CN115852719B

CN115852719B - Silicon-containing color fixing auxiliary agent and application thereof in cotton printing and dyeing

Info

Publication number: CN115852719B
Application number: CN202211231714.4A
Authority: CN
Inventors: 濮坚锋; 蒋国强; 胡铭; 吴广全
Original assignee: Zhejiang Yuexin Dyeing & Printing Co ltd
Current assignee: Zhejiang Yuexin Technology Co ltd
Priority date: 2022-09-30
Filing date: 2022-09-30
Publication date: 2024-03-26
Anticipated expiration: 2042-09-30
Also published as: CN115852719A

Abstract

The invention discloses a silicon-containing fixation aid which is prepared by quaternization reaction of tertiary amino silicone oil and (2-chloroethanesulfonyl) ethylene. The fixation aid can adopt a one-pot method to fix and finish dyed cotton fabrics at the same time, and specifically comprises the following steps: washing and drying the dyed cotton fabric, immersing the dyed cotton fabric in a siliceous fixation aid, immersing the dyed cotton fabric at 60 ℃ for 30min, adding alkali to adjust pH=7-8, and preserving heat for 20min; and then washing, soaping, washing and drying the treated cotton fabric. The method shortens the process flow and simultaneously solves the problems of pollution emission and low rubbing color fastness of the color fixing process in the prior art.

Description

Silicon-containing color fixing auxiliary agent and application thereof in cotton printing and dyeing

Technical Field

The invention belongs to the technical field of printing and dyeing, and particularly relates to a silicon-containing color fixing auxiliary agent and application thereof in cotton printing and dyeing.

Background

Cotton and other cellulosic fibers are often dyed with reactive dyes. In the reactive dye dyeing process, a large amount of salt is required to be added to promote dye-uptake, and fixation is required to be carried out under high-alkali conditions in the later dyeing period. In the fixation process, a part of reactive dye reacts with cellulose fiber under the action of alkali to form covalent bond combination; at the same time, the dye which does not react with the fiber is partially hydrolyzed under alkaline conditions and adsorbed on the fiber. These unfixed dyes directly lead to a decrease in the color fastness of the dyed fabric. Therefore, in practical production, a color fixing agent is commonly used for fixing the dyed fabric so as to improve color fastness. With the development of society, people are increasingly researching environment-friendly formaldehyde-free color fixing agents. The polyamine type color fixing agent is a high molecular compound formed by the reaction of diethylenetriamine and dicyandiamide and the steps of condensation, deamination, polycondensation and the like, and the structure of the polyamine type color fixing agent contains more reactive groups and can be combined with dye and fiber in a covalent bond way, so that the color fastness of the fabric is improved. However, a large amount of ammonia gas is generated during the reaction, which makes the production limited. The other is a polycation type color fixing agent (polydimethyldiallyl ammonium chloride, PDADMAC) which is prepared by polymerizing a cationic monomer of dimethyldiallyl ammonium chloride (DADMAC) in an aqueous solution through free radicals. PDADMAC has positive charges with higher density, can be combined with dye anions in an ionic bond way, and improves the color fastness of the fabric. However, due to the excellent water solubility of PDADMAC, the color-fixed fabrics have poor washing fastness, and most of the dye still enters the water phase through washing under the action of mechanical external force. Therefore, the development of a novel fixing agent and the application of the novel fixing agent to reactive dye cotton dyeing are of great significance.

Disclosure of Invention

Aiming at the technical current situation of dyeing cotton fixation, the invention provides a silicon-containing fixation auxiliary agent, which can be used for simultaneously fixing and finishing dyed cotton fabric by a one-pot method, shortens the process flow, and simultaneously solves the problems of pollution emission and low friction-resistant color fastness of the fixation process in the prior art.

The invention is realized in such a way that the invention provides the following technical scheme: a silicon-containing fixation aid has the following molecular structure:

wherein m/n=1 to 5:1.

Further, the preparation method of the modified silicone oil comprises the following steps:

hydrolyzing N, N-diethyl amine propyl methyl dimethoxy silane with anhydrous diethyl ether as solvent under alkaline condition to prepare total grafted tertiary amino silicone oil; further, the N, N-diethyl amine propyl methyl dimethoxy silane is mixed with D according to the metering ratio ₄ Mixing with MM, and heating to react under the catalysis of tetramethylammonium hydroxide silicon alkoxide to prepare tertiary amino silicone oil.

And (3) taking ethanol as a solvent, and carrying out quaternization reaction on tertiary amino silicone oil and (2-chloroethanesulfonyl) ethylene to obtain the modified silicone oil.

The invention provides a silicon-containing fixation aid which is applied to cotton fabrics, and the specific application comprises the following steps:

(1) Washing and drying the dyed cotton fabric, immersing the dyed cotton fabric in a modified silicone oil solution, immersing the dyed cotton fabric at 60 ℃ for 30min, adding alkali to adjust pH=7-8, and preserving heat for 20min.

(2) And (3) washing, soaping, water washing and drying the treated cotton fabric.

Further, in the step (1), the modified silicone oil solution is an aqueous solution, the bath ratio is 1:10, and the dosage is 5% o.w.f.

Further, in the step (1), the alkali is NaOH or Na ₂ CO ₃ One or more of the following.

Further, the drying in the step (2) refers to pre-drying the cotton fabric at 80-100 ℃ for 5-20 min and then baking at 120-140 ℃ for 2-20 min.

Color fixation finishing process principle:

after the pH is regulated to be alkaline, hydroxyl groups of the cotton fabric are protonated and crosslinked with vinyl groups in the silicone oil, so that the silicone oil is bonded on the fabric, the adhesion rate of the curing finishing agent is improved, and the fabric is endowed with lasting antibacterial property, flexibility and color fastness.

The invention has the following advantages and beneficial effects:

(1) The cotton fabric provided by the invention has soft hand feeling, and the friction color fastness and the soaping color fastness are greatly improved compared with the common color fixation finishing process (soft finishing after alkali fixation) by the aid of the color fixation alkali liquor.

(2) The invention provides a silicon-containing color fixing auxiliary agent, which can be used for fixing and finishing dyed cotton fabrics simultaneously by a one-pot method, shortens the process flow, and simultaneously solves the problems of pollution emission and low friction and color fastness of the color fixing process in the prior art.

Drawings

FIG. 1 shows tertiary amino silicone oil (PtAMS-2) ¹ H-NMR。

FIG. 2 shows a modified silicone oil (PtAMS-2 as a raw material) ¹ H-NMR。

Detailed Description

The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.

The invention tests:

(1) Softness test: the effect of the finishing agent on the treated fabric is evaluated by feeling the combination factors such as the bulk, softness, rebound resilience and smoothness of the treated fabric by touching with hands, and the hand feeling is classified into 5 grades, the higher the grade is, the better the grade is, the 5 grades are the best, and the grade 1 is the lowest.

(2) Color fastness testing:

the fastness to soaping is determined according to the method of GB/T3921-2008 "fastness to soaping for textile color fastness test".

The rubbing fastness was determined according to GB/T3920-2008 "rubbing fastness to fabric fastness test".

Example 1

Preparing modified silicone oil.

S1: preparation of tertiary amino silicone oil

100mL of anhydrous diethyl ether and 60g of N, N-diethylaminopropyl methyl dimethoxy silane are added into a three-neck flask equipped with an electric stirrer, a thermometer and a reflux condenser, the mixture is stirred and heated to 40 ℃, 17g of 20wt% NaOH aqueous solution is slowly added dropwise, the hydrolysate is poured into a separating funnel after 4 hours, the mixture is washed with water until the pH value is 8, and an ether layer is prepared by using anhydrous MgSO ₄ Drying, filtering and evaporating diethyl ether to obtain the full-grafted tertiary amino silicone oil, wherein the amine value measured by a non-aqueous titration method is 4.24mmol/g.

Is provided with N ₂ Adding full-grafted tertiary amino silicone oil into a four-neck flask of a protection device, an electric stirrer, a thermometer and a condenser tube, and D ₄ And (2) the MM and the tetramethylammonium hydroxide accounting for 1 weight percent of the total mass of the raw materials are heated to 90 ℃ to react for 9 hours, then heated to 150 ℃ and stirred for 30 minutes to decompose the catalyst. And (3) removing small molecular low-boiling substances by rotary evaporation at 120 ℃ to obtain the target product tertiary amino silicone oil.

The amine number and molecular weight of the tertiary amino silicone oil (PtAMS) at various dosages are shown in the following table.

TABLE 1

The number average molecular weight (Mn) was measured by using a Waters 515-2414 type gel permeation chromatograph, chloroform as the mobile phase, a flow rate of 1mL/min, a detector temperature of 35℃and a column temperature of 40℃and a narrow distribution of Polystyrene (PS) as the standard.

S2: preparation of modified silicone oil

Adding tertiary amino silicone oil, absolute ethyl alcohol and heating to 90 ℃ into a three-port reaction bottle provided with a thermometer, a stirring device and a condenser tube, starting to dropwise add an ethanol solution of (2-chloroethanesulfonyl) ethylene, carrying out heat preservation reflux reaction for 30h, removing a solvent by evaporation, dissolving and dialyzing for 3d again by water to remove (2-chloroethanesulfonyl) ethylene, and drying to obtain the modified silicone oil. The ratio of the amine group molar quantity of the tertiary amino silicone oil to the molar quantity of the (2-chloroethanesulfonyl) ethylene is 1:3.

example 2

The cotton fabric adopts bleached and mercerized pure cotton knitted fabric (21 counts, 180 g/m) ² And (3) cargo number: DM1, manufacturer: guangzhou Fuguang Kongya textile dyeing and finishing plant), cotton fabrics are dyed using the following conditions: the dye is active scarlet 3BS (purchased from Zhejiang leap soil Co., ltd.) with the dosage of 3% o.w.f, the bath ratio of 1:10, the temperature of 60 ℃ and the time of 60min; washing with water (bath ratio 1:10, temperature 60 ℃ for 10 min); drying (120 ℃ C., 20 min) was performed.

And (3) immersing the dyed cloth in a modified silicone oil solution for fixation, immersing at 60 ℃ for 30min (bath ratio is 1:10, the dosage is 5% o.w.f.), adding NaOH solid to adjust pH=7-8, preserving heat for 20min, and taking out the fabric for the next step.

Firstly, washing with water (bath ratio 1:10, temperature 60 ℃ C., time 10 min), and then, washing with soap (2 g/L DB-5, bath ratio 1:10, temperature 90 ℃ C., time 20 min); then water washing (bath ratio 1:10, temperature 60 ℃ C., time 10 min); drying (120 ℃ C., 20 min).

The treatment recipe for the swatches is shown in table 2 below.

TABLE 2

Sample of	Modified silicone oil numbering
		Sample cloth 1	PtAMS-1
Sample cloth 2	PtAMS-2
		Sample cloth 3	PtAMS-3
Sample cloth 4	PtAMS-4

Comparative example 1

The cotton fabric is dyed, fixed and finished in a conventional manner and is marked as sample 5.

The specific flow is as follows: padding dyeing, drying (80 ℃), impregnating fixation, steaming (100 ℃,70 seconds), washing (bath ratio 1:10, 60 ℃,10 minutes), soaping (2 g/L DB-5, bath ratio 1:10, 90 ℃,20 minutes), washing (bath ratio 1:10, 60 ℃,10 minutes), drying (80 ℃), padding finishing liquid, drying (10 minutes pre-baking at 90 ℃,5 minutes baking at 120 ℃).

Padding and dyeing: active scarlet 3BS (the dosage is 3% o.w.f), anhydrous sodium sulphate 50g/L; the rolling surplus rate is 65 percent.

Color fixing liquid: 6g/L sodium hydroxide, 20g/L sodium carbonate and 200g/L sodium chloride; the bath ratio is 1:10, the temperature is 60 ℃, and the time is 60min.

Finishing liquid: amino silicone oil (amine value 0.6mmol/g, viscosity 5000cP, purchased from Jinan Xinglong chemical industry Co., ltd.) 30%, emulsifier 5% (TO-5/TO-7=1:1), and water in balance; the rolling surplus rate is 80 percent.

Comparative example 2

The fixing liquid in comparative example 1 is changed to a commercial formaldehyde-free fixing agent GD-80 (purchased from Federal Kete), and the fixing liquid is specifically: aldehyde-free fixing agent GD-804g/L; the bath ratio was 1:10, the temperature was 60℃for 60 min), and the sample was designated as sample 6.

The results of each test of the finished fabric are shown in Table 3.

Table 3:

the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims

1. A silicon-containing color-fixing aid, characterized in that it has the following molecular structure:

In the formula, m/n=1～5:1.

2. The preparation method of a silicon-containing color fixing aid according to claim 1, characterized in that it includes the following steps: using anhydrous ether as a solvent, N, N-diethylamine propyl methyl dimethyl Oxysilane is hydrolyzed under alkaline conditions to prepare fully grafted tertiary amino silicone oil; further, N,N-diethylaminepropylmethyldimethoxysilane is mixed with octamethylcyclotetrasiloxane in a stoichiometric ratio D ₄ is mixed with hexamethyldisiloxane MM, and heated to react under the catalysis of tetramethylammonium silicon alkoxide to prepare tertiary amino silicone oil;

Using ethanol as the solvent, tertiary amino silicone oil and (2-chloroethanesulfonyl)ethylene are subjected to quaternization reaction to prepare modified silicone oil; the amine value of the tertiary amino silicone oil is 1.6 to 3.5 mmol/g; The molar ratio of the amine group of the amino silicone oil and the molar amount of (2-chloroethanesulfonyl)ethylene is 1:3.

3. Application of a silicon-containing color-fixing aid according to claim 1, characterized in that the silicon-containing color-fixing aid is applied to pure cotton fabrics.

4. Application of a silicon-containing color-fixing aid according to claim 3, characterized in that the specific application method of the silicon-containing color-fixing aid is as follows:

(1) Wash and dry the dyed fabric and then immerse it in the modified silicone oil solution. After immersing it at 60°C for 30 minutes, add alkali to adjust the pH = 7 to 8 and keep it warm for 20 minutes;

(2) Wash, soap, wash and dry the treated fabrics.

5. Application of a silicon-containing color fixing aid according to claim 4, characterized in that the modified silicone oil solution in step (1) is an aqueous solution, the liquor ratio is 1:10, and the dosage is 5% o.w.f. .

6. Application of a silicon-containing color fixing aid according to claim 4, characterized in that the base in step (1) is one or more of NaOH and Na ₂ CO ₃ .

7. The application of a silicon-containing color fixing aid according to claim 4, characterized in that the drying in step (2) refers to pre-drying the cotton fabric at 80°C to 100°C for 5min to 20min, and then Bake at 120℃～140℃ for 2min～20min.