TW201313839A - Acid dye blends for polyamide and wool - Google Patents

Abstract

The invention relates to an acid dye blend comprising (a) 20 to 95 wt% of at least one dye A having the general structure (A) and (b) 5 to 80 wt% of at least one dye B having the general structure (B).

Description

Acid dye blend for polyamine and wool

The present invention relates to an acid dye blend comprising a) from 20 to 95% by weight of at least one dye A having the general structure (A) And b) 5 to 80% by weight of at least one dye B having the general structure (B)

Acid dyes are mainly used to dye wool, other animal hair, silk and polyamide. Although these fibers are chemically similar (polyaminocarboxylic acids), in particular on the one hand the physical differences between wool and hair and on the other hand polyamines and filaments are extremely large. As a result, the nature of the acid dye to polyamide can be significantly different from that of the wool. These are for example

- its color itself

- Light fastness (usually poor for polyamides compared to wool)

- Cumulative (usually poor for polyamide)

- Wet fastness

Likewise, wool has a reduced holding effect during dyeing and during some final processing, which can result in degradation of many acid dyes used on polyamides during dyeing, as well as tonal changes during final processing.

It is further known that there are many acid dyes that dye the tip of the wool fiber to be significantly different from the root, which can only be insufficiently corrected using certain adjuvants. A very good balance between the root and the tip is essential to give the wooly texture an eye-catching appearance. Therefore, multiple acid dyes are typically blended into a product to give the wool an eye-catching appearance. However, these blends are not suitable for dyeing polydecylamine to a medium or deep combination of color systems because of the hindrance effect of the various components (due to the low color buildup of some of the blending components required) . Therefore, only a very small number of acid dye blends are recommended for use with both polyamido and wool and especially for their blends. A few commercially available examples are low moisture fastness "stain dyes" for dyeing polyamide/wool carpet yarns. Acid dye blends for apparel materials comprising wool and polyamides are particularly lacking in producing good appearance for both wool and polyamide The blue component, which can be used with the yellow component and the red component for the dyeing of the reproducible combination color, has the necessary fastness to cleaning, sweat and processing.

It has now surprisingly been found that the acid dye blends described below provide good reproducible dyeing of polyamides, wool and good moisture fastness to polyamide/wool blend fibers.

The present invention provides an acid dye blend comprising a) from 20 to 95% by weight (preferably from 30 to 95% by weight and more preferably from 50 to 90% by weight) of at least one dye A having the general structure (A)

Wherein R1, R2, R3 and R4 are each independently H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, -NR12R13, C ₁ -C ₆ -alkylene-NR12R13; H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, -NR12R13, C ₁ -C ₆ -alkylene-NR12R13, sulfonic acid group, R50 is H, C ₁ -C ₆ - Alkyl, C ₅ -C ₆ -cycloalkyl; R 12 is H, C ₁ -C ₆ -alkyl; R ₁₃ is -CO-CH ₂ -Cl, -SO ₂ -phenyl, wherein phenyl is substituted or Unsubstituted; M is H, alkali metal, ammonium; and b) 5 to 80% by weight (preferably 5 to 70% by weight and more preferably 10 to 50% by weight) of at least one dye B having the general structure (B)

Wherein R6 is H, phenyl, wherein the phenyl group is the substituted or unsubstituted, R7 is H, a sulfonic acid group, R8 is H, C ₁ -C ₄ - alkoxy, or R7 and R8 with the adjacent C = The C double bond combines to form a substituted or unsubstituted benzene ring, R9 is H, a sulfonic acid group, M is H, an alkali metal, ammonium or a single negative charge, wherein the weight percentage is the total weight of each of the acid dye blends. Benchmark.

The positive charge in formula (B) is typically neutralized with a negative charge of the sulfonic acid group in the molecule or with one equivalent of an anion such as Cl ^- , 1/2SO ₄ ^2- .

In the above definition, the sulfonic acid group is a group of the formula SO ₃ M.

M is preferably a single negative charge, hydrogen, alkali metal or ammonium.

In the above definition, the alkali metal is preferably Li, Na, or K, especially Na.

In the above definition, the ammonium is preferably NH ₄ ⁺ or (C ₁ -C ₄ -alkyl)NH ₃ ⁺ .

In the above definition, "substituted phenyl" or "substituted benzene ring" is preferably one or more selected from C ₁ -C ₄ -alkyl, halogen, C ₁ -C ₄ -alkoxy, hydroxy The substituent of the sulfonic acid group, the amine group or the nitro group is substituted one or more times, preferably one, two or three times. Substituents such as methyl, Cl, amine, methoxy, ethoxy and sulfonic acid groups are particularly preferred.

A preferred embodiment, R1, R2, R3, R4 are each independently preferably based H, methyl, methoxy, NR12R13 or C ₁ -C ₆ - alkylene -NR12R13, wherein R12 is preferably hydrogen or methyl and R13 is -CO-CH ₂ -Cl or -SO ₂ - phenyl, wherein the phenyl group is the substituted or unsubstituted.

In a preferred embodiment, R5 is hydrogen, methyl or sulfonic acid.

In a preferred embodiment, R50 is hydrogen, methyl, ethyl, branched C ₃ -C ₆ - alkyl, cyclopentyl or cyclohexyl, especially methyl, isopropyl or cyclohexyl.

In a preferred embodiment, R6 is hydrogen, unsubstituted phenyl or phenyl substituted with amino-, sulfonate- and/or ethoxy-.

In a preferred embodiment, R8 is hydrogen or methoxy, or is similarly In a preferred embodiment, R7 and R8 are combined with an adjacent C=C double bond to form an unsubstituted or sulfonic acid substituted benzene ring.

Preferably, the dye of the formula (A) is one in which R1 to R4 in the dye of the formula (A) is NR12R13 or C ₁ -C ₂ -alkylene-NR12R13, wherein R12 is hydrogen or methyl and R13 is SO ₂ -(4-tolyl), while the remaining R1 to R4 are each hydrogen or methyl and are the same or different, and R5 is hydrogen, methyl or sulfonic acid group, and M and R50 are each as defined above.

Particularly preferred is the dye of formula (A) wherein R 2 or R 3 is NR 12 R 13 or C ₁ -C ₂ -alkylene-NR 12 R 13 wherein R 12 is hydrogen or methyl and R ₁₃ is SO ₂ -(4-tolyl), and the rest R1 to R4 are each hydrogen or methyl and are the same or different, and R5 is hydrogen, methyl or sulfonic acid group, and M and R50 are each as defined above.

A very preferred dye of the formula (A) is that R 2 or R 3 is NR 12 R 13 or CH ₂ -NR 12 R 13 wherein R 12 is hydrogen or methyl and R ₁₃ is SO ₂ -(4-tolyl), and the remaining R 1 to R 4 are each hydrogen. R5 is hydrogen, methyl or sulfonic acid group, and M and R50 are each as defined above.

Further preferably the formula (A) is a dye wherein both of R1 to R4 is a C ₁ -C ₂ - alkylene -NR12R13, wherein R12 is hydrogen or methyl and R13 is -CO-CH ₂ -Cl, while the remaining R1 to R4 are each hydrogen or methyl and are the same or different, R5 is hydrogen, methyl or sulfonic acid group, and M and R50 are each as defined above.

Particularly preferred dyes of the formula (A) are those wherein R 2 and R 4 are each independently C ₁ -C ₂ -alkylene-NHCO-CH ₂ -Cl and R 1 , R 3 and R 5 are each hydrogen or methyl, and M and R 50 are each as above Defined by.

A very preferred dye of the formula (A) is that each of R2 and R4 is -CH ₂ -NHCO-CH ₂ -Cl and each of R1, R3 and R5 is a methyl group, and each of M and R50 is as defined above.

Preferably, the dye of the formula (B) is a phenyl group wherein R6 is unsubstituted, and R7 and R8 are combined with an adjacent C=C double bond to form a sulfonic acid group-substituted benzene ring, and R9 is hydrogen, and M is as above Definer.

Further preferred dyes of formula (B) are those wherein R6 is hydrogen or unsubstituted phenyl, R7 is hydrogen or sulfonic acid, R8 is hydrogen or methoxy, and R9 is hydrogen or sulfonic acid, and M is as above Defined by.

Further preferred dyes of formula (B) are those wherein R6 is phenyl substituted with amino-, sulfonate- and/or ethoxy-, R7 is hydrogen or sulfonic acid, R8 is hydrogen, and R9 is hydrogen, And M is as defined above.

The dyes of the formulae (A) and (B) are known per se and can be obtained by known methods, such as those described below: Ullmann, 6th ed., 10.1002/14356007.a02_355, pages 1-68 Ullmann, 6th ed., 10.1002/14356007.a03_213.pub3, pages 1-42.

The invention further provides a process for the manufacture of an acid dye blend as described above, which process comprises at least one dye A and at least one dye B in a weight ratio specified above, for example in the form of a dry powder, a press cake or preferably an aqueous solution. mixing. Dyes A and B can also be mixed with each other prior to the dye bath.

The dye blends of the present invention are particularly suitable for dyeing or printing blue-based fibrous materials composed of natural or synthetic polyamines. The dye blends of the present invention are also suitable for the preparation of ink jet printing inks and for the use of such ink jet printing inks for printing fibrous materials composed of natural and/or synthetic polyamide or cellulose (e.g., paper).

The invention further provides for the use of the dye composition for dyeing and/or printing fibrous materials composed of natural or synthetic polyamides or blends thereof (e.g., polyamide/wool).

The invention further provides for the use of the dye composition for the preparation of ink jet printing inks and for the printing of fibrous materials consisting of natural or synthetic polyamides or blended fabrics of such fibers, such as nylon/wool.

The dyeing is carried out according to known methods such as a continuous method, a dip dyeing method, a foam dyeing method or an ink jet method.

It is preferably at a temperature of 30 to 140 ° C (preferably at 80 to 120 ° C and more preferably at a temperature of 80 to 100 ° C), and is subjected to a dip dyeing method at a liquid ratio ranging from 3:1 to 40:1. Dyeing.

The substrate to be dyed can be present, for example, in the form of a yarn, a woven fabric, a looped knit or a carpet. Even for substrates that need to be handled with care, such as lamb wool, Smir, alpaca and mohair can also be fully effective for full-form dyeing. The dye blends of the invention are particularly suitable for the dyeing of fine denier fibers (microfibers).

The dye blends of the present invention are highly compatible with known acid dyes. Therefore, the dye blend can be used alone in the dyeing or printing process or as a blue component in a combined color dyeing or printing composition together with other dyes of the same class, the so-called same grade means having an acid dye process The dyeing properties can be compared, such as the firm nature and the dyeing rate on the substrate by dyeing the dye bath. The dyes of the invention are more particularly useful for use with other acid dyes. The ratio of use of the dye blends of the present invention with other acid dyes in combination dyes or printing compositions is determined by the hue to be obtained.

The dye blend of the present invention is particularly suitable for dyeing wool, silk and all nylon types, which can provide high fastness, especially good light fastness and good wet fastness (water washing, alkali) for each. Sexual sweat) staining. The dye blend has a high dye uptake rate. The color mixing ability of the dye blend is also extremely excellent. The color-added dyeing of the substrate has an outstanding quality. Moreover, all dyes have a constant hue under artificial light. In addition, the retort resistance and boiling resistance are also good.

One of the decisive advantages of the dye blends of the present invention is that it is metal free and provides extremely uniform dyeing of wool and polyamide.

The dye blend of the present invention can also be used as a blue component in three primary color dyeing or printing. Tricolor dyeing or printing can be carried out using all conventional and known dyeing and printing methods, such as continuous, dip dyeing, foam dyeing or ink jet.

The composition of the individual dye components in the three primary color dye blends used in the process of the invention will depend on the desired hue. For example, a brown hue may use 20-40% by weight of the yellow component, 40-60% by weight of the orange/red component, and 10-20% by weight of the blue component of the inventive acid dye blend.

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

Example 1a (PA staining):

100 parts of nylon-6 cloth was placed in a 40 ° C dye bath consisting of 2000 parts of water and 1 part of a weak cationic active leveling agent (based on ethoxylated amine propyl fatty acid decylamine). Affinity for dyes, 0.25 parts of the following dye blends (the dye blend consists of 9 parts) And 1 serving The composition consisted of 1-2 parts of 40% acetic acid adjusted to pH 5. After 10 minutes at 40 ° C, the dye bath was heated to 98 ° C at a rate of 1 ° C per minute and then allowed to boil for 45-60 minutes. It was then cooled to 70 ° C during 15 minutes. The dyed polyamine fabric is removed from the bath, rinsed with heat and then cold water, and dried. The results obtained were homochromatic blue polyamine dyeing with good light fastness and wet fastness.

Example 1b (wool dyeing):

100 parts of wool cloth was placed in a 40 ° C dye bath consisting of 4000 parts of water and 1 part of a leveling agent (based on sulphated, ethoxylated fatty acid decylamine), having both sexes and The dye has a weak affinity), 0.4 parts of the dye blend of Example 1a and adjusted to pH 5 with 1-2 parts of 40% acetic acid. After 10 minutes at 40 ° C, the dye bath was heated to boiling at a rate of 1 ° C per minute and then allowed to boil for 40-60 minutes. It was then cooled to 70 ° C during 20 minutes. The dyed wool fabric is removed from the bath, rinsed with heat and then cold water, and dried. The results obtained were dyed blue wool with good light fastness and wet fastness and good dyeability in the fiber (root-tip).

Examples 2 to 30:

The following table lists the dyes of Examples 2 to 30, which were mixed at a ratio of dye B: dye A of 1:9 or 2:8 and used for dyeing in a manner similar to Examples 1a and 1b. The dye blends of the present invention provide easy reproducibility, uniform dyeing with excellent wet fastness and light fastness to a particular substrate (polyamide or wool).

Example 31:

100 parts of nylon-6,6 cloth was placed in a 40 ° C dye bath consisting of 2000 parts of water and 1 part of a weak cationic active leveling agent (based on ethoxylated amine propyl fatty acid decylamine). The substrate and affinity for the dye, 0.3 part of the dye blend of Example 1a and adjusted to pH 5.5 with 1-2 parts of 40% acetic acid. After 10 minutes at 40 ° C, the dye bath was heated to 120 ° C at a rate of 1.5 ° C per minute and then allowed to stand at 120 ° C for 15-25 minutes. It was then cooled to 70 ° C during 25 minutes. The dyed nylon-6,6 fabric was removed from the bath, rinsed with heat and then cold water, and dried. Place The result is a blue polyamine dyeing with good leveling and good light fastness and wet fastness.

Example 32

100 parts of nylon-6 woven fabric was padded with a liquid consisting of: 50 parts of the dye blend of Example 1a, 100 parts of urea, 20 parts of nonionic stability based on butyl diethylene glycol. 15-20 parts acetic acid (to adjust pH to 4) 10 parts weak cationic active leveling agent (based on ethoxylated amine propyl fatty acid decylamine and affinity for dyes), and 810-815 parts Water (to make up to 1000 parts of padding solution).

The impregnated material is rolled up and left in the steam chamber for 3-6 hours at 85-98 ° C for saturation. The dyed fabric is then rinsed with heat and then cold water and dried. The results obtained were blue polyamidamine dyeing with good homogenization and good light fastness and wet fastness.

Example 33

A textile cut sheet material constituting nylon-6 and having a synthetic base fabric composed of cotton, polyamide or polyester is contained in every 1000 parts. The liquid of the presenter was padded: 1 part of the dye blend of Example 1a, 4 parts of a commercially available thickener based on carob powder ether, 2 parts of a nonionic ethylene oxide adduct of higher alkylphenol, 1 part 60 % acetic acid.

Thereafter, printing was carried out with a paste containing the following components per 1000 parts: 20 parts of a commercially available alkoxylated fatty alkylamine (displacement product) 20 parts of a commercially available thickener based on carob powder ether.

The printing was fixed in saturated steam, fixed at 100 ° C for 6 minutes, rinsed and dried. The result obtained was a cover material having a uniform dyed blue and white pattern.

Example 34 (three primary color dyeing)

100 parts of nylon-6,6 cloth was placed in a 40 ° C dye bath consisting of 2000 parts of water and 1 part of a weak cationic active leveling agent (based on ethoxylated amine propyl fatty acid decylamine). Base and affinity for dye), 0.2 parts of red dye in Example 8 of WO 2002/46318, 1.5 parts of commercially available CIAcid Yellow 236 (Nylosan® Yellow FL) formulation and 0.5 part of Blue Dye Blend of Example 1a Composition and adjusted to pH 5 with 1-2 parts of 40% acetic acid. After 10 minutes at 40 ° C, the dye bath was heated to 98 ° C at a rate of 1 ° C per minute and then allowed to boil for 45 to 60 minutes. It was then cooled to 70 ° C during 15 minutes. The dyed fabric is removed from the bath, rinsed with heat and then cold water, and dried. The results obtained were homogenized gray polyamine dyeing with good light fastness and wet fastness.

Example 35

Three of the dye blends of Example 1 were dissolved in 82 parts of demineralized water at 60 ° C and 15 parts of diethylene glycol. After cooling to room temperature, a blue printing ink is obtained which is highly suitable for ink jet printing on paper or polyamide and wool textiles.

Similar results were obtained by carrying out the steps of Examples 31 to 35 with the dye blends of Examples 2 to 30.

Example 36 (wool/polyamide blended fabric dyeing)

100 parts of wool/polyamine blended cloth was placed in a 40 ° C dye bath consisting of 4000 parts of water and 1 part of a leveling agent based on sulfated, ethoxylated fatty acid guanamine. Composition with amphoteric traits and weak affinity for dyes, 0.4 parts of the dye blend of Example 23 and adjusted to pH 5 with 1-2 parts of 40% acetic acid. After 10 minutes at 40 ° C, the dye bath was heated to boiling at a rate of 1 ° C per minute and then allowed to boil for 40-60 minutes. It was then cooled to 70 ° C during 20 minutes. The dyed wool/polyamine blended fabric is removed from the bath, rinsed with heat and then cold water, and dried. The result is a uniform dyed blue wool/polyamide blended fabric with good light fastness and wet fastness and good dyeability in wool fibers (root-tip) and the same color system for polyamide and wool fibers. dyeing.

Comparative Example 37 (three primary color dyeing)

Prepare a dye bath consisting of 4000 parts water, 2 parts CIAcid Orange 67, 1 part CIAcid Red 336, and 3 parts Optilan ^® Blue MF-GL at 40 ° C, and then compare the nylon-6 cloth to the sample 1a. Method dyeing. The results of the dyeing have poor reproducibility (blocking) and poor wet fastness. Conversely, for wool, dyeing with good wet fastness can be achieved.

Comparative Example 38 (three primary color dyeing)

A dyeing bath consisting of 4000 parts of water, 2 parts of C.I. Acid Orange 67, 1 part of C.I. Acid Red 336, and 3 parts of Acid Blue 350 was prepared at 40 ° C, and the wool cloth was dyed in a manner similar to that of Example 1b. The dyed fabric has a speckled appearance.

Conversely, nylon-6 achieves good wet fastness and high reproducibility.

Example 39 (three primary color dyeing)

Prepare a dye blend obtained from 4000 parts of water, 2 parts of C.I. Acid Orange 67, 1 part of C.I. Acid Red 336, and 3 parts of each of Examples 1 to 30 according to the present invention at 40 °C. A dye bath consisting of.

For polyamides, good reproducible dyeing with good wet fastness is achieved.

For wool, a very eye-catching appearance with good wet fastness is also obtained.

Claims (15)

An acid dye blend comprising a) from 20 to 95% by weight of at least one dye A having the general structure (A) Wherein R1, R2, R3 and R4 are each independently H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, -NR12R13, C ₁ -C ₆ -alkylene-NR12R13; H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, -NR12R13, C ₁ -C ₆ -alkylene-NR12R13, sulfonic acid group, R50 is H, C ₁ -C ₆ - Alkyl, C ₅ -C ₆ -cycloalkyl; R 12 is H, C ₁ -C ₆ -alkyl; R ₁₃ is -CO-CH ₂ -Cl, -SO ₂ -phenyl, wherein phenyl is substituted or Unsubstituted; M is H, alkali metal, ammonium; and b) 5 to 80% by weight of at least one dye B having the general structure (B) Wherein R6 is H, phenyl, wherein the phenyl group is the substituted or unsubstituted, R7 is H, a sulfonic acid group, R8 is H, C ₁ -C ₄ - alkoxy, or R7 and R8 with the adjacent C = The C double bond combines to form a substituted or unsubstituted benzene ring, R9 is H, a sulfonic acid group, M is H, an alkali metal, ammonium or a single negative charge, wherein the weight percentage is the total weight of each of the acid dye blends. Benchmark. The acid dye blend according to item 1 of the patent application, which comprises 50 to 90% by weight of at least one dye A of the formula (A) and 10 to 50% by weight of at least one dye B of the formula (B). The scope of the patented blend of acid dyes, Paragraph 1, wherein R1, R2, R3, R4 are each independently hydrogen, methyl, methoxy, NR12R13 or C ₁ -C ₂ - alkylene -NR12R13, wherein R12 is hydrogen or methyl and R13 is -CO-CH ₂ -Cl or -SO ₂ - phenyl, wherein the phenyl group is the substituted or unsubstituted. An acid dye blend according to claim 1 wherein R5 is hydrogen, methyl or sulfonic acid. An acid dye blend according to claim 1 wherein R6 is hydrogen, unsubstituted phenyl or phenyl substituted with amino-, sulfonate- and/or ethoxy-. The scope of the patent acid dye blend as item 1, wherein R50 is hydrogen, methyl, ethyl, branched C ₃ -C ₆ - alkyl, cyclopentyl or cyclohexyl. An acid dye blend according to claim 1 wherein R8 is hydrogen or methoxy. The scope of the patent acid dye blend as item 1, wherein Formula (A) a dye of R1 to R4 is NR12R13 or one C ₁ -C ₂ - alkylene -NR12R13, wherein R12 is hydrogen or methyl group and R13 is SO ₂ - (4- methylphenyl), while the rest of R1 to R4 is hydrogen or methyl and the same or different, and R5 is hydrogen, methyl or sulfonic acid group. The acid dye blend according to any one of claims 1 to 8, wherein in the dye of the formula (B), R6 is an unsubstituted phenyl group, and R7 and R8 are combined with an adjacent C=C double bond to form a A benzene ring substituted with a sulfonic acid group, and R9 is H. Acid dyeing according to any one of the first to eighth patent applications a blend of materials wherein R6 in the dye of formula (B) is hydrogen or an unsubstituted phenyl group; R7 is hydrogen or a sulfonic acid group, R8 is hydrogen or methoxy, and R9 is hydrogen or a sulfonic acid group. The acid dye blend according to any one of claims 1 to 8, wherein in the dye of the formula (B), R6 is a phenyl group substituted with an amine group, a sulfonic acid group and/or an ethoxy group; R7 is hydrogen or a sulfonic acid group, R8 is hydrogen, and R9 is hydrogen. A method of producing an acid dye blend according to one or more of claims 1 to 11 comprising mixing at least one dye A with at least one dye B. Use of an acid dye blend according to one or more of claims 1 to 11 in the dyeing and/or printing of fibrous materials consisting of natural or synthetic polyamines or blends thereof. The use according to claim 13 wherein the fibrous material consists of wool, silk, synthetic polyamide or a mixture thereof. It is used as a blue component in three-color dyeing or printing according to the use of paragraph 13 or 14 of the patent application.