TWI806076B - Dyeing composition of fiber material and its composition dyeing method - Google Patents

Abstract

The present invention is a dyeing composition of a fiber material and a dyeing method of its composition. The fiber material is dyed by using a caffeic acid amide-type surfactant with a specific chemical structure as a fixing agent, including the following dyeing: The composition dyes the fiber material, and the composition comprises: a caffeic acid amide-type surfactant, and based on the total weight of the dyeing composition, the content of the caffeic acid amide type surfactant is 0.001% to 10% by weight; dye, based on the total weight of the dyeing composition, the content of the dye is 0.001% to 10% by weight; and a carrier, based on the total weight of the dyeing composition, the content of the carrier is 80% to 99.998% by weight.

The caffeic acid amide-type surfactant structure of the present invention can enhance the even dyeability of nylon and wool fabrics, and play a better level dyeing effect in the low-temperature dyeing of nylon and wool. When using dyes to dye fiber materials, the biggest problem is uneven dyeing. The present invention uses caffeic acid amide-type surfactants as an auxiliary for dyeing fiber materials, which can promote the dyeing of fiber materials by the dye, regardless of the intensity or leveling of dyeing.

Description

Dyeing composition of fiber material and dyeing method of the composition

The present invention relates to a dyeing composition of fiber material and a dyeing method of the composition. By using caffeic acid amino acid type surfactant as an auxiliary agent to dye fiber material, the color fastness and the color fastness of the dye dyed fiber material can be improved. Level dyeing. The caffeic acid-based surfactant of the present invention can have better compatibility with various types of dyes, surfactants and cosmetic raw materials, and has excellent stability under acidic and alkaline conditions, and is not irritating to the skin. Low toxicity, good biodegradability, and excellent wettability. In addition, as a surfactant, it can effectively reduce the surface tension. The caffeic acid-based surfactant structure of the present invention can enhance the level dyeing of polyamide fibers such as wool and nylon, and play a better leveling effect in the dyeing of polyamide fibers such as wool and nylon .

Acid dyes are generally used for nylon and wool dyeing, and dyeing and finishing auxiliaries for nylon and wool dyeing are developed to (1) increase the solubility of insoluble dyes, increase the solubility of dyes, and thus improve the dispersibility of dyes in water, so that the dyed Fabric unevenness has been improved. In addition, due to the increase in solubility, it is not necessary to add additional dispersants during the preparation of commercial dyeing, and surfactants can be directly added during dyeing without adding other auxiliaries. (2) To improve the level dyeing property, the main force formed between the surfactant and the dye is the van der Waals force. When the external force is greater than this force, the dye molecules will be evenly dyed. Therefore, when using surfactants for dyeing, during the dyeing process, as the environment of the dye solution changes, the auxiliary molecules are slowly released, thereby reducing the initial dyeing rate of the dye, which is conducive to level dyeing. With the increase of dye bath temperature and dyeing time, it will not affect the amount of dye uptake. (3) Increase the amount of dye uptake and reduce the amount of dye in dyeing wastewater. When adding a surfactant for dyeing, the dye is adsorbed to the surface of the fiber in molecular form, and the amount of unfixed dye in the dye bath is reduced, Therefore, the amount of dye uptake can be increased, the amount of residual dye in dyeing wastewater can be reduced, the utilization rate of dyestuffs can be improved, and the difficulty of dyeing wastewater treatment can be reduced, which is very beneficial from ecological and economical considerations.

In recent years, due to the rapid development of industry, there have been two serious problems affecting human existence, one is the energy crisis and the other is environmental pollution. The energy crisis is mainly caused by the massive consumption of petroleum, and the products used by human beings are overly dependent on petroleum raw materials, resulting in a shortage of petroleum energy, and because many products that use petroleum as raw materials are not easy to decompose naturally. A large amount of waste has caused serious environmental pollution on the earth. In order to reduce this phenomenon, the treatment technology of pollutants, the engineering technology of reducing the generation of pollutants and the development of decomposable raw materials have been paid much attention.

Color fixing agent is a kind of surfactant, which can improve the color fastness of dyed and finished fabrics, enhance the washing resistance and friction resistance of fabrics, and can improve the retention rate of dyes on dyed fabrics.

Decomposable surfactants are also known as temporary surfactants or surfactants with controlled half-life (surfactants with controlled half-live). A class of surfactants that can be decomposed into non-surface active substances or transformed into new surface active compounds under the action of heat or light. Such surfactant molecules often contain a weak bond with limited stability between the polar end and the hydrophobic chain. The cleavage of the weak bond will directly destroy the interfacial activity of the molecule, which is commonly referred to as the primary decomposition of the surfactant. According to the different decomposable functional groups, decomposable surfactants can generally be divided into two categories: acetal type and ketal type. Compared with general surfactants, decomposable surfactants have a better concept of environmental protection, and this kind of surfactants can eliminate some complicated situations. In recent years, people's understanding of decomposable surfactants has been continuously deepened and developed. The size of the impact on the environment and the speed of biodegradability have gradually become a very important indicator for judging the quality of surfactants.

Under the trend of global stable development, surfactants provide an excellent environment for the development of related industries, and the requirements for product structure, items, performance and technology are getting higher and higher. Therefore, the development of safe, mild, natural, biodegradable and special surfactants, It provides a good foundation for the development and application of new products.

The purpose of the present invention is to use natural plant caffeic acid as raw material and modify it into a green and environment-friendly caffeic acid amide type surfactant, in addition to the surface activity of reducing surface tension, good wettability, and emulsification and dispersion In addition to the effect, it has low toxicity, biodegradability, and is harmless to the human body. One of the important indicators for evaluating the dyeing performance of dyes is the dyeing depth. Generally, pH 4~6 is used during dyeing. The stronger the acidity, the faster the dyeing will be, but it is easy to produce stains. The caffeic acid amide type interface of the present invention The active agent structure can enhance the level dyeing of wool and nylon fabrics, and play a better level dyeing effect in dyeing. Using the caffeic acid amide type surfactant of the present invention can enhance level dyeing property, dyeing rate and color fixing performance. Acid dyes are used to dye wool and nylon fabrics, mainly using weak acid to neutral dyeing methods. When dyeing, as the temperature rises, the amount of dyeing will also increase, so the factor affecting the dyeing rate is not only pH value, but also temperature is an important factor, so the temperature should be controlled during dyeing. Acid dyes dyed in weakly acidic baths generally have higher affinity to polyamide fibers and poor leveling properties, so surfactants are often used as leveling agents. Dyeing wool and nylon fibers with acid dyes can effectively improve their wet rubbing fastness. The dyes are soluble in water and have a small molecular weight. They have affinity for polyamide fibers such as wool and nylon, but have little affinity for ordinary fibers. The present invention uses caffeic acid amide type surfactant as auxiliary agent for dyeing of fiber materials, the dyeing speed is affected by the complex formed by the dye and surfactant in the dyeing solution, and the molecules of the surfactant are first adsorbed during dyeing. The dye molecules make the dye molecules bigger, and the dyeing speed between the dye molecules and the fibers slows down, so as to achieve the level dyeing effect. In the later stage of dyeing, the dyeing speed must be accelerated, the dye residue should be reduced, and the desired hue concentration can be achieved. In order to avoid uneven dyeing of the fiber material, the caffeic acid amide type surfactant of the present invention is added here to increase its excellent dyeing effect.

The dyeing composition containing the caffeic acid-based surfactant of the present invention not only conforms to the concept of green and environmental protection, but also has excellent color fixing effect in the dyeing of pigments, especially in polyamides such as wool and nylon. Fiber dyeing.

The present invention is a dyeing composition of fiber material and the dyeing method of the composition The method comprises dyeing the fiber material by using the following dyeing composition, which contains a caffeic acid amide type surfactant with a specific structure, a dyestuff, and a carrier. Among them, the caffeic acid amide type surfactant is used as a dyeing and finishing auxiliary agent, and the caffeic acid amide type surfactant contains an ester group structure, which has a certain solubilizing effect on the wool scale layer, which is beneficial to the dye ion like fiber Internal diffusion and penetration. The present invention uses caffeic acid-based surfactants as auxiliary agents to dye wool and nylon fibers. It is found that the dyeing properties of the dyes on fiber materials can be improved, and the dyeing rate and level dyeing property are quite excellent.

The dyestuff described in the present invention is selected from: acid dyes, vegetable pigment dyes, and the vegetable dyes are selected from: dragon fruit, purple cabbage, madder, turmeric, henna, comfrey, safflower, indigo, pomegranate, sumac, Sophora japonica, potato nut, betel nut, roselle, scutellaria baicalensis and other plant pigments and dyes.

The fiber material of the present invention is selected from polyamide fiber materials such as nylon, wool, fox fur, camel hair, feather, rabbit hair, etc.

The present invention relates to a dyeing composition for fiber materials and a method for dyeing the composition, including dyeing fiber materials with the following dyeing composition, the dyeing composition includes caffeic acid amino acid type surfactant with a specific structure , dyes, carriers. Based on the total weight of the dyeing composition, the content of the caffeic acid-based surfactant is 0.001% by weight to 10% by weight; the content of the dye is 0.001% by weight to 10% by weight; the content of the carrier is 80% by weight to 99.998% by weight. The dyeing composition of the present invention utilizes the caffeic acid amide type surfactant as a dyeing auxiliary agent to help the fiber dyeing during the dyeing process.

The caffeic acid amino acid type surfactant of the present invention has the structure of general formula (I), the preparation of this caffeamide amino acid type surfactant, with polyethylene glycol, amido acid salt, Dihydrocaffeic acid is the main raw material, and the synthesis includes step (a) acidification of amide acid salt, which is to convert amide acid salt into Inorganic acid is acidified into amidodiacid compound; and the synthesis of step (b) caffeic acid amido acid type surfactant is that dihydrocaffeic acid and amidodiacid compound are polymerized by different EO chain lengths. Ethylene glycol chains to synthesize a series of caffeic acid-based surfactants. Polyethylene glycol (different EO chains: PEG200, PEG400, PEG600, PEG1000) is used as a hydrophilic segment to finally synthesize caffeic acid-based surfactants, whose structure contains hydrophilic and hydrophobic groups. Dispersed or emulsified in aqueous solution, it has the advantages of non-toxic, non-polluting, biodegradable and good biocompatibility, making it more widely applicable in industry. The present invention utilizes caffeic acid amino acid type surfactant as auxiliary agent for fiber material dyeing, and the structure of caffeic acid amino acid type surfactant diffuses and penetrates inside polyamide fibers such as wool and nylon, and finds that The dyeing effect is very good, regardless of the dyeing rate or level dyeing property, especially for nylon fibers, it has excellent industrial applicability and market substitution.

A dyeing composition of fiber material and the dyeing method of the composition, including dyeing the fiber material by using the following dyeing composition, the composition includes a caffeic acid amide type surfactant with a specific structure, a dye, a carrier agent. The dyeing composition comprises: caffeic acid amino acid type surfactant, based on the total weight of the dyeing composition, the content of the caffeyl amino acid type surfactant is 0.001% by weight to 10% by weight %; dye, based on the total weight of the dyeing composition, the content of the dye is 0.001% by weight to 10% by weight; and carrier, based on the total weight of the dyeing composition, the content of the carrier It is 80% by weight to 99.998% by weight, wherein, the caffeamide type surfactant has the chemical structure of the following general formula (I):

n: the number of repeating units of polyethylene glycol, the value is 2~10000

y: The number of repetitions of the -CH ₂ - segment next to the longer-chain acid group in the amidodiacid compound, and its value is an integer from 1 to 30

R: A long-chain saturated or unsaturated hydrocarbon organic group with a carbon chain number of 6-30.

The dyeing composition of the fiber material of the present invention, wherein the caffeic acid amide acid type surfactant is polyethylene glycol, amide acid salt, dihydrocaffeic acid as the main raw material, and the synthesis includes step (a) amide Acidification of amino acid hydrochloride is to acidify amido acid salt with inorganic acid into amidodiacid compound; and step (b) synthesis of caffeic acid amido acid type surfactant is to combine dihydrocaffeic acid and acyl Amino diacid compounds are linked by polyethylene glycol chains with different EO chain lengths to synthesize a series of caffeic acid amino acid-type surfactants. Because of their special chemical structure, they are easily adsorbed at very low concentrations. On the surface or interface of the solution, and then change the free energy of the surface or interface of the solution to reduce the surface tension and produce characteristics such as wetting, penetration, foam, emulsification, dispersion and melting.

The dyeing composition of the fiber material of the present invention, wherein, said caffeic acid amido acid type surfactant is to take polyethylene glycol, amido acid salt, dihydrocaffeic acid as main raw material, synthesis comprises step (a ) Acidification of amido acid salt is acidification of amido acid salt with inorganic acid into amidodiacid compound; Acid and amidodiacid compounds are linked by polyethylene glycol chains of different EO chain lengths to synthesize a series of caffeamide acid-type surfactants, which have good biodegradability and will not pollute the environment , and a water-soluble caffeic acid-based surfactant with excellent properties. Caffeic acid amino acid of the present invention Type surfactant, with excellent chemical stability and low skin irritation, can have better compatibility with various types of dyes, surfactants and cosmetic raw materials, and has excellent stability under acidic and alkaline conditions , low skin irritation, good biodegradability, and excellent wettability, combining the advantages of these two materials. The caffeic acid-based surfactant of the present invention has excellent dispersing and emulsifying ability, wetting and lubricating, and improving the luster and texture, and at the same time has the characteristics of biodegradable, natural and environmental protection, and can be applied to textile dyeing The whole industry is an excellent dyeing and finishing auxiliary agent. After the fabric is dyed and fixed in the presence of the caffeic acid-type surfactant auxiliary agent of the present invention, it has no harm to the skin and is suitable for dyeing and finishing. The waste water after use can be decomposed by microorganisms and is non-polluting to the environment. The dyeing method of fiber material of the present invention is to utilize caffeic acid amide type surfactant as the auxiliary agent of fiber material dyeing, and the speed of dyeing is affected by the complex that dyestuff and surfactant form in the dyeing liquor, when dyeing Surfactant molecules first adsorb dye molecules, making the dye molecules larger, slowing down the dyeing rate of dye molecules and fibers, and achieving a level dyeing effect, which solves the problem of uneven dyeing when dyeing wool and nylon fabrics with dyes.

式中，n表示聚乙二醇重複單位數，其值為2~10000；y表示醯胺基二酸化合物中緊鄰較長鏈酸基之-CH₂-段之重複數量，其值為1~30之整數；R為碳鏈數6~30之長鏈飽和或不飽和碳氫有機基團。 The dyeing composition of the fiber material of the present invention, wherein, the preparation of the caffeic acid amino acid type surfactant is made of biodegradable, non-toxic to human body polyethylene glycol, amido acid salt, diacetate Hydrocaffeic acid is the main raw material, and the synthesis includes step (a) acidification of amido acid hydrochloride, which is to acidify amido acid salt with inorganic acid into amidodiacid compound; and step (b) caffeamide acid The synthesis of caffeic acid-based surfactants is to synthesize a series of natural and environmentally friendly caffeic acid-based surfactants by linking dihydrocaffeic acid and amidodiacid compounds through polyethylene glycol chains of different EO chain lengths. . The caffeic acid amino acid type surfactant of the present invention has the structure of general formula (I), as shown below

In the formula, n represents the number of repeating units of polyethylene glycol, and its value is 2 to 10000; y represents the repeating number of the -CH ₂ - segment next to the longer chain acid group in the amido diacid compound, and its value is 1 to 10000. An integer of 30; R is a long-chain saturated or unsaturated hydrocarbon organic group with 6 to 30 carbon chains.

Preparation of the caffeic acid-type surfactant described in the dyeing method of the present invention

Comprising the following synthetic steps (a) to (b):

(a) acidification of amide acid hydrochloride

Acidifying the amido acid salt with a mineral acid into an amidodiacid compound;

(b) Synthesis of caffeic acid-type surfactant

The dihydrocaffeic acid and amidodiacid compounds are linked by polyethylene glycols of different chain lengths (different EO chains: PEG200, PEG400, PEG600, PEG1000) to synthesize a series of caffeic acid amido acid types Surfactant.

The preparation method of the caffeamide acid-type surfactant of the present invention, the step (a) acidifies the amido acid salt with an inorganic acid into an amidodiacid compound, wherein the concentration of the inorganic acid is 0.1-3M.

The preparation method of the caffeic acid amido acid type surfactant of the present invention, wherein, step (b) is to place the polyethylene glycol of different chain length, dihydrocaffeic acid, and amido diacid compound in reaction bottle , add a catalyst, and react at a temperature of 80-180°C for 4-10 hours to obtain a series of polymers Ethylene glycol-modified caffeic acid-type surfactant product.

In the caffeic acid-based surfactant of the present invention, different EO chains are changed: PEG200, PEG400, PEG600, and PEG1000 are used as the hydrophilic segment. The product codes are PEG200, PEG400, PEG600, PEG1000 respectively.

The preparation method of caffeic acid amino acid type surfactant of the present invention, wherein, the catalyst of step (b) is selected from: 4-2 methylaminopyridine (DMAP), titanium isopropoxide (titanium isopropoxide), sulfuric acid ( Sulfuric acid), hydrochloric acid (Hydrochloric acid) at least one.

The synthesis reaction formula of the caffeic acid amino acid type surfactant of the present invention is as follows: Wherein the amido acid salt compound is example with sodium lauryl glutamate, polyethylene glycol (change different EO chains: PEG200, PEG400, PEG600, PEG1000) as the hydrophilic segment.

本發明所合成為一系列咖啡酸醯胺基酸型界面活性劑。代號分別為PEG200、PEG400、PEG600、PEG1000。

The present invention synthesizes a series of caffeic acid amino acid type surfactants. The code names are PEG200, PEG400, PEG600 and PEG1000 respectively.

The dyeing method of the fiber material of the present invention utilizes the synthesized caffeic acid amino acid type surfactant as auxiliary agent and dyestuff to dye the fiber material, because of the structure of the caffeyl amino acid type surfactant, it is found that the dyeing The effect is very good, regardless of dyeing rate or level dyeing, especially for nylon fibers, to get deep dyeing and uniform effect.

In the present invention, a series of synthesized caffeic acid-type surfactants are interacted with acid dyes CIAcid Red 114 and CIAcid Yellow 42, and the absorbance of the maximum absorption wavelength (λ _max ) is measured by an ultraviolet spectrometer , fix the acid dye concentration, change the concentration of the product, and get the interaction between the dye and the auxiliaries.

According to the dyeing method of the fiber material of the present invention, the dyeing composition is used to dye the fiber material in the embodiment, including the following steps. In the exhaust dyeing step, the fiber material is immersed in the dyeing composition at room temperature. In the slow dyeing step, the dyeing composition and the fiber material soaked in it are heated to 50°C to 110°C at a heating rate of 0.5°C/min to 5°C/min. In the dyeing step, the temperature of the dyed composition and the fiber material soaked therein is kept at 50° C. to 110° C. for 20 minutes to 90 minutes. In the step of cooling out of the vat, the dyeing composition and the fiber material soaked in it are lowered to 40°C to 80°C at a cooling rate of 0.5°C/min~5°C/min, and then the fiber material is taken out of the dyeing composition.

The dyeing method of the fiber material of the present invention comprises the following steps: providing the fiber material and providing a dyeing composition, wherein based on the total weight of the dyeing composition, the dyeing composition contains caffeamide at a content of 0.001% by weight to 10% by weight An acid-based surfactant, a dye with a content of 0.001% to 10% by weight, and a carrier with a content of 80% to 99.998% by weight. The fiber material is dyed with the dyeing composition.

In an embodiment of the present invention, the dye can be adsorbed on the surface of the fiber material through the dyeing process through molecular force (such as hydrogen bond or van der Waals force).

Based on the total weight of the dyeing composition, the content of the dye is 0.001% to 10% by weight, and preferably 0.01% to 5% by weight. In addition, the content of the dye can be adjusted according to the actual dyeing conditions. When the content of the dye is less than 0.001% by weight, the fiber material cannot be effectively dyed to the desired color; and when the content of the dye is greater than 10% by weight, excess dye may remain on the fiber material. material, which in turn causes the problem of waste of dyestuffs.

In the embodiment of the present invention, the function of the carrier is to provide an environment in which the dye and the caffeic acid-type surfactant in the dyeing composition can be mixed and/or aggregated arbitrarily. The carrier is, for example, water, ethanol, acetone or a mixed solution thereof. Based on the total weight of the dyeing composition, the content of the carrier is 80% by weight to 99.998% by weight.

In addition, in the embodiment of the present invention, the dyeing composition may further include a pH adjusting agent for adjusting the pH of the dyeing composition. At room temperature, the pH of the dyeing composition can be, for example, 2-6, and the pH adjusting agent is, for example, glacial acetic acid, formic acid, phosphoric acid or hydrochloric acid. When the pH value of the dyeing composition is in the above range, it will be able to affect the charging of the fiber material, and also improve the degree of dye dispersion and the speed of its combination with the fiber material.

In the dyeing composition according to the embodiment of the dyeing method of the fiber material of the present invention, the content of the caffeic acid-type surfactant is, for example, 0.01% to 5% by weight based on the total weight of the dyeing composition.

In the dyeing composition according to an embodiment of the present invention, based on the total weight of the dyeing composition, the content of the dye is, for example, 0.01% by weight to 5% by weight.

In the dyeing composition according to an embodiment of the present invention, the pH value of the dyeing composition at room temperature is, for example, 2-6.

Based on the above, it can be seen that since the dyeing composition contains caffeic acid amino acid type surfactant, when the dyeing composition is used to dye the fiber material, the dyeing composition can have a good dye uptake rate to the fiber material and level dyeing, so as to achieve the effect of deep dyeing and easy dyeing of fiber materials, especially fiber materials, which also makes The dyed fiber material has good washing fastness and light fastness.

In the dyeing method provided in this embodiment, the fiber material and the dyeing composition described in the above embodiments are firstly provided, and then the fiber material is dyed by using the dyeing composition. In the dyeing procedure, the liquor ratio of the fiber material to the dyeing composition is, for example, about 1:40. For example, if it is desired to dye a fiber material with a weight of 2.5 grams, it can be soaked in a dyeing composition with a weight of 100 grams.

When using the dyeing composition of the present invention to dye fiber materials, it may include exhaust dyeing steps, slow dyeing steps, dyeing steps and cooling out of vats. Each step will be described in detail below.

In an embodiment of the present invention, the exhaust dyeing step is, for example, dipping the fiber material into the dyeing composition at room temperature. After the exhaust dyeing step, a slow dyeing step is performed. In the slow dyeing step, for example, the dyeing composition and the fiber material soaked therein are heated to 50° C. to 110° C. at a heating rate of 0.5° C./min to 5° C./min. In the exhaust dyeing step and slow dyeing step, the dyestuff in the dyeing composition can be preliminarily adsorbed on the surface of the fiber material, and then the fiber material is dyed into a color corresponding to the dyestuff.

After the exhaust dyeing step and slow dyeing step, a dyeing step is performed. The dyeing step is, for example, maintaining the temperature of the dyed composition and the fiber material soaked therein at 50° C. to 110° C. for 20 minutes to 90 minutes. In the above-mentioned exhaust dyeing step, slow dyeing step and dyeing step, since the dyeing composition of the present invention contains a caffeic acid amino acid type surfactant, at a temperature of 50° C. to 110° C., the dyeing composition has no effect on the fiber material. That is, it has good dye uptake and level dyeing, so that the dyed fiber material has good washing fastness and light fastness.

After the dyeing step, the step of cooling out of the cylinder is carried out. The step of cooling out of the vat, for example, is to lower the temperature of the dyeing composition and the fiber material soaked in it to about 40°C~80°C at a cooling rate of 0.5°C/min~5°C/min, and then take the fiber material out of the dyeing composition . In addition, after the step of cooling down and leaving the vat, the dyed fiber material can be washed, dehydrated and naturally air-dried.

Based on the above-mentioned dyeing results, listed in Tables 1 to 11, it can be seen that in the dyeing method of the present invention, due to the use of dyeing compositions containing caffeic acid-based surfactants to carry out plant-based natural pigments or acid dyes on fiber materials Therefore, the dyed fiber material has good dyeing rate and level dyeing property.

Hereinafter, the features of the present invention will be described more specifically with reference to experimental examples and comparative examples. Although the following experiments are described, materials used, their amounts and ratios, details of treatments, procedures of treatments, and the like can be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be limitedly interpreted by the experiments described below.

Preparation and property determination of caffeic acid amino acid type surfactant of the present invention

Materials used:

(1) Dihydrocaffeic acid

(2) Sodium lauryl glutamate

(3) Hydrochloric acid (Hydrochloric acid)

HCL

(4) Polyethylene glycol (different EO chains: PEG200, PEG400, PEG600, PEG1000)

(5) 4-Dimethylaminopyridine (DMAP, 4-dimethylaminopyridine)

(6) Dye

(a) Caffeine

(b) Curcumin

The synthesis of caffeic acid amino acid type surfactant of the present invention, is to comprise (a) to (b) synthetic steps are as follows:

(a) acidification of amide acid hydrochloride

Add 30mole of sodium lauryl glutamate (amic acid salt) to 30mole of 1M dilute hydrochloric acid to make Sodium cinnamic glutamate hydrochloride was acidified, and after drying in a hot air circulation oven, product A was obtained.

(b) Synthesis of caffeic acid-type surfactant

Put 30 moles of polyethylene glycol (changes in different polyoxyethylene (EO) chains: PEG200, PEG400, PEG600, PEG1000), 30 moles of dihydrocaffeic acid and 30 moles of lauryl glutamic acid in a magnetic stirring and temperature control bar In the four-necked reaction flask, 4-dimethylaminopyridine (DMAP) was used as a catalyst and reacted at a temperature of 130° C. for 6 hours to obtain a series of polyethylene glycol-modified caffeic acid-type surfactant products B.

The caffeic acid amido acid type surfactant product of the present invention, take polyethylene glycol (change different EO chain: PEG200, PEG400, PEG600, PEG1000), dihydrocaffeic acid, amido acid salt as main raw material, synthesis Including step (a) acidification of amido acid salt, which is to acidify amido acid salt into amido diacid compound with inorganic acid; and step (b) synthesis of caffeic acid amido acid type surfactant, which is Dihydrocaffeic acid and amidodiacid compounds are linked by polyethylene glycol with different EO chain lengths to synthesize a series of caffeamide-type surfactants and obtain a series of caffeamide-type surfactants. Surfactant. The product codes are PEG200, PEG400, PEG600, PEG1000 respectively.

Pigment dye of the present invention also comprises natural plant pigment dye except general acidic direct dye, such as coffee pigment, curcumin, dragon fruit pigment, wherein, the preparation of plant natural pigment dye, for example, utilizing dragon fruit fruit juice machine Extraction of vegetable and fruit liquid by means of extraction, because dragon fruit has residual impurities after extraction, it must be filtered through an air suction filter to obtain the plant-based natural pigment we need. Purple cabbage extracts the vegetable and fruit liquid by using a juice machine or boiling water. Because purple cabbage has residual impurities after extraction, it must be filtered through an air suction filter to obtain the plant-based natural pigments we need.

The main component of wool fiber is keratin, which is composed of a variety of α-amino acid residues, which can be linked into long-chain helical molecules, which contain carboxyl groups, amine groups and hydroxyl groups, etc., forming salt bonds and hydrogen between molecules. keys etc. The long chains are linked by cross bonds formed by cystine disulfide bonds. Plant-based natural pigment dyes are mostly acid dyes. The chemical structure of acid dyes usually contains -OH groups, -COOH groups, and -SO ₃ H groups. They can dye wool or nylon fibers in acidic, weakly acidic or neutral dye baths.

The acidic groups in plant-based natural pigment dyes are mostly -OH groups, -SO ₃ H groups, and -COOH groups. These groups are easily soluble in water, and they dissociate into dye cations in water, which are anionic and require the help of acids. It can be dyed by ionic bonding. The dyeing operation is simple, the color is bright, and the washing fastness is medium.

Dyeing test, one of the important indicators for evaluating the dyeing performance of dyes is the dyeing depth. The Kubelka-Munk dyeing depth equation establishes a certain functional relationship between the absorption coefficient K and scattering coefficient S of the measured object and the concentration C of the colored substance in the solid sample. The larger the calculated K/S value, the darker the surface color of the solid sample, that is, the higher the concentration of colored substances, the better the dyeing performance of the dye. Surfactants can act as wetting agents, leveling agents, solubilizers, and precipitation preventive agents. Therefore, the interaction between dyes and surfactants is very important in many dyeing processes, such as fabric dyeing and photo printing. , inkjet technology and other processes.

Level dyeing, CIB LAB is based on the theory that a color cannot be both green and red at the same time, nor can it be both blue and yellow at the same time. Therefore, a single value can be used to describe red/green, yellow/blue characteristics. The CIB LAB tolerance formula centers on the standard, and then gives individual L*a*b* values, plus or minus (+/-) error ranges.

△L*=L*sample-L*standard (brightness difference, + shallower)

△a*=a*sample-a*standard (+ redder, - greener)

△b*=b*sample-b*standard (+ yellowish, - blue)

The experiment of the present invention uses natural vegetable acid dyes (coffee pigment, curcumin), and adjusts the pH to 4.5 with acetic acid, so that Van der Waals force and hydrogen bonds can interact in a weakly acidic environment to obtain better coloring rate and The degree of color is high, but acid dyes dye wool and nylon fibers, and it is not easy to level dye, so the caffeic acid amide acid type surfactant of the present invention is used to increase the level dyeing and dyeing rate.

In the dyeing method of the fiber material of the present invention, the dye concentration of 1% o.w.f (1 gram is diluted to 80 grams with a carrier to form a mass percentage of 1%, that is, the dye used accounts for 1% of the total dye solution) and auxiliary agents are prepared respectively (Caffeic acid amino acid type surfactant) a dyeing composition composed of a concentration of 0.05wt% (mass percentage) and a carrier (water), used to dye nylon fiber cloth, and then proofing by Ruby dyeing Machine, spectrophotometer and other instruments are used to analyze various related properties, and to explore the effect of adding dyes or auxiliaries on the dyeing of nylon fabrics.

Dyeability: When using dyes to dye wool and nylon fabrics, the biggest problem is uneven dyeing, so it is necessary to use a leveling agent to achieve the leveling effect. The dyeing speed is affected by the complex formed by the dye and the surfactant in the dyeing solution. When dyeing, the surfactant molecule first adsorbs the dye molecule to make the dye molecule larger, and the dyeing speed of the dye molecule and the fiber slows down to achieve uniform dyeing. dye effect. In the later stage of dyeing, the dyeing speed must be accelerated, the dye residue should be reduced, and the desired hue concentration can be achieved. Use the computer dyeing machine (Drum Dyeing Testing Matching) to dye, and then use the computer color matching system (Color Matching System, CS-5) to test.

Experimental Drugs and Materials

nylon fabric

Acetic Acid, Glacial CH ₃ COOH, molecular weight 60.05, grade 1 reagent, purchased from Japan Pharmaceutical Co., Ltd.

Auxiliary agent: caffeic acid amino acid type surfactant

Dyes: coffee pigment, curcumin

Experimental procedure

1. Weigh 2 grams of nylon fiber cloth

2. Prepare dyeing composition 100ml

A. The concentration of the prepared dyes is: 1% o.w.f (mass percentage, the dye used accounts for 1% of the total dye solution).

B, preparation concentration is the auxiliary agent of 0.05% (mass percentage), and auxiliary agent is selected from: the caffeic acid amide type surfactant of different EO chain length.

C. Adjust pH to 4.5 with acetic acid, liquor ratio: 1:40

3. Dip dyeing step, respectively put the fiber material and the dyeing composition into steel cylinders at room temperature.

4. In the slow dyeing step, the dyeing composition and the fiber material soaked in it are heated to 70, 80°C at a heating rate of 1°C/min under the dyeing conditions of the RUBI dyeing proofer.

5. In the dyeing step, keep the dyed composition and the fiber material soaked in it at 70, 80°C for 30 minutes.

6. In the step of cooling out of the vat, the dyeing composition and the fiber material soaked in it are lowered to 50°C at a cooling rate of 1°C/min, and then the fiber material is taken out of the vat from the dyeing composition.

7. Wash and dry in the shade

8. Dyeing

The dyeing bath formula was prepared according to the dyeing conditions. No additives were added to the cylinder of the first tank, and different additives synthesized were added to the cylinders of the other tanks. Put the fiber fabric into the steel bottle, fasten the bottle cap, set the initial temperature at 50°C, and increase it by 1°C every minute. When the temperature reaches 70°C, put the steel cylinders on the cylinder holder of the computer dyeing machine. After 5 minutes, take out one of the steel cylinders, wash the fabric in the cylinder fully, and then dry it naturally. At 70 and 80°C, take out the rest of the cylinders, wash them with water and dry them naturally. With the computer color matching system (Applied Color System), make it in a stable state, first perform a calibration test, and then officially enter the test.

Staining strength and evaluation results

When the dyeing and finishing industry uses dyes for dyeing, it is necessary to add dye guides to the dye solution to make the dyes easily enter the fiber and achieve the purpose of deep dyeing and less residual liquid. The dye-introducing agent must have good dispersibility, so as to help the dye to diffuse into the fiber, prevent dye agglomeration, not inhibit final dyeing, and have moderate retardation and level dyeing properties. In addition, it is also required that the foaming property is small and has no effect on the color fastness. One of the important indicators for evaluating the dyeing performance of dyes is the dyeing depth. The Kubelka-Munk staining depth equation establishes a certain functional relationship between the absorption coefficient K and scattering coefficient S of the measured object and the concentration C of the colored substance in the solid sample. The larger the calculated K/S value, the darker the surface color of the solid sample, that is, the higher the concentration of colored substances, the better the dyeing performance of the dye.

Use the dyeing composition containing caffeic acid amino acid type surfactant of the present invention, carry out the test of the dyeing property after nylon fiber cloth dyeing is as follows:

Spectrophotometric analysis

Use the Gretag Macbeth Color-Eye 2180UV/2180 spectrophotometric colorimeter, the nylon fiber cloth after dyeing with comparative example (do not add the auxiliary agent of caffeic acid amide type surfactant of the present invention) as standard Samples, respectively evaluate the composition of each dye in the experimental example The dyeing strength and color difference of the dyed nylon fiber cloth obtained from the obtained product are recorded in Tables 1 to 4, and 5 to 6.

Shading Strength is calculated according to the Kubelka-Munk Theory. In the following Tables 1 to 4 and Tables 5 to 6, the coloring strength of the comparative example (standard sample) will be set to 100.0.

For the caffeic acid-based surfactant of the present invention with an added amount of 0.05%, the analysis results of the color difference of the coloring strength are shown in Table 1~Table 4, Table 5~Table 6, for changing different EO chains: PEG200, PEG400, PEG600, PEG1000 reaction synthesis obtained a series of natural caffeic acid amino acid type surfactants as auxiliary agents and dyeing at different temperatures, the results showed that the dye dispersibility was due to the addition of caffeic acid amino acid type surfactants, and its dispersibility The better, since the caffeic acid-based surfactant can partially dissolve the agglomerated dye, the dye is less likely to agglomerate, that is, it has better dispersibility for the dye.

Tables 1 to 2 show the dyeability of natural coffee pigments on nylon fabrics at 70°C and 80°C, and Table 1 shows the dyeability of nylon fabrics at 70°C, using natural coffee pigments and a series of caffeic acids of the present invention The dyeing color difference △E result of the amide acid-type surfactant as an auxiliary agent (fixing agent), the color difference test results show that its level of dyeing is better. The product code PEG400 has the highest K/S value, and the dyeing effect is better than other products with EO chain length. A series of caffeic acid-based surfactant products synthesized by the present invention are used as auxiliary agents at 70°C. The K/S value of dyed nylon fabric is larger than the K/S value of using commercially available anionic and nonionic surfactants, indicating that the dyeing effect of using the surfactant of the present invention as an auxiliary agent is better than that of commercially available surfactant auxiliary agents. It is the best, and the dyeing effect of the product code PEG400 is the best.

Table 2 Dyeability on nylon fabric at 80°C, using natural coffee pigment and Using a series of caffeic acid-based surfactants of the present invention as the dyeing color difference results of auxiliary agents (color fixing agents), the color difference ΔE value of the product code PEG400 is smaller than other products at 80 ° C, showing uniformity. The dyeing effect is better. The product code PEG400 has the highest K/S value, which shows that its dyeing effect is better than other products with EO chain length. When a series of caffeic acid-type surfactants are synthesized as auxiliary agents, when dyeing at 80 ° C The K/S value of K/S value is larger than the K/S value of commercially available anionic and nonionic surfactant auxiliary agents, which means that the dyeing effect of the auxiliary agent of the present invention is better than that of other commercially available auxiliary agents, among which the product code PEG400 Dyeing works best.

Table 3 Dyeability on nylon fabrics at 70°C, dyeing color difference results using natural curcumin and a series of caffeic acid-based surfactants of the present invention as auxiliary agents (color fixing agents), in color difference The test results show that its level dyeing degree is better, and the color difference ΔE value of the product coded PEG200 at 70°C is smaller than that of other EO chain lengths, which shows that its level dyeing effect is better. Comparing different EO chain lengths, the product code PEG1000 has the highest K/S value as an auxiliary agent, showing that its dyeing effect is better than other products with EO chain lengths. A series of caffeic acid-based surfactant products were synthesized. As an auxiliary agent, the K/S value of dyeing at 70°C is larger than the K/S value of commercially available anionic and nonionic surfactant auxiliary agents, which shows that the dyeing effect of the auxiliary agent of the present invention is better than that of commercially available auxiliary agents when dyeing fabrics. The auxiliary agent is better, and the auxiliary agent with the product code PEG1000 has the best dyeing effect.

Table 4 Dyeability on nylon fabric at 80°C, dyeing color difference results using natural curcumin and a series of caffeic acid-based surfactants of the present invention as auxiliary agents (color fixing agent), in color difference The test results show that its level dyeing degree is better, and the color difference △E value of the product coded PEG200 at 80°C is smaller than that of other EO chain lengths, which shows that its level dyeing effect is better. Comparing different EO chain lengths, the product code PEG1000 as an auxiliary has the highest K/S value, showing that its dyeing effect is better than other products with EO chain lengths. The K/S value of the surfactant product as an auxiliary agent is larger than the K/S value of the auxiliary agent dyeing of commercially available anionic and nonionic surfactants, showing that the dyeing effect of the auxiliary agent of the present invention is better than that of the commercially available Auxiliaries are the best, and the dyeing effect of the auxiliaries with the product code PEG1000 is the best. The synthesized caffeic acid amino acid type surfactant of the present invention is a natural decomposable type, which can reduce environmental pollution. Comprehensive relevant data show that adding the auxiliary agent of the present invention is helpful for the dye uptake rate and level dyeing property. Adding appropriate additives can achieve the best dyeing effect.

In the dyeing test, Table 1 to Table 6 show that the caffeic acid-based surfactant of the present invention is used as an auxiliary agent to dye the fiber material, which shows that the caffeic acid-based surfactant of the present invention It has interaction with acid dyes, when the additive is added, the maximum absorption wavelength (λmax) obviously shifts to the short wavelength direction, resulting in blue shift phenomenon (Blue Shift), the addition of surfactant can cause the dye to disperse and dissolve, so that the dyeing rate after dyeing can be improved.

In the dyeing experiment, the caffeic acid amide type surfactant of the present invention is used as an auxiliary agent to dye the fiber material, which can improve the dyeing yield compared with commercially available anionic and nonionic surfactants in the dyeing process. , and the dyeing rate is better than commercially available anionic and nonionic surfactants.

The above examples show that the caffeic acid amide type surfactant of the present invention is used as an auxiliary agent to carry out the dyeing of the fiber material, the auxiliary agent of the present invention has an interaction with the acid dye, and the addition of the surfactant can make The dye produces dispersing and dissolving effect, which improves the dyeing rate after dyeing. At pH 4.5, the saturated adsorption capacity of the dye is equivalent to the content of the terminal amino group of the fiber, so the dye uptake speed is faster and unevenness is likely to occur, but through the caffeic acid amide type surfactant of the present invention Adding it can form a complex (Complex) with the dye first, reduce the solubility of the dye, make the molecules release slowly, inspire the slow dyeing effect, and have the effect of improving the level dyeing property.

A series of natural caffeic acid-based surfactants synthesized by the present invention, according to the experiments of the research team of the present invention, prove that the caffeic acid-based surfactants have low foaming properties, reduced surface tension, wettability, Surface activity such as emulsification and dispersion, the caffeic acid amino acid type surface active agent synthesized by the present invention has good surface activity and can be applied to many processing, textile dyeing and finishing and mixing dispersants, and has biodegradability , the caffeic acid amide type surfactant of the present invention is used as an auxiliary agent in the dyeing of fiber materials, which can promote the dyeing effect of dyes on fiber materials, and because of its non-toxicity and biodegradability, Reduce environmental pollution, greatly improve its economic benefits and practical performance.

The inventive features, content and advantages of the present invention and the effects achieved by this The invention is detailed as above in the form of the embodiment, and the list used in the text is only for illustration and auxiliary description, and the scale of the attached list should not limit the actual implementation of the invention. The scope is described first.

Claims (10)

A kind of dyeing composition of fiber material, this composition comprises: caffeic acid amide type surfactant, in terms of the total weight of described dyeing composition, the content of described caffeyl amino acid type surfactant is 0.001% by weight to 10% by weight; dye, based on the total weight of the dyeing composition, the content of the dye is 0.001% by weight to 10% by weight; and a carrier, based on the total weight of the dyeing composition, The content of the carrier is 80% by weight to 99.998% by weight, wherein, the caffeamide type surfactant has the chemical structure of the following general formula (I):

In the formula, n represents the repeating number of polyethylene glycol, and its value is 2-10000; y represents the repeating number of the -CH ₂ - segment next to the longer-chain acid group in the amido diacid compound, and its value is 1-30 Integer; R is a long-chain saturated or unsaturated hydrocarbon organic group with 6 to 30 carbon chains. A dyeing method for fiber materials, comprising dyeing fiber materials with the following dyeing composition, the composition comprising: caffeic acid amino acid type surfactant, based on the total weight of the dyeing composition, the coffee The content of the acid amido acid type surfactant is 0.001% by weight to 10% by weight; the dye, based on the total weight of the dyeing composition, the content of the dye is 0.001% by weight to 10% by weight; and the carrier , based on the total weight of the dyeing composition, the content of the carrier is 80% by weight to 99.998% by weight, wherein the caffeic acid amide type surfactant has the chemical composition of the following general formula (I): structure:

In the formula, n represents the repeating number of polyethylene glycol, and its value is 2-10000; y represents the repeating number of the -CH ₂ - segment next to the longer-chain acid group in the amido diacid compound, and its value is 1-30 Integer; R is a long-chain saturated or unsaturated hydrocarbon organic group with 6 to 30 carbon chains. The dyeing method of fiber material as described in item 2 of the scope of the patent application, wherein the carrier is selected from: water, ethanol, acetone or their mixed solutions. The dyeing method of fiber material as described in item 2 of the scope of the patent application, wherein the content of the caffeic acid-based surfactant is 0.01% to 5% by weight based on the total weight of the dyed composition. The dyeing method of fiber material as described in claim 2 of the patent application, wherein based on the total weight of the dyed composition, the content of the dye is 0.01% by weight to 5% by weight. The dyeing method of fiber material as described in item 2 of the scope of the patent application, wherein the pH value of the dyeing composition at room temperature ranges from 2 to 6. The dyeing method of fiber material as described in item 2 of the scope of patent application, wherein the fiber material Materials selected from: nylon, wool, fox fur, camel hair, feathers, rabbit fur. The dyeing method of fiber materials as described in item 2 of the scope of the patent application, wherein the dyes include: acid dyes, vegetable natural pigment dyes, wherein the plant natural pigment dyes are selected from: dragon fruit, purple cabbage, madder, turmeric, nails Pigments of flowers, comfrey, safflower, indigo, pomegranate, sumac, Sophora japonica, potato nut, betel nut, roselle, and skullcap. The dyeing method of the fiber material as described in item 2 of the scope of the patent application, wherein the dyeing composition is used to dye the fiber material, including: an exhaust dyeing step, the fiber material is immersed in the dyeing composition at room temperature In the slow dyeing step, the dyeing composition and the fiber material soaked in it are heated to 50°C~110°C at a heating rate of 0.5°C/min~5°C/min; in the dyeing step, the temperature is 50°C~110 temperature of the dyed composition and the fiber material soaked in it for 20 minutes to 90 minutes; and the step of cooling the temperature out of the vat, the dyed composition and the dyed composition and the After the fiber material immersed therein is lowered to 40° C. to 80° C., the fiber material is taken out from the dyeing composition. A fiber product obtained by dyeing fiber materials with the dyeing composition for fiber materials in item 1 of the patent application or the dyeing method for fiber materials in any one of items 2 to 9.