Yellow dye composition and dyeing process

Abstract

The invention provides a yellow dye composition and a dyeing process. The yellow dye composition comprises a dye A, a dye B, a dye C and an auxiliary agent, wherein the weight ratio of the dye A to the dye B to the dye C to the auxiliary agent is (30-50): (25-40): (0-10): (30-40). Wherein the dye A is the most important component, and a large pi conjugated system is formed by an azo bond, a pyrazole ring and two benzene rings.

Description

Technical Field

[0001] This invention relates to the field of dye technology, and in particular to a yellow dye composition and dyeing process. Background Technology

[0002] In the textile printing and dyeing field, wool fibers, due to their molecular structure being rich in active groups such as amino and hydroxyl groups, require dyes with much higher affinity and fastness properties than conventional fibers such as cotton and synthetic fibers. Furthermore, as golden yellow is one of the mainstream colors for wool fabrics, existing dyes still have significant shortcomings.

[0003] On the one hand, when traditional golden dyes are applied to wool, the wash fastness is generally insufficient. Whether it is the gentle conditions of daily household washing or the strong mechanical force and high pH environment of industrial batch washing, the color is prone to fading and staining other fabrics, making it difficult for wool products to meet the demands of the high-end market in terms of color durability.

[0004] On the other hand, existing golden yellow dyes are highly photosensitive. After wool fabrics are exposed to light (such as daily drying or outdoor use), the dye molecules are prone to photo-oxidation and photo-degradation reactions, resulting in yellowing and decreased brightness, which seriously affects the durability of the product's appearance. This problem is particularly prominent in the field of high-end wool clothing and home textiles, which have high requirements for weather resistance.

[0005] To adapt to the dyeing characteristics of wool fibers, the industry has tried to improve performance by compounding dyes. However, most compounding systems only focus on improving a single fastness index, making it difficult to simultaneously take into account both wash fastness and light stability. Moreover, most existing compounding dyes are general-purpose formulations that are not specifically designed for the structural characteristics of wool fibers, and in practical applications, there are still problems such as insufficient affinity and large fluctuations in color fastness. Summary of the Invention

[0006] The purpose of this invention is to provide a yellow dye composition and dyeing process suitable for wool fabrics.

[0007] To solve at least one of the above-mentioned technical problems, the yellow dye composition provided by the present invention includes dye A, dye B, dye C and auxiliaries, wherein the weight ratio of dye A, dye B, dye C and auxiliaries is (30-50):(25-40):(0-10):(30-40).

[0008] Wherein, the general formula of dye A is ;

[0009] Wherein, the general formula for dye B is: ;

[0010] Wherein, the general formula for dye C is: ;

[0011] Among them, D1, D2, D3, and D4 are each independent. ;

[0012] R1 is independently selected from -SO2CH=CH2, -SO2C2H4OSO3M2, etc. or ;

[0013] R2 and R3 are each independently selected from -H, -SO3M1, -OCH3, and -CH3;

[0014] R4 and R5 are each independently selected from -H, -SO3M1, -OCH3, and -CH3;

[0015] R6 is independently selected from -SO2CH=CH2 or -SO2C2H4OSO3M2;

[0016] X is independently selected from -Cl or -H;

[0017] M, M1, and M2 are each independently selected from hydrogen, potassium, sodium, lithium, and ammonium.

[0018] Optionally, in the molecular structure of dye A, the substituent R1 is attached to the aromatic ring bound to -N=N-. When R1 is -SO2C2H4OSO3M2, the position of R1 is either para or meta of -N=N-. or The position of R1 is the opposite, intermediate, or adjacent position of -N=N-.

[0019] Optionally, -SO3M is connected to and On the connected aromatic ring, the -SO3M position is The optimal solubility is achieved at the paraposition of the ligand.

[0020] Optional, R1 is or At least one of R2 and R3 is -SO3M1.

[0021] Optionally, dye A is a mixture of one or more of the following structural formulas:

[0022] Equation (1-1),

[0023] Equation (1-2),

[0024] Equation (1-3),

[0025] Equation (1-4)

[0026] Equation (1-5),

[0027] Equation (1-6)

[0028] Equation (1-7)

[0029] Equation (1-8)

[0030] Equation (1-9)

[0031] Equation (1-10),

[0032] Equation (1-11),

[0033] Equation (1-12),

[0034] Equation (1-13),

[0035] Equation (1-14),

[0036] Equation (1-15),

[0037] Equation (1-16)

[0038] Equation (1-17)

[0039] Equation (1-18),

[0040] Equation (1-19).

[0041] Optionally, dye B is a mixture of one or more of the following structural formulas:

[0042] Equation (2-1),

[0043] Equation (2-2),

[0044] Equation (2-3),

[0045] Equation (2-4),

[0046] Equation (2-5),

[0047] Equation (2-6)

[0048] Equation (2-7).

[0049] Optionally, dye C is a mixture of one or more of the following structural formulas:

[0050] Equation (3-1),

[0051] Equation (3-2).

[0052] Equation (3-3),

[0053] Equation (3-4),

[0054] Equation (3-5),

[0055] Equation (3-6)

[0056] Equation (3-7).

[0057] Optionally, dye A is any of the compounds shown in structural formulas (1-2), (1-8), (1-9), (1-10), and (1-11), dye B is the compound shown in structural formula (2-1), and dye C is the compound shown in structural formula (3-1).

[0058] Optionally, the additives may be one or a mixture of any two or more of the following: sodium sulfate, sodium hexametaphosphate, methylnaphthalenesulfonic acid formaldehyde condensate, and naphthalenesulfonic acid formaldehyde condensate.

[0059] The present invention also provides a dyeing process for the yellow dye composition described above, comprising:

[0060] S1: Maintain the dye bath temperature at 40℃, add the leveling agent and yellow dye composition in sequence, and adjust the pH of the dye bath to 4-4.5;

[0061] S2: Increase the temperature to 98℃ at a rate of 1℃ / min - 1.5℃ / min, and maintain the temperature at 98℃ for 30-60 minutes for staining;

[0062] S3: Wash with water;

[0063] S4: Alkali washing.

[0064] Optionally, step S4 includes:

[0065] S41: Adjust the pH of the bath solution to 8.5-9;

[0066] S42: After heating, keep warm at 80℃ for 20 minutes;

[0067] S43: Wash with water after the heat preservation is completed.

[0068] In summary, the yellow dye composition of the present invention, which combines dye A, dye B, dye C (optional) and auxiliaries, has significantly improved wash fastness, light stability and leveling properties compared to commercially available yellow dyes.

[0069] Dye A is the most important component, formed by a large π-conjugated system consisting of an azo bond (-N=N-) with a pyrazole ring and two benzene rings. Furthermore, by introducing elements selected from -SO2CH=CH2, -SO2C2H4OSO3M2, etc., onto the benzene ring connected to the azo bond (-N=N-),... or Substituents can achieve substitution, resulting in better effects.

[0070] Furthermore, the inventors originally believed that the core active sites of wool fibers are the amino (-NH2) and hydroxyl (-OH) groups in protein molecules, while halogen atoms (Br) have strong electron-withdrawing properties, which can enhance the electrophilicity of the carbonyl group (C=O) in the carbamoyl group and improve the binding stability with the amino group of wool fibers; moreover, the Br atom has a larger volume, which can form steric hindrance and inhibit the dissociation of dye molecules during washing. Br-CH=CBr-CO-NH- contains 2 Br atoms, has the strongest electron-withdrawing effect and steric hindrance, can maximize the interaction between dye and fiber, and has the best anti-washing stripping ability; CH2=CHBr-CO-NH- contains 1 Br atom, and since Br is located at the end of the double bond, the electron-withdrawing effect on the carbonyl group is weaker than that of the middle position, and the binding stability is slightly worse.

[0071] However, this invention unexpectedly discovered that in dye A, after CH2=CHBr-CO-NH- substitution, if the benzene ring connected to -N=N- is simultaneously substituted with -SO3M1, the wash fastness, light stability, and leveling effect are all improved compared to Br-CH=CBr-CO-NH-. The leveling effect rating reaches 4-5, the wash fastness reaches 5, and the DE after 48 hours of light exposure is less than or equal to 0.42, representing an improvement of approximately 100% (compared to the effect before substitution). The invention utilizes the more easily prepared CH2=CHBr-CO-NH- substitution, which is the previous stage preparation product of Br-CH=CBr-CO-NH-. This breakthrough overturned the inventors' previous preconceived notions, and the final result exceeded the expectations of those skilled in the art. Detailed Implementation

[0072] The specific embodiments of the present invention will be described in further detail below with reference to examples. These examples are used to illustrate the present invention, but are not intended to limit the scope of the invention.

[0073] Yellow dye compositions were prepared by mixing dyes A, B, and C with auxiliaries according to the proportions and components shown in Table 1 below. In the following examples, the types of auxiliaries can be replaced with others; for example, sodium sulfate can be replaced with sodium hexametaphosphate, methylnaphthalenesulfonic acid formaldehyde condensate, naphthalenesulfonic acid formaldehyde condensate, etc., with similar effects.

[0074] - Yellow dye composition: 2% (relative to the weight of the fabric sample)

[0075] - Leveling agent: 1.5% (ratio to fabric sample weight)

[0076] - Acetic acid / sodium acetate: 1-3 g / L (used for adjusting the pH of the dye bath)

[0077] - pH value of the dye bath: controlled at 4-4.5.

[0078] The dyeing process for dyes includes:

[0079] S1: Maintain the dye bath temperature at 40℃, add the leveling agent and yellow dye composition in sequence, and adjust the pH of the dye bath to 4-4.5;

[0080] S2: Increase the temperature to 98℃ at a rate of 1℃ / min - 1.5℃ / min, and maintain the temperature at 98℃ for 30-60 minutes for staining;

[0081] S3: Wash with water;

[0082] S4: Alkaline washing. This includes: S41: Adjusting the pH of the bath solution to 8.5-9; S42: Heating and then maintaining the temperature at 80℃ for 20 minutes; S43: Washing with water after the heating is complete.

[0083] The results of various tests are shown in Table 2. The test fabric used was wool fabric.

[0084] The wash fastness conforms to ISO 150-C03-1994.

[0085] The total color difference DE was measured using a colorimeter (the unlit area was the standard, and the lit area was the sample). The lit area was natural light.

[0086] Evenness rating (1-5 levels) - Industry uses visual rating, with a maximum of 5 levels.

[0087] In comparison to Example 3, the formula (1-2) in Example 2 is... Replace with After dyeing, the color becomes darker.

[0088] By comparing the experimental data, dye A is the most important. Dye A is any compound shown in structural formulas (1-2), (1-8), (1-9), (1-10), or (1-11), and the best results are obtained.

[0089] Dye B, the compound shown in structural formula (2-1), has the best effect.

[0090] Dye C can be omitted; the compound shown in structural formula (3-1) is the most effective. When dye C is omitted, the combination of formula (1-2): formula (2-1): sodium sulfate exhibits the best ΔE after 48 hours of illumination in all embodiments.

[0091] Whether a halogen atom is substituted on the benzene ring connected to the pyrazole ring has little impact on the final structure. -SO3M is preferably attached to the benzene ring. The alignment.

[0092] Table 1. Formulations in each embodiment and comparative embodiment.

[0093]

[0094] Table 2 Test results of each embodiment and comparative embodiment

[0095]

[0096] Although the present invention has been disclosed above by way of preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art may make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope of protection claimed in the claims.

Claims

1. A yellow dye composition, characterized in that, It includes dye A, dye B, dye C and auxiliaries, wherein the weight ratio of dye A, dye B, dye C and auxiliaries is (30-50):(25-40):(0-10):(30-40). Wherein, the general formula of dye A is: ; Wherein, the general formula of dye B is: ; Wherein, the general formula of dye C is: ; Among them, D1, D2, D3, and D4 are each independent. ; R1 is independently selected from , , ,or ; R2 and R3 are each independently selected from -H, -SO3M1, -OCH3, and -CH3; R4 and R5 are each independently selected from -H, -SO3M1, -OCH3, and -CH3; R6 is independently selected from -SO2CH=CH2 or -SO2C2H4OSO3M2; X is independently selected from -Cl or -H; M, M1, and M2 are each independently selected from hydrogen, potassium, sodium, lithium, and ammonium.

2. The yellow dye composition according to claim 1, characterized in that, In the molecular structure of dye A, substituent R1 is attached to the aromatic ring bound to -N=N-. When R1 is -SO2C2H4OSO3M2, the position of R1 is either para or meta of -N=N-. or The position of R1 is the opposite, intermediate, or adjacent position of -N=N-, and -SO3M is connected to and On the connected aromatic ring, the -SO3M position is The alignment.

3. The yellow dye composition according to claim 2, characterized in that, R1 is or At least one of R2 and R3 is -SO3M1.

4. The yellow dye composition according to claim 2, characterized in that, The dye A is one or a mixture of two or more of the following structural formulas: Equation (1-1), Equation (1-2), Equation (1-3), Equation (1-4) Equation (1-5), Equation (1-6) Equation (1-7) Equation (1-8) Equation (1-9) Equation (1-10), Equation (1-11), Equation (1-12), Equation (1-13), Equation (1-14), Equation (1-15), Equation (1-16) Equation (1-17), Equation (1-18), Equation (1-19).

5. The yellow dye composition according to any one of claims 1 to 4, characterized in that, The dye B is a mixture of one or more of the following structural formulas: Equation (2-1), Equation (2-2), Equation (2-3), Equation (2-4), Equation (2-5), Equation (2-6), Equation (2-7).

6. The yellow dye composition according to any one of claims 1 to 4, characterized in that, The dye C is one or a mixture of two or more of the following structural formulas: Equation (3-1), Equation (3-2). Equation (3-3), Equation (3-4), Equation (3-5), Equation (3-6) Equation (3-7).

7. The yellow dye composition according to any one of claims 1 to 4, characterized in that, The dye A is any compound shown in structural formulas (1-2), (1-8), (1-9), (1-10), and (1-11), the dye B is a compound shown in structural formula (2-1), and the dye C is a compound shown in structural formula (3-1). in, Equation (2-1), Equation (3-1).

8. The yellow dye composition according to any one of claims 1 to 4, characterized in that, The additive is one or a mixture of any two or more of the following: sodium sulfate, sodium hexametaphosphate, methylnaphthalenesulfonic acid formaldehyde condensate, and naphthalenesulfonic acid formaldehyde condensate.

9. A dyeing process using the yellow dye composition according to any one of claims 1 to 8, characterized in that, include: S1: Maintain the dye bath temperature at 40℃, add the leveling agent and the yellow dye composition in sequence, and adjust the pH of the dye bath to 4-4.5; S2: Increase the temperature to 98℃ at a rate of 1℃ / min - 1.5℃ / min, and maintain the temperature at 98℃ for 30-60 minutes for staining; S3: Wash with water; S4: Alkali washing.

10. The yellow dye composition according to claim 9, characterized in that, Step S4 includes: S41: Adjust the pH of the bath solution to 8.5-9; S42: After heating, keep warm at 80℃ for 20 minutes; S43: Wash with water after the heat preservation is completed.

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