Reactive red dye composition and dye product
By optimizing the design of the reactive red dye composition, the problem of insufficient chlorine fastness of existing dyes in chlorine disinfectant environments has been solved, achieving high color fastness of fabrics, and making it suitable for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZHEJIANG KEYONG CHEM CO LTD
- Filing Date
- 2025-12-30
- Publication Date
- 2026-05-12
Smart Images
Figure CN122011801A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a reactive red dye composition, and more particularly to a reactive red dye composition and dye product suitable for printing and dyeing nitrogen-containing and / or hydroxyl-containing fiber materials. Background Technology
[0002] Reactive dyes are widely used in cotton fabric dyeing due to their bright colors and low cost. However, in urban water environments (containing chlorine disinfectants), their chlorine fastness often becomes a weakness, causing clothes to yellow or fade after washing. Vinyl sulfone reactive dyes are commonly used for dyeing cellulosic fiber materials; however, orange-red to bright red fabrics dyed with these azo reactive dyes generally have low chlorine fastness, frequently exhibiting discoloration due to dyeing, and failing to meet the high color fastness requirements of mid- to high-end fabrics. Therefore, the purpose of this invention is to discover new and improved reactive dyes, particularly red reactive dyes, that can be used for dyeing and printing fiber materials to meet the dyeing and printing needs of the mid- to high-end market. Summary of the Invention
[0003] Through optimized design, the inventors have provided a reactive red dye composition with excellent wash fastness, abrasion fastness, and chlorine fastness, which is suitable for printing and dyeing nitrogen-containing and / or hydroxyl-containing fiber materials and their blended fabrics.
[0004] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:
[0005] This invention provides a reactive red dye composition comprising component A and component B, wherein component A is selected from at least one dye compound represented by formula (I), and component B is selected from at least one dye compound represented by formula (II); in the reactive red dye composition, the mass percentage of component A is 5-50%, and the mass percentage of component B is 50-95%.
[0006]
[0007] In formula (Ⅰ):
[0008] R 1 It is a C1 to C4 alkyl group, R 2 R 3 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, M 1 M 2 H or alkali metal, X 1 For halogen, Y 1 For -CH=CH2 or -CH2CH2OSO3M 4 The M 4 It is H or an alkali metal;
[0009] In formula (II):
[0010] R 4 R 5 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, R 6 It is H or C1-C4 alkyl, X 2 For halogens, R 7 R 8 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, Y 2 For -CH=CH2 or -CH2CH2OSO3M 5 The M 5 It is H or an alkali metal.
[0011] In this invention, the C1-C4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C1-C4 alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.
[0012] Furthermore, R 1 It is methyl or ethyl, R 2 R 3 Each can be independently a hydrogen, methyl, methoxy, or sulfonic acid group.
[0013] Furthermore, R 6 It can be H, methyl, ethyl, or hydroxyethyl.
[0014] Furthermore, R 4 R 5 R 7 R 8 Each can be independently represented by H, methyl, methoxy, or sulfonic acid groups.
[0015] Furthermore, the reactive red dye composition comprises component A and component B.
[0016] Specifically, component A is preferably at least one of the dye compounds or their alkali metal salts represented by the following formulas (I-1) to (I-8):
[0017]
[0018]
[0019] Specifically, component B is preferably at least one of the dye compounds or their alkali metal salts represented by the following formulas (II-1) to (II-10):
[0020]
[0021]
[0022]
[0023] The reactive red dye composition of the present invention uses dye compounds (Ⅰ) to (Ⅱ) that are publicly reported dyes and can be synthesized by methods described in the literature, for example by using suitable components known to those skilled in the art and using the necessary proportions by means of conventional diazotization, coupling and condensation reactions.
[0024] Furthermore, in the reactive red dye composition of the present invention, the dye component can be an alkali metal salt, preferably a sodium or potassium salt. It is well known to those skilled in the art that dye compounds in free acid form and dye compounds in alkali metal salt (such as sodium or potassium salts) form have essentially the same dyeing properties. Typically, the structural formulas of various monochrome dye compounds are defined using the free acid form, but in actual synthesis, they are usually prepared and separated in the form of their alkali metal salt (such as sodium or potassium salt), and are also used for dyeing in their salt form, which is also well known to those skilled in the art.
[0025] The reactive red dye composition of the present invention is prepared by mixing the dye components according to the aforementioned ratio. The mixing can be carried out by conventional mechanical means, such as in a grinder, kneader, or homogenizer. During the mixing process, individual dye compounds can exist in the form of powder, granules, aqueous solution, or synthetic solution. When individual dye compounds are mixed in the form of synthetic solution, the composite reactive red dye of the present invention can be separated from the synthetic solution by commonly known methods, such as salting out the dye from the reaction medium with an electrolyte (such as sodium chloride or potassium chloride), or evaporating or spray drying the mixed solution. Therefore, each dye component and its dye composition usually contain conventional electrolyte salts (such as sodium chloride, sodium sulfate, etc.) commonly found in reactive dyes.
[0026] The reactive red dye composition of the present invention, when sold commercially, may be sold without auxiliaries, or may contain conventional auxiliaries found in commercial dyes, such as solubilizers, dispersants, alkali-resistant auxiliaries, dust suppressants, surfactants, buffers, and dyeing accelerators. Therefore, the present invention also provides a reactive red dye product containing the aforementioned reactive red dye composition. Preferably, the reactive red dye product contains the aforementioned reactive red dye composition and auxiliaries. The weight of the auxiliaries does not exceed 40% of the weight of the reactive red dye composition, preferably not exceeding 30%. The auxiliaries preferably include one or any combination of the following: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), CNF (benzylnaphthalenesulfonate formaldehyde condensate), sodium sulfate (industrial sodium sulfate), lignin sulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickeners, etc. All auxiliaries are commercially available conventional varieties.
[0027] The reactive red dye product of this invention is suitable for dyeing and printing on nitrogen-containing and / or hydroxyl-containing fiber materials. These materials can be cellulose fibers, polyamide fibers, and their fabrics. Cellulose fibers are preferably cotton fibers or regenerated fibers, but may also include other plant fibers, such as hemp fibers or fabrics. Polyamide fibers are preferably animal fibers, including leather, wool, or silk, as well as synthetic fibers such as nylon 6 and nylon 66. When dyeing the aforementioned fiber materials using the reactive red dye product of this invention, known reactive dyeing methods can be followed, such as the commonly used reactive dye immersion dyeing method and pad dyeing method. Immersion dyeing involves immersing the fabric in a dye bath, allowing the dye to gradually coat the fabric. This typically requires processes such as dyeing, fixing, washing, soaping, washing, dehydration, and drying.
[0028] Padding dyeing involves first immersing the fabric in a dye solution, then passing the fabric through rollers to evenly roll the dye solution into the fabric, followed by steaming or hot melting treatment. It typically involves processes such as padding with dye solution, drying, (padding with fixing solution), steaming or baking, washing, soaping, washing, and drying.
[0029] Generally, the amount of dye used varies depending on the desired color on the fabric. When using immersion dyeing, the owf (color depth) is typically 0.1%–10% (dye weight percentage of fabric), the liquor ratio is 1:2–1:60 (fabric to dye liquor weight ratio, preferably 1:10–1:30), the initial dyeing temperature is controlled at 30–60℃, the dyeing time is 10–30 minutes, the soaping temperature is 85–95℃, the soaping time is 10–15 minutes, the fixing temperature is 60–100℃, the fixing time is 10–50 minutes, and the fixing pH value is 9–11. When using pad dyeing, the pad residue of cellulose fibers is typically 60–80%, the steaming temperature is 100–103℃, and the steaming time is 1–3 minutes. Currently, cold pad-batch dyeing is commonly used in pad dyeing. In this method, dye and alkaline substances are introduced into the pad dyeing machine and the dye is rolled up and piled at room temperature for 2–30 hours for fixing, followed by thorough rinsing.
[0030] The reactive red dye composition and products described in this invention have outstanding color fastness, especially chlorine fastness, when used for printing and dyeing nitrogen-containing and / or hydroxyl-containing fiber materials. Detailed Implementation
[0031] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto:
[0032] The dye compounds used in the embodiments of the present invention are prepared and separated in the form of sodium salts during the actual synthesis process, and are also used for dyeing in the form of sodium salts. However, for ease of writing, all chemical formulas of the dye compounds in the embodiments are represented in the form of free acids. Their dyeing performance is equivalent to that of sodium salts. The "parts" mentioned below refer to parts by mass.
[0033] Example 1:
[0034] 30 parts of the dye compound shown in formula (Ⅰ-1), 70 parts of the dye compound shown in formula (Ⅱ-1), and 16 parts of sodium sulfate were mechanically mixed to obtain a composite dye that was used to dye cotton a deep red color using a conventional immersion dyeing method.
[0035]
[0036] Example 2:
[0037] 20 parts of the dye compound shown in formula (Ⅰ-2), 70 parts of the dye compound shown in formula (Ⅱ-2), 10 parts of CI Reactive Red 195, and 12 parts of sodium sulfate were mechanically mixed to obtain a composite dye that was used to dye cotton a deep red using conventional immersion dyeing methods.
[0038]
[0039] Examples 3-20
[0040] According to the method described in any one of Examples 1 to 2, the dyes in the proportions listed in Table 1 are mechanically mixed, and the cotton is dyed red using the conventional reactive dye dyeing method.
[0041] Table 1
[0042]
[0043] Application Examples
[0044] The reactive dyes prepared in Examples 1-20 of this invention were dissolved in water, and 50 g / L of sodium sulfate was added to prepare dye solutions. The dyeing concentration was 4% (dye to fabric weight), the liquor ratio was 1:20 (fabric weight in grams to dye solution volume in milliliters), and the cotton fabric was placed in the solution at 60°C for 30 minutes for adsorption. Then, alkali (20 g / L sodium carbonate) was added for color fixation for 45 minutes. The dyed fabric was washed, soaped, and dried to obtain a red dyed fabric. The color fastness to washing, color fastness to rubbing, and color fastness to chlorine water were tested according to the methods in ISO 105C10-2006, ISO 105X12, and ISO 105-E03, respectively. The results are shown in Table 2 below.
[0045] Table 2
[0046]
[0047] The reactive red dye provided by this invention has excellent color fastness to washing and rubbing, especially its color fastness to chlorine water is significantly improved compared to grades 2-3 on the market, which can meet the printing and dyeing needs of mid-range or high-end textiles.
Claims
1. A reactive red dye composition comprising component A and component B, wherein component A is selected from at least one dye compound of formula (I), and component B is selected from at least one dye compound of formula (II); wherein the reactive red dye composition comprises component A at a mass percentage of 5-50%, and component B at a mass percentage of 50-95%. In formula (Ⅰ): R 1 It is a C1 to C4 alkyl group, R 2 R 3 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, M 1 M 2 H or alkali metal, X 1 For halogen, Y 1 For -CH=CH2 or -CH2CH2OSO3M 4 The M 4 It is H or an alkali metal; In formula (II): R 4 R 5 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, R 6 It is H or C1-C4 alkyl, X 2 For halogens, R 7 R 8 Each group is independently H, C1-C4 alkyl, C1-C4 alkoxy, or sulfonic acid group, Y 2 For -CH=CH2 or -CH2CH2OSO3M 5 The M 5 It is H or an alkali metal.
2. The reactive red dye composition as described in claim 1, comprising component A and component B, wherein, The mass percentage of component A is 5-50%, and the mass percentage of component B is 50-95%.
3. The reactive red dye composition according to claim 1, characterized in that: Component A is selected from at least one of the dye compounds or their alkali metal salts represented by formulas (I-1) to (I-8):
4. The reactive red dye composition according to claim 1, characterized in that: Component B is selected from at least one of the dye compounds or their alkali metal salts represented by formulas (II-1) to (II-10):
5. The reactive red dye composition according to claim 1, characterized in that: R 1 It is methyl or ethyl, R 2 R 3 Each can be independently a hydrogen, methyl, methoxy, or sulfonic acid group, R 6 H, methyl, ethyl, or hydroxyethyl, R 4 R 5 R 7 R 8 Each can be independently represented by H, methyl, methoxy, or sulfonic acid groups.
6. The reactive red dye composition according to any one of claims 3-4, characterized in that: The alkali metal salt is a sodium salt or a potassium salt.
7. A reactive red dye product, characterized in that: The composition contains the reactive red dye composition according to any one of claims 1 to 4 and the auxiliary agent, wherein the auxiliary agent is naphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, dispersant CNF, sodium sulfate, lignin sulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and thickener.
8. The reactive red dye product as described in claim 7, wherein the weight of the auxiliary agent does not exceed 40% of the weight of the reactive red dye composition.
9. The reactive red dye product as described in claim 7 or 8, for dyeing applications on nitrogen-containing and / or hydroxyl-containing materials.