycloalkylene leftovers, z. B. 1,4-cyclohexylene or 1,4-Dimethylencyclohexylenreste and mixtures thereof, mean
R ³ and R ^{5 are} arylene or alkarylene, such as. For example, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2'-biphenylene, 4,4'-biphenylene and mixtures thereof,
a and d each represent a number between 1 and 500,
b is a number between 1 and 200,
wherein the sum of a, b and d is at least 5;
c is a number between 1 and 20.

Preference is given to oligo- and polyesters of the formula (1) in which
R ¹ and R ^{7 are} methyl and / or ethyl,
R ² , R ⁴ , R ^{6 are} ethylene, 1,2-propylene, or mixtures thereof,
R ³ and R ^{5 are} 1,4-phenylene and 1,3-phenylene,
a, b and d are a number between 1 and 100, the sum of a, b and d being at least 5;
c is a number between 1 and 10
mean.

The ratio of the oligo- and polyester to the colorant can be between 1:10 ^-6 and 1: 100, preferably between 1: 2 and 1: 100, in particular between 1: 5 to 1:20.

Oligo- and polyesters of the formula (I) are as in EP-A-0 964 015 described produced.

The WO 2005/056742 A1 describes a method for preventing color position on textile fabric during a decoloring process, especially during a stonewashing process using a terephthalic acid polyester-polyether. Colorant preparations are not proposed there.

Preferred as a coloring component is a polymer dye consisting of a chromophore, preferably from the group of triphenylmethanes, azo, phthalocyanine, anthraquinone, aza [18] annulen, formazan-copper complex, triphendioxazine, nitroso, nitro, diarylmethane, triarylmethane, xanthene, Acridine, methine, thiazole, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyl ketone and stilbene, and polyether polyol chains. Such polymer dyes are for example made US 5,043,013 known.

preferred Colorants are also acid dyes, in particular blue and yellow acid dyes, or mixtures with differently colored acid dyes. examples for Acid dyes are C.I. Acid Blue 9, Acid Blue 80; acid Violet 12, Acid Green 3, Acid Yellow 17, Acid Yellow 23, Acid Red 52 and Acid Red 388.

preferred Colorants are also reactive dyes, such as. B. C.I. Reactive Black 5, C.I. Reactive Blue 2, C.I. Reactive Blue 4, C.I. Reactive Blue 5, C.I. Reactive Blue 7, C.I. Reactive Blue 9, C.I. Reactive Blue 15, C.I. Reactive Blue 19, C.I. Reactive Blue 27, C.I. Reactive Violet 3, C.I. Reactive Violet 5, C.I. Reactive Red 2, C.I. Reactive Red 23, C.I. Reactive Red 24, C.I. Reactive Orange 4, C.I. Reactive Orange 13, C.I. Reactive Orange 16, C.I. Reactive Orange 78, C. I. Reactive Yellow 1, C.I. Reactive Yellow 3, C.I. Reactive Yellow 13, C.I. Reactive Yellow 14, C.I. Reactive Yellow 17, C.I. Reactive Yellow 22 and C.I. Reactive Yellow 95.

Other additional additives, such as. B. preservatives, surfactants, Wetting agents, antistatic agents, resins, waxes, pH regulators, perfumes, Chelating agents (such as EDTA), bactericides, fungicides, stabilizers, Polymer additives such as guar gum, polyethylene oxide and cyclodextrins as well as pigments, in combination with the inventive Colorant preparations are used.

In front the use of the inventive Colorant preparations diluted with suitable solvents become. Such solvents include water, polar organic solvents, such as alcohols or ketones, one. In general, colorant becomes in proportion diluted to solvent in the range 1: 0.1 to 1: 100, preferably 1: 0.5 to 1:50 and particularly preferably 1: 1 until 1:20 lies.

object The invention also provides a process for the preparation of the colorant preparations by dissolving, grinding or melting the polymer and the Colorant, conveniently under elevated Temperature, z. B. from 30 to 200 ° C.

The invention also provides the use of the colorant preparation according to the invention for coloring cleaning agents, such as fabric softeners or detergents, as well as inks, color pencils and markers, for. B. Pattern spray markers for lawn. These specific formulations may also contain larger amounts of additives and liquid carriers, such as water, lower alcohols, e.g. For example, ethanol, methanol and isopropanol, glycol ethers, alkylene glycols, phenols.

As already described, the inventive Preparations quite simply from different surfaces (Skin, clothing, white boards and other) are removed. Further precipitated from these (aqueous) solutions no solid matter. These preparations are particularly preferred in liquid household agents like detergents and Fabric softener used.

In In the following examples, parts are parts by weight.

example 1

4 parts of CI Acid Blue 80 are added to 96 parts of polyoxyalkylene terephthalate of the formula (1) with R ¹ and R ⁷ = methyl, R ² and R ⁶ = ethylene, R ³ and R ⁵ = 1,4-phenylene, R ⁴ = 1,2-propylene, a, b and d is on average about 90, c is on average about 5, given. The mixture is warmed to 45 ° C and stirred for 10 min. The obtained preparation can be used without further modifications.

Example 2

10 Parts of C.I. Acid Blue 80 are added to 90 parts of polyoxyalkylene terephthalate given according to Example 1. The mixture will open Heated to 50 ° C and stirred for 30 min. The obtained preparation can be used without further modifications become.

Example 3

10 Parts of C.I. Acid Yellow 17 are added to 90 parts of polyoxyalkylene terephthalate given according to Example 1. The mixture will open Heated to 50 ° C and stirred for 25 min. The obtained preparation can be used without further modifications become.

Example 4

6 parts of CI Acid Yellow 17 are added to 94 parts of polyoxyalkyl terephthalate with R ¹ and R ⁷ = methyl, R ² and R ⁶ = 1,2-propylene, R ³ and R ⁵ = 1,4-phenylene, R ⁴ = 1, On average, 2-propylene, a, b, and d is about 120, c is about 10 on average. The mixture is warmed to 50 ° C and stirred for 20 min. The obtained preparation can be used without further modifications.

Example 5

8th Parts C.I. Acid Yellow 17 and 2 parts C.I. Acid Blue 80 to 90 parts of polyoxyalkylene terephthalate according to Example 4 given. The mixture is heated to 50 ° C and stirred for 25 min. The obtained preparation can be used without further modifications.

Example 6

18 Parts C.I. Acid Yellow 17 and 2 parts C.I. Acid Blue 80 to 80 parts of polyoxyalkylene terephthalate according to Example 4 given. The mixture is heated to 50 ° C and stirred for 20 min. The obtained preparation can be used without further modifications.

Example 7

10 parts of ^® Liquitint Blue HP (polyoxyalkene-modified reactive dye, available from Milliken) are added to 90 parts of polyoxyalkylene terephthalate according to Example 1. The mixture is warmed to 50 ° C and stirred for 25 min. The obtained preparation can be used without further modifications.

Example 8

30 parts of polyglycerol-modified CI Reactive Blue 19 are added to 70 parts of polyoxyalkylene terephthalate according to Example 1. The mixture is warmed to 50 ° C and stirred for 20 min. The obtained Preparation can be used without further modifications.

Example 9

19 Parts C.I. Acid Yellow 17 and 1 part C.I. Acid Blue 80 to 80 parts of polyoxyalkylene terephthalate according to Example 4 given. The mixture is used in an IKA mill for Ground for 10 s. The resulting preparation is dissolved in water and can be used without further modifications.

Example 10

5 Parts of C.I. Acid Blue 80 are added to 95 parts of polyoxyalkylene terephthalate given according to Example 4. The mixture is in an IKA mill for 10 s ground. The obtained Preparation can be used without further modifications.

The Preparations of Examples 1 to 10 are in water or polar Solvents incorporated and on hue, migration and Stability examined:

Example 11

The Preparation of Example 1 is poured into water and stirred until a homogeneous colored formulation is obtained.

Example 12

The Preparation of Example 3 is poured into water and stirred until a homogeneous colored formulation is obtained.

Example 13

The preparation of Example 1 is poured into water and stirred until a homogeneous colored formulation is obtained. The dissolved preparation has a homogeneous dark blue color and was used for the in WO-01/88043 skin staining test described. The results of the skin stain test were compared with the results of ^® Liquitint Blue HP (polyoxyalkylene modified reactive dye, available from Milliken Chemical Company) and Acid Blue 80. The preparation of Example 1 showed the lowest staining behavior.

Example 14

The formulation of Example 4 is added to water and stirred until a homogeneous colored formulation is obtained. The dissolved preparation has a homogeneous yellow hue and was used for the in WO-01/88043 skin staining test described. The results of the skin stain test were compared with the results of Liquitint Yellow (polyoxyalkylene modified reactive dye available from Milliken Chemical Company) and Acid Yellow 17. The formulation of Example 4 showed the lowest staining behavior.

Example 15

The preparation of Example 1 is poured into water and stirred until a homogeneous colored formulation is obtained. The dissolved preparation has a homogeneous dark blue color and was for a tissue Anfärbungstest in a commercially available fabric softeners ^(® Softlan Soft & Mild Hypoallergenic, Fa. Colgate) is used.

• – Aufbringen des gefärbten Weichspülers auf Multi-Faser-Test-Streifen (MFTS) (0,15 g auf jeden Streifen)
• – Einwirken lassen auf den MFTS für 30 Minuten bei Raumtemperatur
• – Füllen der Linitest (Fa. Heraeus) Becher mit je einem MFTS. Ein Becher enthält als Referenz den ungefärbten Weichspüler.
• – Ein Waschzyklus mit 200 ml kaltem Wasser, der 10 Minuten dauert (vergleichbar mit dem Spülzyklus in einer Haushaltswaschmaschine).
• – Nach dem Ausspülen durchläuft der MFTS einen Schleudergang einer Waschmaschine, um das enthaltenen (farbige) Wasser zu entfernen.
• – Coloristische Messung mit einer Elrepho 3000 (Fa. Datacolor)

The staining test:

• Application of Dyed Fabric Conditioner to Multi-Fiber Test Strips (MFTS) (0.15 g on each strip)
• - Allow to act on the MFTS for 30 minutes at room temperature
• - Fill the Linitest (Heraeus) cups with one MFTS each. A cup contains as reference the undyed fabric softener.
• - One wash cycle with 200 ml of cold water, which lasts 10 minutes (comparable to the rinse cycle in a household washing machine).
• - After rinsing the MFTS goes through a spin cycle of a washing machine to the enthal removed (colored) water.
• Coloristic measurement with an Elrepho 3000 (Datacolor)

The results of the tissue staining test were compared with the results of Acid Blue 80 and Liquitint Blue HP (polyoxyalkylene modified reactive dye). The preparation of Example 1 showed the lowest staining behavior on cotton. (Table 1) Table 1 example AE Acid Dye (Acid Blue 80) 2.74 Liquitint Blue HP 3.77 example 1 1:48

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 5116410 [0003]
• EP 0557115 A1 [0003]
• WO 98/36032 A1 [0003]
• WO 01/88043 [0004, 0036, 0037]
• - EP 0964015 A [0012]
• WO 2005/056742 A1 [0013]
• US 5043013 [0014]

Claims (10)

Washable colorant preparation containing a colorant from the group of acid dyes, polymer dyes, reactive dyes and solvent dyes, and oligo- or polyesters of the formula (1)

wherein R ¹ and R ^{7 is} a linear or branched C ₁ -C ₁₈ alkyl radical, R ² , R ⁴ , R ^{6 are} independently C ₁ -C ₈ -alkylene radicals, R ³ and R ^{5 are} arylene or alkarylene, a and d each is a number between 1 and 500, b is a number between 1 and 200, the sum of a, b and d being at least 5; c is a number between 1 and 20. Colorant preparation according to claim 1, characterized in that R ¹ and R ^{7 is} methyl and / or ethyl, R ² , R ⁴ , R ^{6 is} ethylene, 1,2-propylene, or mixtures thereof, R ³ and R ^{5 is} 1,4-phenylene or 1,3-phenylene, a, b and d is a number between 1 and 100, wherein the sum of a, b and d is at least 5; c is a number between 1 and 10. Colorant preparation according to claim 1 or 2, characterized in that the colorant is a yellow or blue acid dye is. Colorant preparation according to claim 3, characterized in that the colorant is C.I. Acid Blue 80 or C.I. Acid Yellow 17 is. Colorant preparation according to one or more of claims 1 to 4, characterized in that the ratio of the oligo- or polyester of formula (1) to the colorant is between 1:10 ^-6 and 1: 100. Colorant preparation according to one or more of Claims 1 to 5, characterized in that the ratio of the oligo- or polyester of the formula (1) to the colorant between 1: 5 and 1:20 lies. Colorant preparation according to one or more of Claims 1 to 6, characterized in that aids from the group of preservatives, surfactants, wetting agents, antistatic agents, Resins, waxes, pH regulators, perfumes, chelating agents, bactericides, Fungicides, stabilizers, polymer additives and pigments are. Colorant preparation according to one or more of Claims 1 to 7, characterized in that the solvent from the group of water and the polar organic solvents are included. Process for the preparation of colorant preparations according to one or more of claims 1 to 8 by loosening, Milling or melting the oligo- or polyester of the formula (1) and the colorant. Use of the colorant preparation after one or more of claims 1 to 8 for coloring of cleaning agents, such as fabric softeners or detergents as well as inks, color pencils and markers.