A darkening agent for washable cotton, preparation method and application thereof

Abstract

The present invention provides a darkening agent for washable cotton, a preparation method and an application thereof. The darkening agent for washable cotton comprises, by weight, 10 to 30 parts of modified amino silicone oil, 1 to 6 parts of emulsifier, 0.05 to 0.4 parts of glacial acetic acid, and the remaining parts are softened water. The darkening agent provided in the present invention utilizes an alkaline crosslinking agent to modify the amino silicone oil, so that the amino silicone oil has high reactivity; the amino silicone oil modified by the alkaline crosslinking agent can react with the hydroxyl group in the cotton fiber, so that the darkening agent is more firmly combined with the cotton fiber, thereby obtaining excellent water-washing resistance. Even after washing 50 times, the fabric still has a darkening effect.

Description

Technical Field

[0001] The invention relates to the technical field of cotton textile washing, and in particular to a darkening agent for washable cotton, a preparation method and application thereof. Background Art

[0002] The textile printing and dyeing industry is a "nail household" for industrial wastewater and pollutant emissions in the entire social production, and the discharge of wastewater and other pollutants has remained high. Therefore, starting from the existing production processes, equipment, materials, etc., reducing energy consumption and achieving green production are the key and difficulty of dyeing and finishing production technology. Darkening technology can reduce the amount of dyes and auxiliaries used; reduce water and air emissions in all aspects of production, which is of great significance to the green production of the printing and dyeing industry and has received more and more attention. In addition, from the perspective of reducing production costs, it is also urgent to use darkening technology to reduce the use of dyes and improve production efficiency.

[0003] At present, the darkening effect is mainly achieved by using a darkening agent to form a low-refractive-index film on the surface of the fabric. Such darkening agents mainly include silicone resin polymers, acrylates, polyurethanes and fluorine-containing resins. Among them, fluorine-containing resins have the best darkening effect, but their high cost limits their use. The darkening effect of the fabric is significantly improved after finishing with acrylate darkening agents, but the hand feel is hard, which affects daily use; the most widely used darkening agent is the silicone darkening agent, which can achieve a high darkening effect while also greatly improving the hand feel of the fabric.

[0004] At present, there are many patents and literatures on the use of silicone darkening agents, and certain research progress has been made; for example, patent number CN109456485 A proposes the use of acrylate compounds to modify amino silicone oil to improve the overall color depth of fabrics. Patent CN112458771B uses octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as the main raw materials to synthesize a darkening agent, which has an excellent darkening effect when applied to nylon. Patent publication number CN 110055760B uses hydroxyethyl methacrylate to modify silicone oil, and compound hydroxylated graphene quantum dots with modified silicone oil. The synergistic effect of the two further improves the darkening effect of the fabric. Patent CN110485166A introduces mercaptoalkyl active groups into the silicone side chain to form a branched structure, which increases the complexity of the fabric surface and thus improves the product's darkening effect.

[0005] However, since conventional organosilicon darkening agents do not contain groups that can cross-link with fibers, organosilicon darkening agents are not durable and washable, which is also a major disadvantage of conventional organosilicon darkening agents. It is necessary to find a new darkening agent that overcomes this problem. Summary of the invention

[0006] The object of the present invention is to provide a darkening agent for washable cotton, a preparation method and application thereof, so as to solve the above-mentioned problems existing in the prior art.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a darkening agent for washable cotton, which comprises, by weight, 10 to 30 parts of modified amino silicone oil, 1 to 6 parts of emulsifier, 0.05 to 0.4 parts of glacial acetic acid, and the remainder is softened water.

[0009] Preferably, the modified amino silicone oil is synthesized by reacting an alkaline crosslinking agent with a high amino value amino silicone oil having a side chain structure of N-β-aminoethyl-γ-aminopropyldimethoxysilane to obtain the modified amino silicone oil; the emulsifier is selected from one or more of C6 to C18 fatty alcohol polyoxyethylene ethers.

[0010] Preferably, the alkaline crosslinking agent includes trichloro-s-triazine, dichloro-s-triazine, acryloyl chloride or chloroacetyl chloride.

[0011] Preferably, the synthesis route of the basic crosslinking agent modified silicone darkening agent is as follows:

[0012] (1) Synthesis route of trichlorotriazine modified amino silicone oil:

[0013]

[0014] (2) Synthesis route of dichlorotriazine modified amino silicone oil:

[0015]

[0016]

[0017] (3) Acryloyl chloride modified amino silicone oil

[0018]

[0019] (4) Chloroacetyl chloride modified amino silicone oil:

[0020]

[0021] The value range of m is: 40~80, and the value range of n is: 2~8.

[0022] In a second aspect, the present invention provides a method for preparing a darkening agent for washable cotton, comprising the following steps:

[0023] S1, amino silicone oil modified by alkaline crosslinking agent: add 90-100 parts of amino silicone oil to a reaction kettle, then add alkaline crosslinking agent in three times (0.5-3.4 parts each time), adjust the pH to 4-5 with acetic acid, react at 20°C-30°C for 3-4 hours, then separate the modified silicone oil by reduced pressure distillation to obtain amino silicone oil modified by alkaline crosslinking agent;

[0024] S2, emulsification of modified amino silicone oil: add 10-30 parts of the basic crosslinking agent modified amino silicone oil and 1-6 parts of emulsifier in step S1 into the emulsifying kettle, then add softened water (20-35 parts) three times, continue to stir at high speed for 20min after each addition of water, then add 0.05-0.4 parts of glacial acetic acid, and finally homogenize for 30-60min to obtain a uniformly and stably dispersed modified amino silicone oil emulsion, that is, a darkening agent for washable cotton.

[0025] Preferably, the basic cross-linking agent is added three times in a ratio of 1:1:1.2.

[0026] In a third aspect, the present invention further provides the use of the darkening agent for washable cotton described in the first aspect in cotton textiles.

[0027] Preferably, the use of the darkening agent for washable cotton in cotton textiles comprises the following steps:

[0028] The washable cotton darkening agent described in the first aspect is used, 40-80 g / L of cotton fabric finishing liquid is prepared, the pH is adjusted to 10-12, the cotton textile is dipped and rolled, the liquid carrying rate of the fabric after dipping and rolling is 50%-90%, and it is dried at 140°C-160°C.

[0029] Preferably, soda ash is used to adjust the pH of the finishing liquid.

[0030] The beneficial effects of the present invention are:

[0031] The present invention provides a darkening agent for washable cotton, a preparation method and an application thereof. The darkening agent provided in the present invention utilizes an alkaline crosslinking agent to modify amino silicone oil, so that the amino silicone oil has high reactivity; the amino silicone oil modified by the alkaline crosslinking agent can react with hydroxyl groups in cotton fibers, so that the darkening agent and the cotton fibers are more firmly combined, thereby obtaining excellent washability. Even after being washed 50 times, the fabric still has a darkening effect. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below. It should be understood that the specific implementation methods described herein are only used to explain the present invention and are not used to limit the present invention.

[0033] Example 1

[0034] This embodiment provides a darkening agent for washable cotton, comprising 17.8 parts of trichloro-s-triazine-modified amino silicone oil, 2.7 parts of emulsifier, 0.1 parts of glacial acetic acid, and 79.4 parts of water;

[0035] The preparation method includes the synthesis of trichloro-s-triazine modified amino silicone oil and its emulsification method:

[0036] (1) Synthesis of trichlorotriazine modified amino silicone oil:

[0037] By weight ratio, amino silicone oil: 97.4%

[0038] Trichlorotriazine: 2.6%

[0039] Total: 100%

[0040] Its synthetic route is:

[0041]

[0042] The preparation method is as follows:

[0043] Add amino silicone oil to the reactor, then add trichlorotriazine in three times at a ratio of 1:1:1.2, adjust the pH to 4 with acetic acid, react at 30°C for 4 hours, and separate the modified silicone oil by reduced pressure distillation to obtain trichlorotriazine-modified amino silicone oil.

[0044] (2) Trichlorotriazine modified amino silicone oil emulsification:

[0045] Ratio: Trichlorotriazine modified amino silicone oil: 17.8%

[0046] Fatty alcohol polyoxyethylene ether AEO-5: 2.7%

[0047] Softened water: 79.4%

[0048] Glacial acetic acid: 0.1%

[0049] Total: 100%

[0050] Add the trichloro-s-triazine modified amino silicone oil synthesized in step (1) and emulsifier fatty alcohol polyoxyethylene ether AEO-5 into the emulsifier kettle, then add softened water three times, continue to stir at high speed for 20 minutes after each addition of water, then add glacial acetic acid, and finally homogenize for 45 minutes to obtain a uniformly and stably dispersed modified amino silicone oil emulsion 1#.

[0051] Example 2

[0052] This embodiment provides a darkening agent for washable cotton, comprising 20.0 parts of dichloro-s-triazine-modified amino silicone oil, 2.3 parts of emulsifier, 0.1 parts of glacial acetic acid, and 77.6 parts of water;

[0053] The preparation method includes the synthesis of dichloro-s-triazine modified amino silicone oil and its emulsification method:

[0054] (1) Synthesis of dichlorotriazine modified amino silicone oil:

[0055] Ratio: Amino silicone oil: 97.2%

[0056] Dichlorotriazine: 2.8%

[0057] Total: 100%

[0058] Its synthetic route is:

[0059]

[0060] The preparation method is as follows:

[0061] Add amino silicone oil to the reactor, then add dichlorotriazine in three times at a ratio of 1:1:1.2, adjust the pH to 4.5 with acetic acid, react at 30°C for 3.5 hours, and then separate the modified silicone oil by reduced pressure distillation to obtain dichlorotriazine-modified amino silicone oil.

[0062] (2) Dichlorotriazine modified amino silicone oil emulsification:

[0063] Ratio: Dichlorotriazine modified amino silicone oil: 20.0%

[0064] Fatty alcohol polyoxyethylene ether AEO-5: 1.1%

[0065] Fatty alcohol polyoxyethylene ether AEO-7: 1.2

[0066] Softened water: 77.6%

[0067] Glacial acetic acid: 0.1%

[0068] Total: 100%

[0069] Add the dichlorotriazine modified amino silicone oil, fatty alcohol polyoxyethylene ether AEO-5 and fatty alcohol polyoxyethylene ether AEO-7 synthesized in step (1) into the emulsifying kettle; then add softened water three times, continue stirring at high speed for 20 minutes after each addition of water, then add glacial acetic acid, and finally homogenize for 60 minutes to obtain a uniformly and stably dispersed modified amino silicone oil emulsion 2#.

[0070] Example 3

[0071] This embodiment provides a darkening agent for washable cotton, comprising 30 parts of acryloyl chloride modified amino silicone oil, 6 parts of emulsifier, 0.4 parts of glacial acetic acid, and 63.6 parts of water; the preparation method includes the synthesis of acryloyl chloride modified amino silicone oil and its emulsification method:

[0072] (1) Synthesis of acryloyl chloride modified amino silicone oil:

[0073] Ratio: Amino silicone oil: 97.3%

[0074] Acryloyl chloride: 2.7%

[0075] Total: 100%

[0076] Its synthetic route is:

[0077]

[0078] The preparation method is as follows:

[0079] Add amino silicone oil to the reactor, and then add acryloyl chloride in three times at a ratio of 1:1:1.2. Use acetic acid to adjust the pH to 5. React at 20°C for 3 hours, and then separate the modified silicone oil by reduced pressure distillation to obtain acryloyl chloride-modified amino silicone oil.

[0080] (2) Acryloyl chloride modified amino silicone oil emulsification:

[0081] Ratio: Acryloyl chloride modified amino silicone oil: 10.0%

[0082] Fatty alcohol polyoxyethylene ether AEO-5: 1.0%

[0083] Softened water: 88.95%

[0084] Glacial acetic acid: 0.05%

[0085] Total: 100%

[0086] Add the acryloyl chloride modified amino silicone oil and fatty alcohol polyoxyethylene ether AEO-5 synthesized in step (1) into the emulsifying kettle, then add softened water three times, continue to stir at high speed for 20 min after each addition of water, then add glacial acetic acid, and finally homogenize for 40 min to obtain a uniformly and stably dispersed modified amino silicone oil emulsion 3#.

[0087] Example 4

[0088] This embodiment provides a darkening agent for washable cotton, comprising 17.8 parts of amino silicone oil modified by a basic crosslinking agent, 2.8 parts of an emulsifier, 0.1 parts of glacial acetic acid, and 79.3 parts of water;

[0089] The preparation method includes the synthesis of chloroacetyl chloride modified amino silicone oil and its emulsification method:

[0090] (1) Synthesis of chloroacetyl chloride modified amino silicone oil:

[0091] Ratio: Amino silicone oil: 97.5%

[0092] Acryloyl chloride: 2.5%

[0093] Total: 100%

[0094] Its synthetic route is:

[0095]

[0096] The preparation method is as follows:

[0097] Add amino silicone oil and chloroacetyl chloride into the reaction kettle; adjust the pH to 4 with acetic acid, react at 25° C. for 3.5 hours, and then separate the modified silicone oil by vacuum distillation to obtain chloroacetyl chloride modified amino silicone oil.

[0098] (2) Chloroacetyl chloride modified amino silicone oil emulsification:

[0099] Ratio: Chloroacetyl chloride modified amino silicone oil: 17.8%

[0100] Fatty alcohol polyoxyethylene ether AEO-7: 2.8%

[0101] Softened water: 79.3%

[0102] Glacial acetic acid: 0.1%

[0103] Total: 100%

[0104] Add the alkaline crosslinker modified silicone oil synthesized in step (1) and fatty alcohol polyoxyethylene ether AEO-7 into the emulsifying kettle, then add softened water three times, continue to stir at high speed for 20 minutes after each addition of water, then add glacial acetic acid, and finally homogenize for 40 minutes to obtain a uniformly and stably dispersed modified amino silicone oil emulsion 4#.

[0105] Example 5

[0106] This embodiment provides an application of a washable cotton darkening agent in cotton textiles, which specifically includes the following process:

[0107] The washable cotton darkening agent provided in Examples 1-4 was used to prepare 40-80 g / L of cotton fabric finishing liquid, respectively, and the pH was adjusted to 10-12. The selected cotton textile fabric was dipped and rolled. The liquid carrying rate of the fabric after dipping and rolling was 50%-90%, and it was dried at 140°C-160°C.

[0108] The fabrics and dyes used for evaluation in this example are as follows:

[0109] Fabric A: Cotton sulphur black woven fabric (Dye brand: Runtu sulphur black 2BR)

[0110] Fabric B: Cotton reactive black woven fabric (Dye brand: Runtu reactive black ED-H)

[0111] Fabric C: Cotton reactive dark blue woven fabric (Dye brand: Runtu reactive dark blue R-2GLN)

[0112] Fabric D: Cotton reactive red woven fabric (Dye brand: Runtu reactive red R-2BF)

[0113] In order to further compare the deepening effect and obtain the performance evaluation results of the embodiment, four existing deepening agents are also provided in this embodiment for comparative testing. The specific operation process in this embodiment is as follows:

[0114] Darkening finishing formula: Taking the effective ingredient of modified amino silicone oil emulsion 1# as the standard, convert the dosage of other darkening agents and compare the effects of each darkening agent in parallel, as shown in the following table:

[0115]

[0116] Darkening agent finishing method:

[0117] One dip and one roll (using soda ash to adjust the pH value of the prepared finishing liquid to 12, pressure: 2kg / m 2 ; Speed: 50 m / min) → Dry at 150°C (6-section oven).

[0118] The deepening effect evaluation method used in this embodiment is:

[0119] The "strength difference value" of the fabric is tested using a Datacolor Spectro 1000 colorimeter. The strength value of the unfinished fabric (standard sample) is 100%. The higher the strength difference value of the treated fabric, the better the darkening effect.

[0120] Washing standard for finished fabrics: AATCC 135(Ⅱ)27±3℃Ai

[0121] After the above test process, the evaluation results of the deepening performance of each fabric are as follows:

[0122] Table 1. Darkening effect of finishing of cotton vulcanized black woven fabric

[0123]

[0124]

[0125] Table 2. Darkening effect of finishing of cotton reactive black woven fabric

[0126]

[0127] Table 3. Darkening effect of finishing of cotton active dark blue woven fabric

[0128]

[0129]

[0130] Table 4. Darkening effect of finishing of cotton active red woven fabric

[0131]

[0132] From the large amount of data in the above table, it can be seen that the alkaline crosslinker modified organic silicon darkening agent 1#-4# provided in the present invention has good washing resistance for these types of dye-dyed cotton woven fabrics, and the initial darkening effect reaches more than 35%. After 50 times of water washing, the fabrics treated with 1#~4# modified amino silicone oil emulsions still have a darkening effect, while the fabrics treated with the other darkening agents in the table no longer have a darkening effect after 30 times of water washing, but instead have a phenomenon of decreased depth; from the above comparison, it can be seen that the modified amino silicone oil emulsions 1#~4# provided in the present invention have excellent darkening and water-washing resistance.

[0133] By adopting the above technical solution disclosed in the present invention, the following beneficial effects are obtained:

[0134] The present invention provides a darkening agent for washable cotton, a preparation method and an application thereof. The darkening agent provided in the present invention utilizes an alkaline crosslinking agent to modify amino silicone oil, so that the amino silicone oil has high reactivity; the amino silicone oil modified by the alkaline crosslinking agent can react with hydroxyl groups in cotton fibers, so that the darkening agent and the cotton fibers are more firmly combined, thereby obtaining excellent washability. Even after being washed 50 times, the fabric still has a good darkening effect.

[0135] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be considered as the scope of protection of the present invention.

Claims

1. A darkening agent for washable cotton, characterized in that: By weight, it comprises 10 to 30 parts of modified amino silicone oil, 1 to 6 parts of emulsifier, 0.05 to 0.4 parts of glacial acetic acid, and the remaining part is softened water; The modified amino silicone oil is synthesized by reacting an alkaline crosslinking agent with an amino silicone oil with a high amino value whose side chain structure is N-β-aminoethyl-γ-aminopropyldimethoxysilane; The alkaline crosslinking agent includes trichloro-s-triazine, dichloro-s-triazine, acryloyl chloride or chloroacetyl chloride; The synthetic route of alkaline crosslinker modified amino silicone oil is as follows: (1) Synthesis route of trichlorotriazine modified amino silicone oil: (2) Synthesis route of dichlorotriazine modified amino silicone oil: (2) Synthesis route of acryloyl chloride modified amino silicone oil: (4) Synthesis route of chloroacetyl chloride modified amino silicone oil: m value range: 40~80, n value range: 2~8; The darkening agent is prepared by the following steps: S1, amino silicone oil modified by alkaline crosslinking agent: add 90-100 parts of amino silicone oil to a reaction kettle, then add alkaline crosslinking agent in 3 times, 0.5-3.4 parts each time, adjust the pH to 4-5 with acetic acid, react at 20℃-30℃ for 3-4 hours, then separate the modified silicone oil by reduced pressure distillation to obtain amino silicone oil modified by alkaline crosslinking agent; S2, emulsification of modified amino silicone oil: add 10-30 parts of the basic crosslinking agent modified amino silicone oil and 1-6 parts of the emulsifier in step S1 into the emulsification kettle, then add 20-35 parts of softened water three times, continue to stir at high speed for 20 minutes after each addition of water, then add 0.05-0.4 parts of glacial acetic acid, and finally homogenize for 30-60 minutes to obtain a uniformly and stably dispersed modified amino silicone oil emulsion.

2. The darkening agent for washable cotton according to claim 1, characterized in that: The emulsifier is selected from one or more of C6-C18 fatty alcohol polyoxyethylene ethers.

3. The darkening agent for washable cotton according to claim 1, characterized in that: The basic cross-linking agent is added three times in a ratio of 1:1:1.

2.

4. Use of the darkening agent for washable cotton according to any one of claims 1 to 3 in cotton textiles.

5. The use of the darkening agent for washable cotton in cotton textiles according to claim 4, characterized in that: The following steps are involved: The washable cotton darkening agent according to any one of claims 1 to 3 is used to prepare 40-80 g / L of cotton fabric finishing liquid, the pH is adjusted to 10-12, and the fabric is dipped and rolled. The fabric has a liquid rate of 50% to 90% after dipping and rolling, and is dried at 140°C to 160°C.

6. The use of the darkening agent for washable cotton in cotton textiles according to claim 5, characterized in that: Use soda ash to adjust pH.

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