CN117802799A - Dyeing method for post-adjusting pH value of dye liquor and implementation device - Google Patents
Dyeing method for post-adjusting pH value of dye liquor and implementation device Download PDFInfo
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Abstract
The invention belongs to the technical field of textile printing and dyeing, and relates to a dyeing method for adjusting the pH value of a dye liquor after the dyeing, namely adding an acid solution to adjust the pH value of the dye liquor during dyeing, wherein the dyeing comprises a heating stage, and the operation of adding the acid solution to adjust the pH value of the dye liquor is carried out in the heating stage; the realization device comprises an acid material tank, a feed pump, an electromagnetic valve, a flowmeter, a closed dye vat, a safety valve, a pressure gauge, a thermometer and a PLC controller; the acid material tank, the feed pump, the electromagnetic valve, the flowmeter and the closed dye vat are connected in sequence; the feeding pump, the safety valve and the acid material tank are connected in sequence; the pressure gauge is connected with the airtight dye vat; the thermometer is connected with the airtight dye vat; the PLC controller is connected with the feed pump, the pressure gauge, the thermometer, the electromagnetic valve, the flowmeter and the safety valve at the same time. The invention effectively solves the problems of color spots, color points, uneven dyeing and the like of the cloth cover and low one-time dyeing success rate in the prior art.
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing, and relates to a dyeing method for post-adjusting the pH value of dye liquor and a realization device thereof.
Background
When the commercial disperse dye is produced, a dispersing agent is added for grinding, and the obtained disperse dye with the nano-micron particle size can maintain the dispersion stability of the dye in the aqueous solution and the dyeing process after being prepared into a dye solution.
At present, the most commonly used disperse dye dispersant is sodium lignin sulfonate, and document 1 (static layer-by-layer self-assembly research of sodium lignin sulfonate under different pH conditions, high molecular report, 2010,6, 699-704) describes that sodium lignin sulfonate contains 9.28wt% of sulfonate, 3.87wt% of carboxyl and 1.59wt% of phenolic hydroxyl; and document 2 (Guo Jizhen, chen Anji. Organic acid base principle [ M ]. Xiamen: xiamen university Press. 1991.) and document 3 (static layer-by-layer self-assembly study of sodium lignin sulfonate under different pH conditions, high molecular theory report, 2010,6, 699-704) describe that pKa of benzenesulfonic acid and α -naphthalenesulfonic acid are 1.5 and 0.74, respectively, pKa of carboxylic acid is between 3 and 5, pKa of phenolic hydroxyl group is about 9 to 10, and only sulfonate is ionized at pH < 3.5; when the pH is in the range of 3.5-9, the sulfonate is completely ionized, and the ionization degree of the carboxyl increases with the rise of the pH value; and only at pH > 9, the phenolic hydroxyl groups begin to ionize. Thus, the degree of ionization of sulfonate, carboxyl, and phenolic hydroxyl groups determines the dispersing ability of the dispersant.
For the conventional dyeing process (the process flow is shown in figure 2) of the disperse dye, after the dye liquor is prepared, the pH value is 7-9, in order to prevent the disperse dye from hydrolysis under alkaline conditions, the dye bath is required to be regulated to be weak acid (namely, the pH value is regulated to be 5-6) before dyeing, at the moment, all the sulfonate of the sodium lignin sulfonate is ionized, but the ionization degree of carboxyl is poor, and the phenolic hydroxyl is not ionized at all, so that the dispersing dye is adsorbed on the surface of the dye, the electrostatic repulsive force provided by the dispersing dye is weak, and the disperse dye is difficult to maintain stable dispersing effect. Particularly, for the disperse dye with high molecular weight, good flatness, high water washing resistance and high sublimation fastness, the dye is easy to gather in the process that the dye liquor is heated from room temperature to the temperature required by dyeing, so that the phenomena of color spots, color points, uneven dyeing and the like of the cloth surface are caused, and the disperse dye with high color fastness has low one-time dyeing success rate.
For weak acid dye with high color fastness, the molecular weight is relatively large, hydrophilic groups such as sulfonate, carboxyl and hydroxyl are contained in the structure, the pH of the dye liquor is 7-9 after the dye liquor is prepared, and in order to prevent the weak acid dye with high color fastness from hydrolysis under alkaline conditions, according to a conventional dyeing process (the process flow is shown in figure 4), the dye bath is required to be adjusted to the weak acid condition with pH=4-6 before dyeing, and the specific pH is different according to different dyes. However, under the weak acidic condition of ph=4-6, hydrophilic groups such as sulfonate, carboxyl and hydroxyl in dye molecules have low ionization degree, poor dye solubility and easy dye agglomeration, so that the phenomena of color spots, color points, uneven dyeing and the like on the cloth cover occur, and the dyeing one-time success rate is low.
For the neutral dye with high color fastness, the molecular structure is complex and large, hydrophilic groups in the molecule comprise sulfonyl amino, methylsulfonyl and the like, the pH of the dye liquor is 7-9 after the dye liquor is prepared, the pH of the dye liquor is required to be regulated to 6-7 according to a conventional dyeing process (the process flow is shown in figure 6) in order to prevent the neutral dye with high color fastness from being hydrolyzed, but the solubility of the dye is reduced under the condition that the pH is 6-7, the dye is easy to agglomerate, the ionization degree of amino in polyamide fiber is higher, the dye attraction force after agglomeration is stronger, the phenomena of color spots, color points, uneven dyeing and the like on the cloth surface are caused, and the one-time dyeing success rate is low.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a dye dyeing method and device for adjusting the pH value of dye liquor.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the dyeing method for adjusting the pH value of the dye liquor after the dyeing comprises the steps of adding an acidic solution to adjust the pH value of the dye liquor during dyeing, wherein the dyeing comprises a heating stage, and the operation of adding the acidic solution to adjust the pH value of the dye liquor is carried out in the heating stage;
when the acid solution starts to be added, the temperature of the dye solution is T 2 The method comprises the steps of carrying out a first treatment on the surface of the When the addition of the acid solution is stopped, the temperature of the dye liquor is T 3 ，T 3 >T 2 ；
The dye in the dye solution is disperse dye, when the acid solution is added, the ionization degree of carboxyl of the dispersing agent in the disperse dye is more than 50%, T 2 80-100 ℃; when the addition of the acid solution is stopped, the ionization degree of carboxyl groups of the dispersing agent in the disperse dye is less than 30 percent, T 3 110-120 ℃;
or the dye in the dye liquor is weak acid dye, when the acid solution is added, the ionization degree of carboxyl in the weak acid dye structure is more than 50%, T 2 50-60 ℃; when the addition of the acid solution is stopped, the ionization degree of carboxyl in the weak acid dye structure is less than 30 percent, T 3 80-90 ℃;
or the dye in the dye liquor is neutral dye, the product to be dyed is polyamide fiber, polyamide fiber pure textile or polyamide fiber blended fabric (such as polyamide fiber and cotton fiber blended fabric, polyamide fiber and wool fiber blended fabric, polyamide fiber and viscose fiber blended fabric, polyamide fiber and tencel fiber blended fabric and the like), when the acid solution is added, the ionization degree of amino groups in the polyamide fiber is less than 30 percent, T 2 50-60 ℃; when the addition of the acid solution is stopped, the ionization degree of amino groups in the polyamide fiber is more than 50 percent, T 3 80-90 ℃.
The mechanism of the invention is as follows:
According to the process for adjusting the pH value of the dye liquor after the dyeing, the pH value is adjusted without adding an acid solution before the disperse dye is dyed, the pH value of a dispersing agent and a disperse dye aqueous solution system is in the range of 7-9, and when the dyeing is started, the ionization degree of carboxyl ions in a dispersing agent structure is far greater than that of the dispersing agent under the acid condition, so that the dispersing effect of the dispersing agent on disperse dye crystals is improved;
in the heating stage, the common disperse dye is easy to hydrolyze under the alkaline and high-temperature conditions, so that an acidic solution is required to be added to adjust the pH value of the dye liquor in the stage;
the adding time of the acid solution is very important, if the acid solution is added too early, the carboxylic acid in the structure of the dispersing agent is not ionized, the acting force between the carboxylic acid and water is far smaller than that of carboxyl ions, the water solubility of the dispersing agent is reduced, the dispersing effect of the dye is maintained by means of electrostatic repulsive force between carboxyl anions among the dispersing agents, the dispersing effect of the dispersing agent of the carboxylic acid structure is poor, crystals of the disperse dye are easy to agglomerate, and uneven dyeing phenomena such as color spots and the like appear when the dye is adsorbed on the fiber; if the acid solution is added too late, after the temperature of the dye solution is raised to more than 120 ℃, groups such as ester bonds, cyano groups and the like in disperse dye structural molecules and ester bonds in a polyester fiber macromolecular structure are easy to hydrolyze under neutral or alkaline conditions, so that dyeing light is dark and fiber strength is reduced; according to the invention, the carboxyl ionization degree of the dispersing agent in the disperse dye is more than 50%, and the acid solution is added when the temperature of the dye liquor is 80-100 ℃, so that the ionization degree of carboxylic acid in the dispersing agent structure can be reduced in the process of adding acid, but the thermal movement of molecules is maintained by means of higher temperature, and the disperse dye can still maintain better dispersion stability in water;
The addition rate of the acid solution is also very important, if the addition rate of the acid solution is too high, the ionization degree of carboxylic acid in the structure of the dispersing agent is reduced too fast, and the water solubility of the dispersing agent and the electrostatic repulsive force among molecules are reduced too fast, so that dye aggregation is caused; if the adding rate of the acid solution is too slow, the heating rate must be reduced, otherwise, when the temperature is increased to 120 ℃, the pH value is still higher, so that the dye and the fiber are hydrolyzed, but after the heating rate is reduced, the dye time is too long, and the production efficiency is obviously reduced; on the basis of selecting proper time to add the acid solution, the invention controls the carboxyl ionization degree of the dispersing agent in the disperse dye to be less than 30% and the temperature of the dye liquor to be 110-120 ℃ when the acid solution is stopped, thus ensuring the moderate adding rate of the acid solution.
For weak acid dye with high color fastness, the molecular weight is larger, hydrophilic groups such as sulfonate, carboxyl and hydroxyl are contained in the structure, after the dye liquor is prepared, the pH value is 7-9, the ionization degree of sulfonate, carboxyl and hydroxyl in the molecule is relatively higher, the solubility of the dye is good, for example, according to the conventional dyeing process, after the dye liquor is added into a dye vat, the dye bath is firstly adjusted to the weak acid condition with the pH value of 4-6, the ionization degree of hydrophilic groups such as carboxyl and hydroxyl in the dye molecule is reduced, the solubility of the dye is poor, the dye is easy to agglomerate, the phenomena such as color spots, color points, uneven dyeing and the like are caused on the cloth surface, and the dyeing one-time success rate is low;
In the invention, the pH value of the dye liquor is maintained to be alkalescent at the initial dyeing stage, and an acidic solution is added at the temperature rising stage to adjust the pH value of the dye liquor so as to realize level dyeing;
the adding time of the acid solution is very important, if the acid solution is added too early, the carboxylic acid in the acid dye structure is not easy to ionize, the acting force between the carboxylic acid and water is far smaller than that of carboxyl ions, the water solubility of the acid dye is reduced, the acid dye is easy to aggregate, and the phenomena of uneven dyeing such as color point and color spot appear when the dye is adsorbed on the fiber; if the acid solution is added too late, after the temperature of the dye liquor is raised to more than 80 ℃, amino in the polyamide fiber structure does not show positive electricity, the affinity of the acid dye and the fiber is low, and the dyeing rate is low; according to the invention, the acid solution is added when the ionization degree of carboxyl in the weak acid dye structure is more than 50% and the temperature of the dye liquor is 50-60 ℃, so that the ionization degree of carboxylic acid in the acid dye structure can be reduced in the process of adding acid, but the thermal movement of molecules is maintained by means of higher temperature, and the acid dye can still maintain better solubility in water;
the addition rate of the acid solution is also very important, and if the addition rate of the acid solution is too high, the ionization degree of carboxylic acid in the acid dye structure is reduced too fast, the water solubility of the acid dye is reduced too fast, and dye aggregation is caused; if the adding rate of the acid solution is too slow, the heating rate must be reduced, otherwise, when the temperature is increased to 98 ℃, the pH value is still higher, so that the affinity between the fiber and the dye is lower, the dye-uptake is lower, but after the heating rate is reduced, the dye time is too long, and the production efficiency is obviously reduced; on the basis of selecting proper time to add the acid solution, the invention controls the ionization degree of carboxyl in the weak acid dye structure to be less than 30% and the temperature of the dye liquor to be 80-90 ℃ when the acid solution is stopped, thus ensuring the moderate adding rate of the acid solution.
For neutral dyes with high color fastness, the molecular structure is large and complex, hydrophilic groups in the molecules comprise sulfonamido groups, methylsulfonyl groups and the like, the pH value of the dye liquor is 7-9 after the dye liquor is prepared, the pH value of the dye liquor is required to be regulated to 6-7 according to a conventional dyeing process, the solubility of the dye is reduced under the condition that the pH value is 6-7, the dye is easy to agglomerate, the ionization degree of amino groups in polyamide fibers is higher, the attractive force of the agglomerated dye is stronger, the phenomena of color spots, color points, uneven dyeing and the like on the cloth surface are caused, and the dyeing primary success rate is low;
in the invention, the pH value of the dye liquor is maintained to be alkalescent at the initial dyeing stage, and an acidic solution is added at the temperature rising stage to adjust the pH value of the dye liquor so as to realize level dyeing;
the adding time of the acid solution is very important, if the acid solution is added too early, the electropositivity of amino in the polyamide fiber is increased, the sulfonylamino and methylsulfonyl contained in the neutral dye with oversized structure can generate larger electrostatic attraction with the polyamide fiber, and the neutral dye has higher aggregation degree due to too low temperature, and when the neutral dye is adsorbed on the fiber, uneven dyeing phenomena such as color point and color spots can occur; if the acid solution is added too late, after the temperature of the dye liquor is raised to more than 80 ℃, amino in the polyamide fiber structure does not show positive electricity, the affinity of neutral dye and fiber is low, and the dyeing rate is low; the invention selects the amino ionization degree in the polyamide fiber to be less than 30 percent, and adds the acid solution when the dyeing temperature is 50-60 ℃, so that the amino ionization degree in the polyamide fiber can be increased in the process of adding acid, but the thermal movement of molecules is maintained by virtue of higher temperature, the electrostatic attraction between the fiber and the dye is smaller, and the neutral dye aggregate is slowly depolymerized, so that the fiber is not dyed too fast;
The addition rate of the acidic solution is also very important, and if the addition rate of the acidic solution is too high, the ionization degree of amino groups in the polyamide fibers is too high, the electrostatic attraction between the fibers and the dye is increased too fast, and the aggregated neutral dye dyes the fibers to generate color spots; if the adding rate of the acid solution is too slow, the heating rate must be reduced, otherwise, when the temperature is increased to 98 ℃, the pH value is still higher, so that the affinity between the fiber and the dye is lower, the dye-uptake is lower, but after the heating rate is reduced, the dye time is too long, and the production efficiency is obviously reduced; on the basis of selecting proper time to add the acid solution, the invention controls the ionization degree of the amino groups in the polyamide fiber to be more than 50% and the temperature of the dye liquor to be 80-90 ℃ when the acid solution is stopped, thus ensuring the moderate adding rate of the acid solution.
As a preferable technical scheme:
the dyeing method for post-adjusting the pH value of the dye liquor is characterized in that the concentration of the acidic solution is 0.1-100.0g/L, and the solute in the acidic solution is one or more of organic acid, inorganic acid and strong acid weak alkali salt, and the method is particularly but not limited to formic acid, acetic acid, propionic acid, citric acid, malonic acid, phosphoric acid, sulfuric acid, hydrochloric acid and ammonium sulfate.
The dyeing method for post-regulating the pH value of the dye liquor comprises five stages, namely a dyeing starting stage, a heating stage, a heat preservation stage, a cooling stage and a post-treatment stage in sequence; the dye liquor temperature at the initial dyeing stage is T 1 ，T 1 <T 2 The pH value of the dye liquor is a, and the time consumption is t 1 The method comprises the steps of carrying out a first treatment on the surface of the The dye liquor heating rate in the heating stage is V 1 The method comprises the steps of carrying out a first treatment on the surface of the When the addition of the acid solution is stopped, the pH value of the dye liquor is b, b<a, a; the temperature of the dye liquor in the heat preservation stage is T 4 ，T 4 ≥T 3 Time-consuming t 2 The method comprises the steps of carrying out a first treatment on the surface of the The dye liquor cooling rate in the cooling stage is V 2 。
Dyeing method for post-regulating pH value of dye liquor as described above, t 1 5-30min, t 2 Is 5-90min, V 2 1-20 ℃/min.
The dyeing method for adjusting the pH value of the dye liquor after the dyeing process is described above, wherein the dye in the dye liquor is disperse dye, the dye concentration is 0.1-15.0owf, and the dye liquor contains a leveling agent; the product to be dyed is polyester fiber, polyester fiber pure textile or polyester fiber blended fabric (such as polyester fiber and cotton fiber blended fabric, polyester fiber and wool fiber blended fabric, polyester fiber and viscose fiber blended fabric, polyester fiber and tencel fiber blended fabric, polyester fiber and spandex fiber blended fabric and the like); t (T) 1 At 35-60deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 5-6, T 4 Is 120-135 ℃.
The dyeing method for adjusting the pH value of the dye liquor after the dyeing process is described above, wherein the dye in the dye liquor is weak acid dye, and the dye concentration is 0.1-15.0owf%; the product to be dyed is polyamide fiber, polyamide fiber pure textile or polyamide fiber blended fabric (for example, polyamide fiber and cotton fiber blended fabric, polyamide fiber and wool fiber blended fabric, polyamide fiber and viscose fiber blended fabric, polyamide fiber and tencel fiber blended fabric, polyamide fiber and spandex fiber blended fabric and the like); t (T) 1 30-50deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 4-6, T 4 Is 98 ℃.
The dyeing method for adjusting the pH value of the dye liquor after the dyeing process is adopted, and the dye in the dye liquorIs neutral dye with dye concentration of 0.1-15.0owf%; t (T) 1 30-50deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 6-7, T 4 Is 98 ℃.
The dyeing method for post-regulating the pH value of the dye liquor has the CIELAB color difference of the dyed product relative to the dyed standard sample<0.8, color difference rating of 4-5, appearance defect rating below 10 min/100 m 2 Meets the standard of superior products of the synthetic fiber fabrics in GB/T17253-2018; the primary success rate of dyeing is more than 98%, the primary success rate of dyeing = the number of products qualified at one time per the number of total products of dyeing multiplied by 100%, the products qualified at one time of dyeing are the products which meet the requirements in the dyeing process without the operations of adding, repairing and repairing, and the CIELAB color difference relative to the dyeing standard sample is met <0.8, color difference rating of 4-5, appearance defect rating below 10 min/100 m 2 。
The invention also provides a device for realizing the dyeing method for adjusting the pH value of the dye liquor after any one of the above steps, which comprises an acid material tank, a feed pump, an electromagnetic valve, a flowmeter, a closed dye vat, a safety valve, a pressure gauge, a thermometer and a PLC;
the acid material tank is used for storing an acid solution;
the acid material tank, the feed pump, the electromagnetic valve, the flowmeter and the closed dye vat are connected in sequence;
the feeding pump, the safety valve and the acid material tank are connected in sequence;
the flowmeter is used for monitoring the flow true value of the acid solution;
the pressure gauge is connected with the closed dye vat and is used for monitoring the pressure in the closed dye vat;
the thermometer is connected with the closed dye vat and is used for monitoring the temperature in the closed dye vat;
the PLC is connected with the feed pump, the pressure gauge, the thermometer, the electromagnetic valve, the flowmeter and the safety valve simultaneously, and is used for controlling the pressure monitored by the pressure gauge to be 170-370KPa and the temperature monitored by the thermometer to be T 1 At the same time, the feed pump is started, and the opening degree of the electromagnetic valve and the safety valve are controlled, so that the flow rate of the flow meter is controlledThe amount is in the range of 0.1-25L/min.
When the temperature in the dye vat exceeds 90 ℃, the pressure in the sealed dye vat is gradually increased (170-370 KPa) along with the continuous increase of the temperature, and when the temperature in the dye vat exceeds 90 ℃, the acid solution adding process cannot be realized in all the dye vats in the market at present due to the large internal and external pressure difference, so that the invention develops an acid solution adding device, and the acid solution can be controllably added into the dye vat under the condition that the pressure in the dye vat reaches 170-370KPa, thereby achieving the purpose of adjusting the pH value of the dye liquor.
As a preferable technical scheme:
the device as described above, further comprising a shut-off valve and a filter; the stop valve is arranged on a connecting pipeline of the flowmeter and the closed dye vat, and is used for preventing dye liquor in the closed dye vat from being sprayed out through the connecting pipeline and flowing back into the flowmeter and the whole material injection system when the liquid injection system fails; the filter is arranged on the connecting pipeline of the acid material tank and the feed pump, and the flowmeter and the feed pump are damaged in order to prevent solid impurities in the acid liquid during the filter.
The beneficial effects are that:
(1) The dyeing method for post-adjusting the pH value of the dye liquor can realize uniform dyeing in the dyeing of disperse dyes, weak acid dyes or neutral dyes, particularly the level dyeing property of the disperse dyes, weak acid dyes and neutral dyes with macromolecular structures is obviously improved, the color point of the cloth cover is avoided, the one-time success rate of production dyeing of enterprises is improved, the color correction is avoided, and the cost is reduced.
(2) The device used in the dyeing method for adjusting the pH value of the dye liquor after the invention can realize the adjustment of the pH value by adding the acid solution in the dyeing process under the condition that the pressure of the dye vat is 170-370KPa, thereby adjusting and controlling the solubility and the dyeing rate of the dye and realizing the aim of leveling.
(3) Aiming at the dyeing of disperse dye, weak acid dye and neutral dye, the traditional method is characterized in that the pH value is adjusted by adding acid when the dye liquor is prepared at room temperature, the method is innovatively changed into the method that the pH value is not adjusted by adding acid when the dye liquor is prepared at room temperature, the pH value of the dye liquor is adjusted to a certain extent by adding acid when the dye liquor is heated to a certain temperature, the acid adding rate can be controlled according to the process requirement, and the temperature can be kept to be continuously raised when the acid is added without stopping.
Drawings
FIG. 1 is a schematic diagram of the structure of an apparatus used in the dyeing method of the present invention for post-adjusting the pH of a dye liquor;
FIG. 2 is a flow chart of a conventional dyeing process of disperse dyes;
FIG. 3 is a flow chart of a disperse dye dyeing process in the dyeing method of the invention for post-adjusting the pH value of a dye liquor;
FIG. 4 is a flow chart of a conventional dyeing process for weak acid dyes;
FIG. 5 is a flow chart of a weak acid dye dyeing process in the dyeing method of the invention for post-adjusting the pH value of the dye liquor;
FIG. 6 is a flow chart of a conventional dyeing process for neutral dyes;
FIG. 7 is a flow chart of a neutral dye dyeing process in the dyeing method for post-adjusting the pH value of the dye liquor according to the invention.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following are test methods for the relevant performance indicators in each of the examples and comparative examples:
degree of carboxyl ionization of dispersant in disperse dye (example 1): the method comprises the following steps:
the first step: preparing a dye liquor, and performing the same as the step (2) of the example 1;
and a second step of: setting the value of n;
and a third step of: taking a part of dye liquor to divide into n parts, wherein 1 part of dye liquor is not added with acid solution, and n-1 parts of acid solutions with different amounts are added (same as in example 1) to obtain n dye liquors with different pH values;
fourth step: measuring the conductivity of n dye solutions with different pH values by using a conductivity meter (manufactured by Shanghai electric science instruments Co., ltd., brand name Lei Ci DDSJ-308F), and judging whether the absolute value of the difference of the conductivities of the two dye solutions with the minimum pH values is less than 10 -5 S·m -1 If yes, entering the next step; otherwise, the value of n is increased, and the third step is returned;
fifth step: alpha corresponding to n dye solutions with different pH values is calculated, and the calculation formula is as follows:
；
wherein lambda is the conductivity of the dye liquor 0 Is the conductivity of the reference solution (essentially the same as the first step of dyeing, except that the dye is replaced by water),the conductivity of the dye liquor with the minimum pH value;
sixth step: measuring the pH value (5) of the dye liquor when the acid solution is stopped in the step (4) of the embodiment 1, and finding the corresponding alpha (namely, finding the alpha corresponding to the dye liquor with the pH value of 5) according to the result of the fifth step, namely, the carboxyl ionization degree of the dispersing agent in the disperse dye.
Degree of ionization of carboxyl groups in the weakly acidic dye structure (example 5): the method comprises the following steps:
the first step: preparing a dye liquor, and performing the same as the step (2) in the example 5;
and a second step of: setting the value of n;
and a third step of: taking a part of dye liquor to divide into n parts, wherein 1 part of dye liquor is not added with acid solution, and n-1 parts of acid solutions with different amounts are added (same as in example 5) to obtain n dye liquors with different pH values;
fourth step: measuring the conductivity of n dye solutions with different pH values by using a conductivity meter (manufactured by Shanghai electric science instruments Co., ltd., brand name Lei Ci DDSJ-308F), and judging whether the absolute value of the difference of the conductivities of the two dye solutions with the minimum pH values is less than 10 -5 S·m -1 If it isThen enter the next step; otherwise, the value of n is increased, and the third step is returned;
fifth step: alpha corresponding to n dye solutions with different pH values is calculated, and the calculation formula is as follows:
；
wherein lambda is the conductivity of the dye liquor 0 Is the conductivity of the reference solution (essentially the same as the first step of dyeing, except that the dye is replaced by water),the conductivity of the dye liquor with the minimum pH value;
sixth step: measuring the pH value (4) of the dye liquor when the step (4) of the embodiment 5 stops adding the acid solution, and finding the corresponding alpha (namely finding the alpha corresponding to the dye liquor with the pH value of 4) according to the result of the fifth step to obtain the carboxyl ionization degree in the weak acid dye structure.
Degree of ionization of amino groups in polyamide fibers: (taking example 9 as an example): the method comprises the following steps:
the first step: a solution was prepared substantially as described in example 9, step (2), except that: the dye is replaced with water;
and a second step of: setting the value of n;
and a third step of: taking a part of the solution to divide into n parts, wherein 1 part of the solution is not added with acid solution, and the other n-1 parts of the solution are added with acid solutions with different amounts (the same as in example 9), so as to obtain n solutions with different pH values;
fourth step: soaking n identical polyamide fibers in n solutions with different pH values to balance the polyamide fibers, taking out the soaked fibers from the solutions, flushing the soaked fibers with deionized water, and then sucking water with filter paper to remove redundant solutions on the surfaces of the fibers, so as to avoid influencing the measurement of conductivity and obtain n polyamide fibers after pickling;
Fifth step: respectively and correspondingly putting n polyamide fibers subjected to pickling into n polyamide fibers with the concentration of 0.01 mol.L -1 Obtaining n to-be-detected liquids in the NaCl solution;
sixth step: measuring the conductivity of n solutions to be measured by using a conductivity meter (manufactured by Shanghai electric science instruments Co., ltd., brand name Lei Ci DDSJ-308F), and judging whether the absolute value of the difference of the conductivities of the two solutions with the minimum pH value is smaller than 10 -5 S·m -1 If yes, entering the next step; otherwise, the value of n is increased, and the third step is returned;
seventh step: and calculating alpha corresponding to the n liquids to be measured, wherein the calculation formula is as follows:
；
wherein lambda is the conductivity of the liquid to be measured 0 Is at a concentration of 0.01 mol.L -1 Is used for the preparation of the NaCl solution,the conductivity of the solution to be measured corresponding to the solution with the minimum pH value;
eighth step: measuring the pH value (6.2) of the dye liquor when the acid solution is stopped in the step (4) of the embodiment 9, and finding the corresponding alpha (namely, finding the alpha corresponding to the solution to be measured and corresponding to the solution with the pH value of 6.2) according to the result of the seventh step to obtain the amino ionization degree in the polyamide fiber.
With respect to a dyeing standard (a target sample with uniform color, specifically, a customer dyeing sample refers to a piece of dyed fabric sample provided by a customer and is used as a standard and reference for dyeing), the customer dyeing sample requires a dye factory to dye according to indexes such as color, color fastness, chromatic aberration and the like so as to meet the requirements and expectations of the customer) of CIELAB chromatic aberration and chromatic aberration grade: measurement of L at 16 points of the sample under D65 illuminant/10 field of view using a DataColor SF650 type color meter * 、a * 、b * The value, calculate the color difference of the sample relative to standard sample according to CIELAB color difference calculation formula in GB/T8424.3-2001, the color difference average value of 16 points is the index of judging the level dyeing property, grade the color difference according to GB/T250-2008, grade the color difference to be 0 to be 5, the color difference to be 4-5 to be 0-0.8, the color difference to be 0.8-1.7The grade is 4, the color difference is 3-4 grade between 1.7-2.5, and the grade of the color difference is more than or equal to grade 4 according to GB/T17253-2018, and the color difference belongs to superior products.
Appearance defect scoring: definitions of defects refer to GB/T30557-2014, appearance defect scores are rated according to scores in an appearance defect scoring table in GB/T17253-2018, and calculated according to an appearance defect scoring specification, and the scores are smaller than 10 scores/100 m 2 Belongs to superior products.
Dyeing one-time success rate: dyeing one-time success rate = number of products qualified at one time/total number of products dyed x 100%, the products qualified at one time means that the dyeing process meets the requirements, and the products do not need to be subjected to the operations of adding, repairing and repairing, namely CIELAB color difference relative to the dyeing standard sample<0.8, color difference grade of 4-5, appearance defect score lower than 10 min/100 m 2 。
The device for realizing the dyeing method for adjusting the pH value of the dye liquor after the dyeing process is shown in figure 1, and comprises an acid material tank 1, a feed pump 2, an electromagnetic valve 3, a flowmeter 4, a closed dye vat 5, a safety valve 6, a pressure gauge 7, a thermometer 8, a PLC (programmable logic controller) 9, a stop valve 10 and a filter 11;
The acid material tank 1 is used for storing an acid solution;
the acid material tank 1, the feed pump 2, the electromagnetic valve 3, the flowmeter 4 and the closed dye vat 5 are connected in sequence;
the feeding pump 2, the safety valve 6 and the acid material tank 1 are connected in sequence;
the flowmeter 4 is used for monitoring the flow true value of the acid solution;
the pressure gauge 7 is connected with the closed dye vat 5 and is used for monitoring the pressure in the closed dye vat 5;
the thermometer 8 is connected with the closed dye vat 5 and is used for monitoring the temperature in the closed dye vat 5;
the PLC 9 is connected with the feed pump 2, the pressure gauge 7, the thermometer 8, the electromagnetic valve 3, the flowmeter 4 and the safety valve 6 at the same time, the PLC 9 is used for controlling the pressure monitored by the pressure gauge 7 to be 170-370KPa and the temperature monitored by the thermometer 8 to be T 1 At this time, the feed pump 2 is started, and simultaneously the opening degrees of the solenoid valve 3 and the relief valve 6 are controlled to control the flow rate of the feed pump 2The flow rate of the flow meter 4 is in the range of 0.1-25L/min;
the stop valve 10 is arranged on a connecting pipeline of the flowmeter 4 and the closed dye vat 5;
the filter 11 is installed on the connecting pipeline of the acid material tank 1 and the feed pump 2.
The flow of the disperse dye dyeing process (examples 1-4) in the dyeing method for post-adjusting the pH value of the dye liquor is shown in FIG. 3.
The flow of the weak acid dye dyeing process (examples 5-8) in the dyeing method for post-adjusting the pH value of the dye liquor is shown in figure 5.
The flow of the neutral dye dyeing process (examples 9-12) in the dyeing method for post-adjusting the pH value of the dye liquor is shown in FIG. 7.
Example 1
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
disperse dye: disperse blue 10183, manufactured by Zhejiang Bo Australian New Material Co., ltd, and the brand name is brilliant blue E-4R;
leveling agent: high temperature leveling agent MDL, manufacturer is Tuo Na trade (Shanghai) limited company;
water;
and (3) dyeing a product: polyester fiber and spandex blended and four-side stretch;
acidic solution: the concentration is 0.1g/L, the solute is sulfuric acid, and the solvent is water;
(2) Preparing dye liquor;
uniformly mixing a disperse dye, a leveling agent and water, and then adjusting the pH value (if the pH value of the mixed solution is ideal, the pH value can not be adjusted), so as to obtain a dye liquor with the pH value of 7; wherein, the concentration of the disperse dye in the dye solution is 0.1owf, and the concentration of the leveling agent is 0.001 owf;
(3) Firstly, adjusting the temperature of the dye liquor to 35 ℃, and then adding a product to be dyed into the dye liquor to soak for 5min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is increased to 80 ℃, stopping adding the acid solution when the temperature is increased to 110 ℃, and preserving the heat for 5min when the temperature is increased to 120 ℃; wherein the heating rate is 20 ℃/min, the carboxyl ionization degree of the dispersing agent in the disperse dye is 65% when the acid solution is added, the carboxyl ionization degree of the dispersing agent in the disperse dye is 28% when the acid solution is stopped, and the pH value of the dye solution is 5 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 20 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap, water and reduction.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.3, the color difference grade reaches 4-5 grade, and the appearance defect score is 5 min/100 m 2 The one-time success rate of dyeing is 99.4 percent.
Example 2
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
disperse dye: disperse red 19986, manufacturer Des Da (Shanghai) trade company, trade name was large Ainisin fluorescent red B;
leveling agent: high temperature leveling agent TF-212K, manufacturer is a transmission intelligent ply company limited company;
water;
and (3) dyeing a product: polyester fiber, spring spun 260T;
acidic solution: the concentration is 1g/L, the solute is phosphoric acid, and the solvent is water;
(2) Preparing dye liquor;
uniformly mixing a disperse dye, a leveling agent and water, and then adjusting the pH value (if the pH value of the mixed solution is ideal, the pH value can not be adjusted), so as to obtain a dye liquor with the pH value of 7; wherein the concentration of the disperse dye in the dye solution is 1.5owf, and the concentration of the leveling agent is 0.05 owf;
(3) Firstly, adjusting the temperature of the dye liquor to 40 ℃, and then adding a product to be dyed into the dye liquor to soak for 10min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 85 ℃, stopping adding the acid solution when the temperature is raised to 115 ℃, and preserving heat for 20min when the temperature is raised to 125 ℃; wherein the heating rate is 15 ℃/min, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 61% when the acid solution is added, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 25% when the acid solution is stopped, and the pH value of the dye solution is 5.2 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 10 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap, water and reduction.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.5, the color difference grade reaches 4-5 grade, and the appearance defect score is 7 min/100 m 2 The one-time success rate of dyeing is 99.1 percent.
Example 3
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
disperse dye: disperse yellow 10149, manufacturer Zhejiang Wanfeng chemical company, trade mark is light yellow WF-6G;
Leveling agent: a Bai Tesi AD-G, manufactured by Henschel chemical industry trade (Shanghai) Co., ltd;
water;
and (3) dyeing a product: polyester fiber and spandex blended and four-side stretch;
acidic solution: the concentration is 20g/L, the solute is acetic acid, and the solvent is water;
(2) Preparing dye liquor;
uniformly mixing a disperse dye, a leveling agent and water, and then adjusting the pH value (if the pH value of the mixed solution is ideal, the pH value can not be adjusted), so as to obtain a dye liquor with the pH value of 8; wherein the concentration of the disperse dye in the dye solution is 2owf, and the concentration of the leveling agent is 0.1 owf;
(3) Firstly, adjusting the temperature of the dye liquor to 50 ℃, and then adding a product to be dyed into the dye liquor to soak for 15min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is increased to 90 ℃, stopping adding the acid solution when the temperature is increased to 120 ℃, and preserving the heat for 60 minutes when the temperature is increased to 130 ℃; wherein the heating rate is 5 ℃/min, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 55% when the acid solution is added, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 22% when the acid solution is stopped, and the pH value of the dye solution is 5.7 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 5 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap, water and reduction.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.6, the color difference grade reaches 4-5 grade, and the appearance defect score is 8 min/100 m 2 The one-time success rate of dyeing is 99%.
Example 4
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
disperse dye: disperse red 10070, manufacturer Zhejiang de Euro chemical manufacturing Co., ltd, brand red FB;
leveling agent: chelating dispersant TF-133CS, manufacturer is a transmission intelligent ply company;
water;
and (3) dyeing a product: polyester fiber, plain peach skin;
acidic solution: the concentration is 100g/L, the solute is a mixture of citric acid and ammonium sulfate with the mass ratio of 1:1, and the solvent is water;
(2) Preparing dye liquor;
uniformly mixing a disperse dye, a leveling agent and water, and then adjusting the pH value (if the pH value of the mixed solution is ideal, the pH value can not be adjusted), thereby obtaining a dye liquor with the pH value of 9; wherein the concentration of the disperse dye in the dye solution is 15owf, and the concentration of the leveling agent is 0.5 owf;
(3) Firstly, adjusting the temperature of the dye liquor to 60 ℃, and then adding a product to be dyed into the dye liquor to soak for 30min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 100 ℃, stopping adding the acid solution when the temperature is raised to 120 ℃, and preserving the heat for 90min when the temperature is raised to 135 ℃; wherein the heating rate is 0.1 ℃/min, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 52% when the acid solution is added, the ionization degree of carboxyl of the dispersing agent in the disperse dye is 19% when the acid solution is stopped, and the pH value of the dye solution is 6 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 1 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap, water and reduction.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.7, the color difference grade reaches 4-5 grade, and the appearance defect score is 9 min/100 m 2 The one-time success rate of dyeing is 98.5%.
Comparative example 1
A dyeing method for post-adjusting the pH of a dye liquor, substantially as in example 4, with the only difference that: in the step (4), the addition of the acidic solution was started when the temperature was raised to 70 ℃, and the degree of ionization of the carboxyl groups of the dispersing agent in the disperse dye was 28% when the addition of the acidic solution was started (the addition rate and the addition amount of the acidic solution in comparative example 1 were the same as in example 4, the degree of ionization of the carboxyl groups of the dispersing agent in the disperse dye when the addition of the acidic solution was stopped, and the pH value adaptability of the dye solution when the addition of the acidic solution was stopped).
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 1.5, the color difference grade is 4 grade, the dyeing once success rate is 90 percent, and the appearance defect score is 15 minutes/100 m 2 。
As can be seen from comparison between comparative example 1 and example 4, the dyeing product of comparative example 1 has a large dyeing color difference, a low primary success rate and serious appearance defects, because the acid solution is added too early, the temperature is low, the ionization degree of carboxyl groups in the dispersing agent is low, the dissolution stability of the disperse dye in water is difficult to maintain, the disperse dye is easy to agglomerate and deposit on the surface of the polyester fiber, the color point of the color pattern is formed, and the operations such as color repair and the like are needed.
Comparative example 2
A dyeing method for post-adjusting the pH of a dye liquor, substantially as in example 4, with the only difference that: in the step (4), the addition of the acid solution was started when the temperature was raised to 105 ℃, and the degree of ionization of the carboxyl groups of the dispersant in the disperse dye was 68% when the addition of the acid solution was started (the addition rate and the addition amount of the acid solution in comparative example 2 were the same as in example 4, the degree of ionization of the carboxyl groups of the dispersant in the disperse dye when the addition of the acid solution was stopped, and the pH value adaptability of the dye solution when the addition of the acid solution was stopped).
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 2.1, the color difference grade is 3-4 grade, the dyeing primary success rate is 88%, and the appearance defect score is 12 min/100 m 2 。
As can be seen from comparison of comparative example 2 and example 4, the dyed product of comparative example 2 has a larger color difference and a lower one-time success rate, because the acidic solution is added too late, the temperature is higher, the pH value is higher, the disperse dye is easy to hydrolyze, and the color change of the hydrolyzed dye is more serious, resulting in a larger color difference.
Example 5
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
weak acid dye: acid ash 20353 is manufactured by Jiaxing city Shunfu chemical industry Co., ltd, and the brand is acid ash A-BL;
water;
and (3) dyeing a product: polyamide fiber, talarone 320T;
acidic solution: the concentration is 0.1g/L, the solute is hydrochloric acid, and the solvent is water;
(2) Preparing dye liquor;
the weak acid dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 7 is obtained; wherein the concentration of the weak acid dye in the dye solution is 1.0owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 30 ℃, and then adding a product to be dyed into the dye liquor to soak for 5min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is increased to 50 ℃, stopping adding the acid solution when the temperature is increased to 80 ℃, and preserving the heat for 5min when the temperature is increased to 98 ℃; wherein the heating rate is 20 ℃/min, the ionization degree of carboxyl in the weak acid dye structure is 55% when the acid solution is started, the ionization degree of carboxyl in the weak acid dye structure is 26% when the acid solution is stopped, and the pH value of the dye liquor is 4 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 20 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.2, the color difference grade reaches 4-5 grade, and the appearance defect score is 3 min/100 m 2 The one-time success rate of dyeing is 99.2 percent.
Example 6
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
weak acid dye: acid ash 20442, manufacturer is Suzhou industrial park day time industry and trade company, and the brand is neutral ash 2BL;
water;
and (3) dyeing a product: extinction polyamide fiber, talarone 228T;
acidic solution: the concentration is 20g/L, the solute is a mixture of sulfuric acid and phosphoric acid with the mass ratio of 1:1, and the solvent is water;
(2) Preparing dye liquor;
the weak acid dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 7.5 is obtained; wherein the concentration of the weak acid dye in the dye liquor is 2.2owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 35 ℃, and then adding a product to be dyed into the dye liquor to soak for 16min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 55 ℃, stopping adding the acid solution when the temperature is raised to 85 ℃, and preserving the heat for 40min when the temperature is raised to 98 ℃; wherein the heating rate is 14 ℃/min, the ionization degree of carboxyl in the weak acid dye structure is 58% when the acid solution is started, the ionization degree of carboxyl in the weak acid dye structure is 21% when the acid solution is stopped, and the pH value of the dye liquor is 4.5 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 16 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.3, the color difference grade reaches 4-5 grade, and the appearance defect score is 5 min/100 m 2 The one-time success rate of dyeing is 98.9%.
Example 7
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
weak acid dye: acid blue 20372, manufactured by Shanghai Yayun textile chemical industry Co., ltd, with the brand name of Yagaret blue M-2RN;
water;
and (3) dyeing a product: extinction polyamide fiber, talarone 228T;
Acidic solution: the concentration is 50g/L, the solute is malonic acid, and the solvent is water;
(2) Preparing dye liquor;
the weak acid dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 9 is obtained; wherein the concentration of the weak acid dye in the dye liquor is 15owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 35 ℃, and then adding a product to be dyed into the dye liquor to soak for 24 minutes;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 52 ℃, stopping adding the acid solution when the temperature is raised to 80 ℃, and preserving the heat for 50min when the temperature is raised to 98 ℃; wherein the heating rate is 5 ℃/min, the ionization degree of carboxyl in the weak acid dye structure is 60% when the acid solution is started, the ionization degree of carboxyl in the weak acid dye structure is 27% when the acid solution is stopped, and the pH value of the dye liquor is 5.3 when the acid solution is stopped;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 10 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.4, the color difference grade reaches 4-5 grade, and the appearance defect score is 9 min/100 m 2 The one-time success rate of dyeing is 98.2 percent.
Comparative example 3
A dyeing method for post-adjusting the pH of a dye liquor, substantially as in example 7, except that: in the step (4), the addition of the acidic solution was started when the temperature was raised to 40℃and the degree of ionization of the carboxyl group in the weakly acidic dye structure was 42% when the addition of the acidic solution was started (the addition rate and addition amount of the acidic solution in comparative example 3 were the same as in example 7, the degree of ionization of the carboxyl group in the weakly acidic dye structure when the addition of the acidic solution was stopped and the pH value adaptability of the dye solution when the addition of the acidic solution was stopped).
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 1.6, the color difference grade reaches 4 grade, the dyeing once success rate is 95%, and the appearance defect score is 18 min/100 m 2 。
As can be seen from comparison of comparative example 3 and example 7, the dyeing product of comparative example 3 has larger chromatic aberration, lower dyeing primary success rate and more serious appearance defects, because the acid solution is added too early, the ionization degree of carboxyl in the acid dye structure is lower, the solubility of the dye in water is lower, and aggregation and precipitation are easy to occur, so that the color and color point problem of the cloth cover occurs.
Comparative example 4
A dyeing method for post-adjusting the pH of a dye liquor, substantially as in example 7, except that: in the step (4), the addition of the acidic solution is started when the temperature is raised to 80 ℃, and the ionization degree of the carboxyl group in the weak acid dye structure is 65% when the addition of the acidic solution is started (the addition rate and the addition amount of the acidic solution in comparative example 4 are the same as those in example 7, and the ionization degree of the carboxyl group in the weak acid dye structure when the addition of the acidic solution is stopped and the pH value adaptability of the dye solution when the addition of the acidic solution is stopped) are changed.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 2.0, the color difference grade reaches 3-4 grade, the dyeing primary success rate is 88%, and the appearance defect score is 11 min/100 m 2 。
As is clear from comparative example 4 and example 7, the dyed product of comparative example 4 has a large color difference, a low dyeing primary success rate, and serious appearance defects, because the acid solution is added too late, the temperature is high, the electropositivity of the amino group in the polyamide fiber is weak, the affinity of the acid dye to the fiber is poor, and the dye-uptake is low, so the color difference is large relative to the standard sample.
Example 8
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
weak acid dye: acid orange 20302, manufacturer is Suzhou industrial park day time industry and trade company, and the brand is acid orange RXL;
water;
and (3) dyeing a product: polyamide fiber and nylon spinning 380T;
acidic solution: the concentration is 100g/L, the solute is a mixture of propionic acid and citric acid with the mass ratio of 1:1, and the solvent is water;
(2) Preparing dye liquor;
the weak acid dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 7.8 is obtained; wherein the concentration of the weak acid dye in the dye liquor is 7.2owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 50 ℃, and then adding a product to be dyed into the dye liquor to soak for 30min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 60 ℃, stopping adding the acid solution when the temperature is raised to 90 ℃, and preserving the heat for 90min when the temperature is raised to 98 ℃; wherein the heating rate is 0.1 ℃/min, the ionization degree of carboxyl in the weak acid dye structure is 56% when the acid solution is started to be added, the ionization degree of carboxyl in the weak acid dye structure is 28% when the acid solution is stopped to be added, and the pH value of the dye solution is 6 when the acid solution is stopped to be added;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 1 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 0.3, the color difference grade reaches 4-5 grade, and the appearance defect score is 7 min/100 m 2 The one-time success rate of dyeing is 98.6%.
Example 9
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
neutral dye: neutral ash 20407 manufactured by Zhejiang brand name and new energy stock company, brand name of ash B-NS;
Water;
and (3) dyeing a product: polyamide/spandex blend fabrics, talon (weft elastic);
acidic solution: the concentration is 0.1g/L, the solute is a mixture of hydrochloric acid and phosphoric acid with the mass ratio of 1:1, and the solvent is water;
(2) Preparing dye liquor;
the neutral dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 7.2 is obtained; wherein the concentration of the neutral dye in the dye liquor is 1.3owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 35 ℃, and then adding a product to be dyed into the dye liquor to soak for 10min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 52 ℃, stopping adding the acid solution when the temperature is raised to 80 ℃, and preserving the heat for 10min when the temperature is raised to 98 ℃; wherein the heating rate is 18 ℃/min, the ionization degree of amino groups in the polyamide fiber is 23% when the acid solution is started to be added, the ionization degree of amino groups in the polyamide fiber is 55% when the acid solution is stopped to be added, and the pH value of the dye liquor is 6.2 when the acid solution is stopped to be added;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 16 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The dyeing uniformity of the final dyeing product reaches 4-5 levels, the CIELAB color difference relative to a dyeing standard sample is 0.65, the dyeing one-time success rate is 99.5%, and the appearance defect score is 7 min/100 m 2 。
Example 10
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
neutral dye: neutral ash 20442, manufacturer is Suzhou industrial park day time industry trade company, trade mark is neutral ash 2BL;
water;
and (3) dyeing a product: polyamide fiber and double-layer nylon yarn spinning;
acidic solution: the concentration is 25g/L, the solute is formic acid, and the solvent is water;
(2) Preparing dye liquor;
the neutral dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 8.6 is obtained; wherein the concentration of the neutral dye in the dye liquor is 14.3owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 40 ℃, and then adding a product to be dyed into the dye liquor to soak for 25min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 58 ℃, stopping adding the acid solution when the temperature is raised to 90 ℃, and preserving the heat for 80 minutes when the temperature is raised to 98 ℃; wherein the heating rate is 0.2 ℃/min, the ionization degree of the amino groups in the polyamide fiber is 28% when the acid solution is started to be added, the ionization degree of the amino groups in the polyamide fiber is 65% when the acid solution is stopped to be added, and the pH value of the dye liquor is 6.8 when the acid solution is stopped to be added;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 5 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The dyeing uniformity of the final dyeing product reaches 4-5 levels, the CIELAB color difference relative to a dyeing standard sample is 0.75, the dyeing one-time success rate is 98.1%, and the appearance defect score is 9 min/100 m 2 。
Comparative example 5
A dyeing method for post-adjusting the pH of a dye liquor, substantially as described in example 10, with the only difference that: in step (4), the addition of the acidic solution is started when the temperature is raised to 45 ℃, and the degree of ionization of the amino groups in the polyamide fiber is 45% when the addition of the acidic solution is started (the addition rate and the addition amount of the acidic solution in comparative example 5 are the same as those in example 10, the degree of ionization of the amino groups in the polyamide fiber when the addition of the acidic solution is stopped, and the pH value adaptability of the dye solution when the addition of the acidic solution is stopped).
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 2.3, the color difference grade reaches 3-4 grade, the dyeing one-time success rate is 86.3%, and the appearance defect score is 13.
As is clear from comparison between comparative example 5 and example 10, the dyeing product of comparative example 5 has larger color difference, lower dyeing primary success rate and more serious appearance defects, because the too early addition of the acidic solution leads to larger ionization degree of amino groups in the polyamide fiber structure, and the sulfonylamino groups and methylsulfonyl groups contained in the neutral dye generate larger electrostatic attraction with the polyamide fiber, and because of lower temperature, the neutral dye has higher aggregation degree, and when the neutral dye is adsorbed on the polyamide fiber, uneven dyeing phenomena such as color point color spots appear.
Comparative example 6
A dyeing method for post-adjusting the pH of a dye liquor, substantially as described in example 10, with the only difference that: in step (4), the acidic solution was added when the temperature was raised to 85℃and the degree of ionization of the amino groups in the polyamide fiber at the start of the addition of the acidic solution was 12% (the addition rate and addition amount of the acidic solution in comparative example 6 were the same as in example 10, the degree of ionization of the amino groups in the polyamide fiber at the stop of the addition of the acidic solution and the pH value adaptability of the dye solution at the stop of the addition of the acidic solution were changed).
The CIELAB color difference of the final dyeing product relative to the dyeing standard sample is 1.8, the color difference grade reaches 3-4 grade, the dyeing one-time success rate is 93.2%, and the appearance defect score is 10.
As is clear from the comparison between the comparative example 6 and the example 10, the dyeing product of the comparative example 6 has larger chromatic aberration and lower dyeing success rate at one time, because the acid solution is added too late, the temperature is higher, the electropositivity of the amino group in the polyamide fiber is weak, the affinity of the neutral dye to the fiber is poor, and the dye-uptake is low, so the chromatic aberration is larger than that of the standard sample.
Example 11
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
neutral dye: neutral black 20805, manufacturer is Jining Xingzhou neutralizing dye technology by the limited company, and the brand is acid black LD;
Water;
and (3) dyeing a product: polyamide fiber, nylon spinning 370T;
acidic solution: the concentration is 75g/L, the solute is a mixture of propionic acid and ammonium sulfate with the mass ratio of 1:1, and the solvent is water;
(2) Preparing dye liquor;
uniformly mixing neutral dye and water, and then regulating the pH value (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so as to obtain a dye liquor with the pH value of 8; wherein the concentration of the neutral dye in the dye liquor is 3.9owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 45 ℃, and then adding a product to be dyed into the dye liquor to soak for 30min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 55 ℃, stopping adding the acid solution when the temperature is raised to 82 ℃, and preserving the heat for 60min when the temperature is raised to 98 ℃; wherein the heating rate is 5 ℃/min, the ionization degree of the amino groups in the polyamide fiber is 22% when the acid solution is started to be added, the ionization degree of the amino groups in the polyamide fiber is 59% when the acid solution is stopped to be added, and the pH value of the dye liquor is 6.2 when the acid solution is stopped to be added;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 13 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The dyeing uniformity of the final dyeing product reaches 4-5 levels, the CIELAB color difference relative to a dyeing standard sample is 0.5, the dyeing one-time success rate is 99.1%, and the appearance defect score is 8 min/100 m 2 。
Example 12
The dyeing method for post-regulating the pH value of the dye liquor adopts the device, and comprises the following specific steps:
(1) Preparing raw materials;
neutral dye: neutral red 20319, manufacturer is Huzhou Heji fine chemical Co., ltd, and brand is neutral purplish red W-B;
water;
and (3) dyeing a product: polyamide/spandex blend fabrics and nylon four-sided stretch;
acidic solution: the concentration is 100g/L, the solute is ammonium sulfate, and the solvent is water;
(2) Preparing dye liquor;
the neutral dye and water are uniformly mixed, and then the pH value is regulated (if the pH value of the mixed solution is ideal, the pH value can not be regulated), so that the dye liquor with the pH value of 7.9 is obtained; wherein the concentration of the neutral dye in the dye liquor is 4.1owf%;
(3) Firstly, adjusting the temperature of the dye liquor to 50 ℃, and then adding a product to be dyed into the dye liquor to soak for 25min;
(4) Continuously heating the dye liquor, starting to add the acid solution when the temperature is raised to 53 ℃, stopping adding the acid solution when the temperature is raised to 84 ℃, and preserving the heat for 45min when the temperature is raised to 98 ℃; wherein the heating rate is 15 ℃/min, the ionization degree of amino groups in the polyamide fiber is 27% when the acid solution is started to be added, the ionization degree of amino groups in the polyamide fiber is 56% when the acid solution is stopped to be added, and the pH value of the dye liquor is 6.4 when the acid solution is stopped to be added;
(5) After the heat preservation is finished, the temperature of the dye liquor is reduced to room temperature; wherein the cooling rate is 10 ℃/min;
(6) And after cooling, washing the dyed product sequentially with water, soap and water.
The dyeing uniformity of the final dyeing product reaches 4-5 levels, the CIELAB color difference relative to a dyeing standard sample is 0.55, the dyeing one-time success rate is 99.2%, and the appearance defect score is 8 min/100 m 2 。
Claims (9)
1. The dyeing method for adjusting the pH value of the dye liquor after the dyeing comprises a temperature-rising stage, and is characterized in that the operation of adjusting the pH value of the dye liquor by adding the acid solution is carried out in the temperature-rising stage;
when the acid solution starts to be added, the temperature of the dye solution is T 2 The method comprises the steps of carrying out a first treatment on the surface of the When the addition of the acid solution is stopped, the temperature of the dye liquor is T 3 ，T 3 >T 2 ；
The dye in the dye solution is a disperse dye, when the acid solution is added, the ionization degree of carboxyl of the dispersing agent in the disperse dye is more than 50%, and T2 is 80-100 ℃; when the addition of the acid solution is stopped, the ionization degree of carboxyl groups of the dispersing agent in the disperse dye is less than 30%, and T3 is 110-120 ℃;
or the dye in the dye liquor is weak acid dye, when the acid solution is added, the ionization degree of carboxyl in the weak acid dye structure is more than 50%, and T2 is 50-60 ℃; when the addition of the acid solution is stopped, the ionization degree of carboxyl in the weak acid dye structure is less than 30%, and T3 is 80-90 ℃;
Or the dye in the dye liquor is neutral dye, the product to be dyed is polyamide fiber, polyamide fiber pure textile or polyamide fiber blended textile, when the acid solution is added, the ionization degree of amino in the polyamide fiber is less than 30%, and T2 is 50-60 ℃; when the addition of the acidic solution is stopped, the ionization degree of the amino groups in the polyamide fiber is more than 50 percent, and the T3 is 80-90 ℃.
2. The dyeing method for post-adjusting the pH value of a dye liquor according to claim 1, wherein the concentration of the acidic solution is 0.1-100.0g/L, and the solute in the acidic solution is one or more of organic acid, inorganic acid and strong acid weak alkali salt.
3. The dyeing method for post-adjusting the pH value of a dye liquor according to claim 1, wherein the dyeing is divided into five stages, namely a dyeing starting stage, a heating stage, a heat preservation stage, a cooling stage and a post-treatment stage; the dye liquor temperature at the initial dyeing stage is T 1 ，T 1 <T 2 The pH value of the dye liquor is a, and the time consumption is t 1 The method comprises the steps of carrying out a first treatment on the surface of the The dye liquor heating rate in the heating stage is V 1 The method comprises the steps of carrying out a first treatment on the surface of the When the addition of the acid solution is stopped, the pH value of the dye liquor is b, b<a, a; the temperature of the dye liquor in the heat preservation stage is T 4 ，T 4 ≥T 3 Time-consuming t 2 The method comprises the steps of carrying out a first treatment on the surface of the The dye liquor cooling rate in the cooling stage is V 2 。
4. A dyeing method for post-adjusting the pH of a dye liquor according to claim 3, wherein the dye in the dye liquor is a disperse dye with a dye concentration of 0.1-15.0owf, and the dye liquor contains a leveling agent; the product to be dyed is polyester fiber, polyester fiber pure textile or polyester fiber blended textile; t (T) 1 At 35-60deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 5-6, T 4 Is 120-135 ℃.
5. A dyeing method for post-adjusting the pH of a dye liquor according to claim 3, wherein the dye in the dye liquor is a weak acid dye with a dye concentration of 0.1-15.0owf%; the product to be dyed is polyamide fiber, polyamide fiber pure textile or polyamide fiber mixtureA textile; t (T) 1 30-50deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 4-6, T 4 Is 98 ℃.
6. A dyeing method for post-adjusting the pH of a dye liquor according to claim 3, wherein the dye in the dye liquor is neutral dye with a dye concentration of 0.1-15.0owf%; t (T) 1 30-50deg.C, a is 7-9,V 1 0.1-20deg.C/min, b is 6-7, T 4 Is 98 ℃.
7. A method of dyeing with post-adjustment of the pH of a dye liquor according to claim 3, characterized in that the dye product exhibits a CIELAB color difference relative to the dye standard<0.8, color difference rating of 4-5, appearance defect rating below 10 min/100 m 2 The method comprises the steps of carrying out a first treatment on the surface of the The primary success rate of dyeing is more than 98%, the primary success rate of dyeing = the number of products qualified at one time per the number of total products of dyeing multiplied by 100%, the products qualified at one time of dyeing are the products which meet the requirements in the dyeing process without the operations of adding, repairing and repairing, and the CIELAB color difference relative to the dyeing standard sample is met <0.8, color difference rating of 4-5, appearance defect rating below 10 min/100 m 2 。
8. An apparatus for implementing a dyeing method for post-conditioning the pH of a dye liquor according to any of claims 3-7, comprising an acid material tank, a feed pump, solenoid valves, flow meters, closed dye vats, safety valves, pressure gauges, thermometers and PLC controllers;
the acid material tank is used for storing an acid solution;
the acid material tank, the feed pump, the electromagnetic valve, the flowmeter and the closed dye vat are connected in sequence;
the feeding pump, the safety valve and the acid material tank are connected in sequence;
the flowmeter is used for monitoring the flow true value of the acid solution;
the pressure gauge is connected with the closed dye vat and is used for monitoring the pressure in the closed dye vat;
the thermometer is connected with the closed dye vat and is used for monitoring the temperature in the closed dye vat;
the PLC is connected with the feed pump, the pressure gauge, the thermometer, the electromagnetic valve, the flowmeter and the safety valve simultaneously, and is used for starting the feed pump when the pressure monitored by the pressure gauge reaches 170-370KPa and the temperature monitored by the thermometer reaches T1, and controlling the opening of the electromagnetic valve and the safety valve and the flow rate of the feed pump so as to control the flow rate of the flowmeter within the range of 0.1-25L/min.
9. The apparatus of claim 8, further comprising a shut-off valve and a filter; the stop valve is arranged on a connecting pipeline of the flowmeter and the closed dye vat; the filter is arranged on a connecting pipeline of the acid material tank and the feed pump.
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| CN101906726A (en) * | 2010-08-19 | 2010-12-08 | 中国纺织科学研究院 | Method for dyeing modified polyester |
| CN103774461A (en) * | 2014-01-27 | 2014-05-07 | 青岛雪达集团有限公司 | Method of dyeing acrylic fiber/hair/copper ammonia fiber blended knitting fabric by use of one-bath two-stage process |
| CN109853266A (en) * | 2019-03-05 | 2019-06-07 | 浙江航民股份有限公司 | A kind of production technology of TR fabric stability dispersion dyeing pH value |
| CN112458672A (en) * | 2020-11-20 | 2021-03-09 | 盛虹集团有限公司 | Dipping dyeing equipment capable of maintaining concentration of dye solution stable and dyeing method |
| CN115142277A (en) * | 2022-08-03 | 2022-10-04 | 浙江迎丰科技股份有限公司 | Polyester cotton dispersing activity one-bath dyeing process and dye liquor component thereof |
| CN115469698A (en) * | 2022-09-06 | 2022-12-13 | 浙江新舒纺织有限公司 | Online controllability improvement process for pH value of cheese dyeing |
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