TWI641744B - A dyeing composition for fiber material and using the same method for dyeing process - Google Patents

Abstract

The invention relates to a dyeing composition of a fiber material and a dyeing program using the same, which can improve the color fastness of the dyed and finished fabric by dyeing the fiber by using hyaluronic acid modified quercetin type surfactant as a fixing agent. degree. Quercetin-type surfactant, which has good compatibility with various types of dyes, surfactants and cosmetic raw materials. It has excellent stability under acidic and alkaline conditions, low skin irritation and biodegradation. It has good properties and excellent wettability. In addition, it is more effective as a surfactant to reduce surface tension. The invention utilizes a quercetin type surfactant as an auxiliary agent for fiber dyeing, and the dyeing effect is very good, and the dyeing rate or the leveling property is excellent.

Description

Dyeing composition of fiber material and dyeing program using same

The invention relates to a dyeing composition of a fiber material and a dyeing program using the same, which can improve the color fastness of the dyed and finished fabric by dyeing the fiber by using hyaluronic acid modified quercetin type surfactant as a fixing agent. degree. Quercetin-type surfactant, which has good compatibility with various types of dyes, surfactants and cosmetic raw materials. It has excellent stability under acidic and alkaline conditions, low skin irritation and biodegradation. It has good properties and excellent wettability. In addition, it is more effective as a surfactant to reduce surface tension. The invention utilizes a quercetin type surfactant as an auxiliary agent for fiber dyeing, and the dyeing effect is very good, and the dyeing rate or the leveling property is excellent. The quercetin type surfactant according to the present invention uses a quercetin derivative which is condensed with diol compound and a diol compound, and is selected from the group consisting of polyethylene glycol (PEG) and polyethylene oxide (PEO). a polyoxyethylene ether segment of polyoxyethylene (POE) and a diacid or an acid anhydride compound are subjected to ring-opening polymerization to obtain a block copolymer having an ether group as a linking group, and a quercetin derivative having an ether group The block copolymer is subjected to esterification reaction, and then condensed with hydrophilic hyaluronic acid to modify the water-insoluble quercetin-type surfactant to have excellent chemical stability and low skin irritation, and at the same time Biodegradable natural environmental protection features can be widely used in dyeing and finishing related industrial applications.

In recent years, due to the rapid development of industry, there have been two serious problems affecting human survival, one is the energy crisis and the other is environmental pollution. The energy crisis was mainly caused by oil A large amount of consumption, the goods used by humans are too dependent on petroleum raw materials, resulting in a shortage of petroleum energy, and because of the petroleum-based products, many are not easy to decompose naturally. A large amount of waste causes serious environmental pollution on the earth. In order to reduce this phenomenon, the treatment technology of pollutants, the engineering technology to reduce pollutants and the development of decomposable raw materials are highly valued.

The fixing agent is a kind of surfactant, which can improve the color fastness of the dyed fabric, enhance the washing resistance and friction resistance of the fabric, and improve the retention of the dye on the dyed fabric.

Decomposable surfactants, also known as temporary surfactants or controlled half-lives, are initially defined as: acid, alkali, and salt after completion of their application. The action of heat or light can be broken down into a non-interfacial active substance or a type of surfactant that is converted into a new interfacial active compound. The polar terminal of the surfactant molecule and the hydrophobic chain often contain a weak bond with limited stability. The cleavage of the weak bond can directly destroy the interfacial activity of the molecule, which is commonly referred to as the primary decomposition of the surfactant. The decomposable surfactant can be generally classified into two types, an acetal type and a ketal type, depending on the decomposable functional group. Compared with general surfactants, decomposable surfactants have a better environmental concept, and such surfactants can eliminate some complicated situations. In recent years, people's understanding of decomposable surfactants has been deepened and developed. The magnitude of the environmental impact and the speed of biodegradability have gradually become an important indicator for judging the quality of surfactants.

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

The object of the present invention is to use natural quercetin as a raw material and to modify it into a green environmentally friendly surfactant by using hyaluronic acid, in addition to reducing the surface tension, good wettability, and interfacial activity of emulsification and dispersion. It has low toxicity, biodegradability, and is harmless to the human body. It is used as a fixing agent for fiber dyeing to improve the color fastness of dyed and finished fabrics.

Nylon fiber is formed by condensation polymerization of amino (-NH-) acid or decylamine. The acid dye is an acidic group containing acid dye. The chemical structure contains -OH group, -SO ₃ H group, -COOH, which can be acidic and weak. The dye in the acid or neutral dye bath, the acidic group is mostly sulfonate, soluble in water and dissociated into dye cations in water. In a weakly acidic environment, van der Waals force and hydrogen bonding can be used to obtain a better coloring rate and coloration, but the acid dye is dyed with nylon, which is not easy to be dyed.

Nylon fiber and acid dye have many applications in the industry. The quercetin-type surfactant of the present invention can effectively apply the acid leveling agent, increase the dyeing and dyeing rate, and reduce the amount of acid dye used. Therefore, the quercetin-type surfactant developed by the present invention can be effectively utilized as a nylon fiber dyeing and fixing agent in related fields, and the reaction conditions and actual process production can be reduced, thereby reducing the process cost and improving the working efficiency of the factory machine. After the modification process, the equipment utilization rate can also be improved to reduce the cost. The quercetin type surfactant of the invention proves to have the effect of uniform dyeing after the experiment, and the dye can be evenly colored on the fiber to reduce the unevenness. The yield is greatly improved, and the color fastness of the dyed and finished fabric can be improved. The raw materials used are natural quercetin, which can improve the pollution caused by industrial additives, and make a contribution to environmental protection.

The quercetin-type surfactant of the present invention has excellent dispersibility, emulsifying ability, wettability, lubricity, gloss and texture characteristics, and has the characteristics of biodegradable natural environmental protection. It is an excellent dyeing and finishing agent for textile dyeing and finishing industry. The fabric is harmless to the skin after being dyed and fixed by synthetic products. The wastewater after dyeing and finishing can be decomposed by microorganisms. Contaminant; the quercetin-type interfacial activity research results of the present invention can be applied as industrial emulsification and textile dyeing and finishing industries, dye dispersion and other technologies.

The present invention relates to a dyeing composition of a fiber material and a dyeing process using the same, which comprises a quercetin-type surfactant as a dyeing and finishing aid, and the present invention uses a quercetin-type surfactant as an auxiliary agent for fiber Dyeing, it was found that the dyeing effect was very good, and the dyeing rate or the leveling property was excellent. The quercetin type surfactant according to the present invention uses a quercetin derivative which is condensed with diol compound and a diol compound, and is selected from the group consisting of polyethylene glycol (PEG) and polyethylene oxide (PEO). , polyoxyethylene (POE) polyoxyethylene ether and diacid, or anhydride compounds Ring-opening polymerization to obtain a block copolymer having an ether group as a linking group, esterifying a quercetin derivative with a block copolymer having an ether group, and condensing with a hydrophilic hyaluronic acid to make water insoluble The quercetin-type surfactant is modified to greatly improve water solubility and interfacial properties, resulting in superior chemical stability and low skin irritation. It also has biodegradable natural environmental properties and can be widely used in dyeing and finishing. And other related industrial uses. The invention relates to a quercetin-type surfactant which is modified by hyaluronic acid as an auxiliary agent for fiber dyeing, and finds that the dyeing effect is very good, and has excellent industrial utilization regardless of dyeing rate or leveling property, especially nylon fiber. Substitute with the market.

A dyeing composition of a fibrous material according to the present invention and a dyeing process using the same, the dyeing composition comprising a quercetin-type surfactant having a specific structure, a dye, and a carrier. The content of the quercetin-type surfactant is from 0.001% by weight to 10% by weight based on the total weight of the dyeing composition; the content of the dye is from 0.001% by weight to 10% by weight; and the content of the carrier is from 80% by weight to 99.998% by weight. . The dyeing composition of the present invention utilizes the quercetin-type surfactant contained therein as a dyeing aid to aid fiber dyeing during the dyeing process. The quercetin-type surfactant of the present invention has the structure of the general formula (I), which is a quercetin derivative which is first condensed by using quercetin and a diol compound, and is selected from the group consisting of: polyethylene The ring-opening polymerization of a polyoxyethylene ether segment of an alcohol, polyethylene oxide or polyoxyethylene with a diacid or an acid anhydride compound to obtain a block copolymer having an ether group as a linking group, and a quercetin derivative The ester-based block copolymer is esterified, and then condensed with hydrophilic hyaluronic acid to modify the water-insoluble quercetin-type surfactant to greatly improve water solubility and interfacial properties, resulting in superior chemistry. It has the characteristics of stability and low skin irritation, and has the characteristics of biodegradable natural environment. It can be widely used in dyeing and finishing related industries, and further improves the efficiency of biodegradable.

A dyeing composition of a fibrous material, comprising: a quercetin-type surfactant, the quercetin-type surfactant is contained in an amount of 0.001% by weight to 10% by weight based on the total weight of the dyeing composition; The dye is contained in an amount of 0.001% by weight to 10% by weight based on the total weight of the dyeing composition; and the carrier is 80% by weight based on the total weight of the dyeing composition. % to 99.998% by weight, wherein the quercetin-type surfactant has a chemical structure of the following formula:

L: is a diol compound residue

G: quercetin residue

x: number of repeats of -CH ₂ - segments in anhydride or diacid compounds

n: polyoxyethyl ether segment repeat unit number

m: hyaluronic acid segment repeat unit number

The dyeing composition of the fiber material of the present invention, the quercetin-type surfactant is composed of quercetin and a hyaluronic acid hydrophilic group, and has a special chemical structure, so it is at a very low concentration. It is easy to be adsorbed on the surface or interface of the solution, thereby changing the free energy of the surface or interface of the solution, so as to reduce the surface tension and produce characteristics such as wetting, penetration, foaming, emulsifying, dispersing and melting.

A dyeing composition of the fibrous material of the present invention, wherein the quercetin-type surfactant is prepared by using quercetin, polyoxyethyl ether (EO) segments and hyaluronic acid to produce a series of biodegradable properties. A water-soluble surfactant that does not pollute the environment and has excellent properties. The quercetin-type surfactant of the present invention is combined with a polyoxyethyl ether (EO) segment through a quercetin derivative, and then reacted with hyaluronic acid to modify water-insoluble quercetin to have a more Excellent chemical stability and low skin irritation, quercetin surfactant has good compatibility with various types of dyes, surfactants and cosmetic raw materials, and has excellent stability under acidic and alkaline conditions. It has low skin irritation, good biodegradability and excellent wettability, combining the advantages of these two materials. By combining a water-insoluble quercetin with a hydrophilic hyaluronic acid by a condensation reaction technique to form a group containing a hydrophilic and hydrophobic property, the water solubility is greatly enhanced and the excellent properties possessed by itself are exhibited, so that it is more useful in use. Extensive industrial applicability, in addition, to further improve the efficiency of biodegradable. The quercetin type surfactant of the invention has excellent dispersing emulsifying ability, moisturizing lubrication and improving luster texture characteristics, and has the characteristics of biodegradable natural environmental protection, and can be widely applied to dyeing and finishing, cosmetics. It has excellent industrial applicability and market substitution in cleaning industry, food emulsification, pharmaceutical emulsification, industrial products and other related industrial applications. It is an excellent dyeing and finishing agent for textile dyeing and finishing industry. The fabric is harmless to the skin after being dyed and fixed by synthetic products. The wastewater after dyeing and finishing can be decomposed by microorganisms. Contaminant; the quercetin-type interfacial activity research result of the invention can be used as a technical application in industrial emulsification, textile dyeing and finishing, dye dispersion and the like.

The dyeing composition of the fibrous material of the present invention, wherein the quercetin-type surfactant is derived from a biodegradable, non-toxic quercetin and a diol compound by polycondensation of quercetin under an acidic catalyst Ring-opening polymerization using polyoxyethylene ether segments of polyethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene (POE) and diacids or anhydride compounds with different molecular weights Obtaining an ether group-containing block copolymer as a spacer, esterifying a quercetin derivative with an ether group block copolymer, adding a hydrolyzed hyaluronic acid, and preparing a condensation reaction A range of natural quercetin-type surfactants. The hydrophobic quercetin is combined with the hydrophilic hyaluronic acid by a condensation reaction technology to greatly increase the water solubility of the surfactant, wherein the ether-containing block copolymer contains a polyoxyethyl ether segment (optional) From: polyethylene glycol, polyethylene oxide, polyoxyethylene) linked to quercetin derivatives, and then formed by reaction with hyaluronic acid. The structure of the general formula (I) is as follows Wherein L is a diol compound residue, G is a quercetin residue, and x is an acid anhydride or a repeating amount of a -CH ₂ - segment of the diacid compound, and has a value of from 1 to 20, wherein the diol compound is selected from the group consisting of A diol compound having 2 to 20 carbon atoms, and n represents a polyoxyethyl ether segment repeating unit number, and has a value of 10 to 5,000, wherein m represents a repeating unit number of hyaluronic acid segments, and the value is 10 to 10,000.

The preparation method of the quercetin-type surfactant of the present invention is a product A, an acid anhydride or a product of a diacid compound reacted with polyethylene glycol, which reacts with quercetin and a diol compound, and then a product A and The product B is condensed to give the product C, which is then reacted with hyaluronic acid to give the crude product.

Preparation of a quercetin type surfactant in the invention The method comprises the following steps: a synthesis step comprising the following (a) to (d): (a) reacting quercetin with a diol compound, adding a catalyst to slowly raise the temperature to 80 to 200 ° C, and reacting for 1 to 8 hours, and then Cool to 50 ~ 110 ° C, add a base (such as alkali metal hydroxide solution) to terminate the reaction, warm up to 120 ~ 200 ° C pumping and decompression to remove excess diol and water and maintain 2 ~ 6 hours, to obtain product A; b) esterifying a polyoxyethylene ether segment alcohol selected from the group consisting of polyethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene (POE), and a diacid or anhydride compound, and placing the bottle in a bottle After heating to 30~80 °C, the diacid or anhydride compound and the polyoxyethylene ether are uniformly mixed, and then the catalyst is added, and the temperature is gradually raised to 110 to 200 ° C, and the reaction is carried out for 2 to 8 hours to obtain the product B; (c) The product A and the product B are placed in a reaction flask and heated to 80-200 ° C, and the water is removed by a water-flow pumping to obtain the product C; (d) the product C and the hyaluronic acid compound are at 60 ° C to 100 ° C. After reacting for 3 to 10 hours, a series of crude quercetin-type surfactants are obtained. The ethanol is used as a solvent to remove unreacted materials by suction filtration, and then the upper layer of the filtrate is extracted. The solvent was removed using a vacuum concentrator to give the final product.

The preparation method of the quercetin type surfactant of the invention, wherein the polyoxyethyl ether segment is selected from the group consisting of polyethylene glycol compound (PEG), polyethylene oxide (PEO) or polyoxyethylene (POE) ).

The invention provides a preparation of a quercetin type surfactant, wherein the catalyst is selected from the group consisting of titanium (IV) tetraisopropoxide, sulfuric acid, hydrochloric acid or a group thereof.

Structural Analysis of Quercetin-type Surfactant of the Invention

IR: Perkin-Elmer Spectrum One (Perkin Elmer Cetus Instruments, Norwalk, CT), samples were concentrated, vacuum dried to remove moisture, and then ground on KBr salt tablets for testing.

Infrared spectrometers (FT-IR) are used to identify compounds by the infrared absorption spectrum generated by the absorption of vibration and rotational energy levels caused by molecular absorption of infrared radiation. Most of them are used for the identification of functional groups. Because all molecules have a fixed energy, the bond is stretched and bent, and the atomic oscillation and shaking cause other molecules to vibrate. However, the functional group of a fixed molecule can only bend or vibrate at a specific frequency of a certain specific energy level, and when the molecule is irradiated with infrared light, the vibration bond can be absorbed only when the frequency of the light is the same as the vibration frequency of the member. energy.

Figure 1 shows the results of infrared FT-IR spectroscopy analysis of the products of the quercetin-type surfactant of the present invention, and Table 2 shows the characteristic absorption peaks corresponding to various functional groups of the synthetic quercetin-type surfactant product, and the results can be seen - The asymmetric stretching vibration of OH and -NH is in the position of 3708~3010cm ^-1 . The stretching vibration of NH group appears in this range. It overlaps with the stretching vibration of OH group, but the peak shape is sharp, and the number of absorption peaks is on the nitrogen. For the number of hydrogen atoms; -CH ₂ asymmetric stretching vibration of 2912 ~ 2882cm ^-1; C = O stretching vibration of the 1770,1680cm ^-1 position; C = C a benzene ring skeleton vibration of 1540 cm ^-1 in a position The position of the asymmetric bending vibration of -CH _{3 is} 2894~3066cm ^-1 ; the symmetric stretching vibration absorption of CO is at the positions of 1141cm ^-1 , 1288cm ^-1 and 1291cm ^{-1 respectively} ; the out-of-plane bending vibration of CH is absorbed in 978cm ^-1 , 854cm ^-1 place.

The dyeing performance analysis of the quercetin-type surfactant of the present invention: the present inventors succeeded in synthesizing the quercetin-type surfactant, and the present invention utilizes the quercetin-type surfactant to perform different color acidity on the nylon fiber material. Dye concentration and different additive concentrations to achieve deep dyeing and uniform effects.

In the dyeing process according to an embodiment of the present invention, dyeing is utilized The composition dyes the nylon fiber material and includes the following steps. In the dip dyeing step, the nylon fiber material is immersed in the dyeing composition at room temperature. In the retarding step, the dyeing composition and the nylon fiber material immersed therein are heated to a temperature of 60 ° C to 110 ° C at a heating rate of 0.5 ° C / min to 5 ° C / min. In the dyeing step, the dyeing composition and the nylon fiber material immersed therein are held at 60 ° C to 110 ° C for 20 minutes to 60 minutes. Cooling and discharging step, the dyeing composition and the nylon fiber material immersed therein are lowered to 40 ° C to 80 ° C at a cooling rate of 0.5 ° C / min to 5 ° C / min, and then the nylon fiber material is taken out from the dyeing composition. .

In the dyeing composition according to an embodiment of the present invention, the content of the quercetin-type surfactant is, for example, 0.01% by weight 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, the content of the dye is, for example, 0.01% by weight 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, the pH of the dyeing composition at room temperature is, for example, 2 to 6.

The dyeing procedure of the fibrous material of the present invention comprises the steps of providing a fibrous material, providing a dyeing composition, wherein the dyeing composition comprises a quercetin-type interface in an amount of from 0.001% by weight to 10% by weight based on the total weight of the dyeing composition. The active agent, the content of the dye is from 0.001% by weight to 10% by weight, and the carrier is contained in an amount of from 80% by weight to 99.998% by weight. The fiber material is dyed using the dye composition.

In an embodiment of the invention, the dye is permeable to the surface of the nylon fiber material by a dyeing process by molecular forces such as hydrogen bonding or van der Waals. on. The dye is an acid dye such as Red No. 114 dye (C.I. Acid Red 114, Dianix Rubine SE-B, manufactured by DyStar Corporation).

The content of the dye is from 0.001% by weight to 10% by weight, based on the total weight of the dyeing composition, and preferably from 0.01% by weight to 5% by weight. Further, the content of the dye can be adjusted depending on 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 a desired color; and when the content of the dye is more than 10% by weight, excess dye may remain in the fiber material, thereby causing waste of dye Or environmental pollution problems.

In an embodiment of the invention, the carrier functions to provide an environment in which the dye and quercetin-type surfactant in the dye composition can be arbitrarily mixed and/or aggregated. The carrier is, for example, water, ethanol, acetone or a mixed solution thereof. The carrier is contained in an amount of from 80% by weight to 99.998% by weight based on the total weight of the dyeing composition.

Further, in an embodiment of the present invention, the dyeing composition may further include a pH adjusting agent for adjusting the pH of the dyeing composition. The pH of the dyeing composition may be, for example, 2 to 6 at room temperature, and the pH adjusting agent is, for example, glacial acetic acid, formic acid, phosphoric acid or hydrochloric acid. When the pH of the dye composition is in the above range, it will be able to affect the charge of the nylon fiber material while also increasing the degree of dye dispersion and the speed at which it is combined with the nylon fiber material.

Based on the above, since the dyeing composition includes a quercetin-type surfactant, when the dyeing composition is used to dye the fiber material, the dyeing composition can have a good dye uptake rate and uniform dyeing on the fiber material. To achieve the effect of fiber dyeing and dyeing, especially nylon fiber materials. The dyed nylon fiber material has good wash fastness and light fastness.

Another embodiment of the present invention provides a dyeing procedure for a fibrous material which dyes a fibrous material using the dyeing composition of the present invention described above. The fibrous material dyed by the dyeing procedure of the present invention can have good wash fastness and light fastness relative to conventional dyeing procedures.

In the dyeing procedure provided in the present embodiment, a nylon fiber material and the dyeing composition described in the above examples were first provided, and then the nylon fiber material was dyed using the dyeing composition. In the dyeing procedure, the bath ratio of the nylon fiber material to the dye composition is, for example, about 1:40. For example, if a nylon fiber material having a weight of 2.5 grams is to be dyed, it may be immersed in a dyeing composition having a weight of 100 grams.

When the fiber material is dyed using the dyeing composition of the present invention, it may include a dip dyeing step, a retarding step, a dyeing step, and a cooling step. Each step will be described in detail below.

In an embodiment of the invention, the dip dyeing step is, for example, by dipping the nylon fiber material into the dyeing composition at room temperature. After the dip step, a slow dyeing step is performed. The retarding step is, for example, heating the dyeing composition and the nylon fiber material immersed therein to a temperature of from 0.5 ° C / min to 5 ° C / min to 60 ° C to 110 ° C. In the dip dyeing step and the retarding step, the dye in the dyeing composition may be initially adsorbed on the surface of the nylon fiber material, thereby dyeing the nylon fiber material to a color corresponding to the dye.

After the dip dyeing step and the retarding step, the dyeing step is carried out. The dyeing step is, for example, dyeing the composition and nylon immersed therein at 60 ° C to 110 ° C. The fiber material is held for 20 minutes to 60 minutes. In the above dyeing step, retarding step, and dyeing step, since the dyeing composition of the present invention contains a quercetin-type surfactant, the dyeing composition has a nylon fiber material at a temperature of 60 ° C to 110 ° C. Good dyeing rate and leveling property, so that the dyed nylon fiber material has good washing fastness and light fastness.

After the dyeing step, a cooling down step is performed. The step of cooling the cylinder is, for example, reducing the dye composition and the fiber material immersed therein to a temperature of about 40 ° C to 80 ° C at a temperature decreasing rate of 0.5 ° C / min to 5 ° C / min, and then removing the fiber material from the dyeing composition. . In addition, after the step of cooling and discharging, the dyed fiber material can be washed, dehydrated and naturally air-dried.

Based on the above dyeing results, as shown in Tables 3 to 8, it is understood that in the dyeing procedure of the present invention, since the nylon fiber material is dyed using the dyeing composition containing the quercetin-type surfactant, the dyed nylon fiber material has Good coloring and leveling.

Figure 1. Infrared spectrum of the quercetin surfactant of the present invention

The features of the present invention will be more specifically described below with reference to experimental examples and comparative examples. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be limited by the experiments described below. Explain sexually.

The preparation and properties of the quercetin-type surfactant of the present invention are determined by using materials:

(1) Quercetin MF: C ₁₅ H ₁₀ O ₇ , Mw: 302.23 g/mol Structure:

(2) Propylene glycol (PG) (Propylene Glycol) MF: C ₃ H ₈ O ₂ , Mw: 76.10 g / mol structure:

(3) Hyaluronic Acid MF: (C ₁₄ H ₂₁ NO ₁₁ )n

(4) Maleic Anhydride (MA) MF: C ₄ H ₂ O ₃ , Mw: 98.06 g/mol Structure:

(5) Polyethylene glycol (PEG) structure: The polyoxyethyl ether segment has a molecular weight of: 2000, 4000, 6000, 8000, 10000 (g/mol) of polyethylene glycol (PEG).

(6) Titanium Isopropoxide MF: [(CH _{3) 2} CHO] ₄ Ti, Mw: 284.26 g/mol

(7) Castor Oil MF: C ₅₇ H ₁₀₄ O ₉ , Mw: 933.61 g/mol

(8) Nonionic surfactant: C ₁₄ H ₂₂ O(C ₂ H ₄ O)n, n is 9 or 10, (Triton X-100)

(9) Anionic surfactant: sodium dodecyl sulfate (SDS)

The synthesis of the quercetin-type surfactant of the present invention comprises the steps of (a) to (d) as follows: (a): 1 mole of quercetin and propylene glycol 1 mole are placed with a Teflon stir bar and warm In a four-bar reaction flask, 1.00 g of Titanium Isopropoxide was added to slowly raise the temperature to 120 ° C, react for 4 hours, then cool to 90 ° C, and add 1.50 g of sodium hydroxide to terminate the reaction. Heat up to 120~140 °C to extract excess propylene glycol and water and maintain for 4 hours to obtain product A; (b): 1mole polyethylene glycol (PEG, Mw: 2000, 4000, 6000, 8000, 10000) and 2 mole of maleic anhydride, placed in a reaction flask, heated to 60 ° C, stirred to homogenize the maleic anhydride and polyethylene glycol, and added 1.00 g of catalyst tetraisopropyl titanate (Titanium Isopropoxide) Slowly raising the temperature to 150 ° C, the reaction is 5 hours, to obtain the product B; (c): the product A and the product B are placed in a reaction flask and heated to 120 ° C, and the water is decompressed by water flow to remove the water to the external H tube. and reacted for 3 hours to give the product C; (d): 1mole product of 1 mole C, and hyaluronic acid compound, a reaction at 80 ℃ ~ 90 ℃ 8 hours. Quercetin series type surfactant crude product, which was then to suction filtration using ethanol as a solvent to remove unreacted materials, the upper layer was re-extracted filtrate, concentrated under vacuum to give the final product The solvent was removed machine.

The quercetin-type surfactant of the present invention is quercetin, propylene glycol, polyethylene glycol (PEG, Mw: 2000, 4000, 60,000, 8000, 10000), maleic anhydride and hyaluronic acid in the experimental examples. The main raw material, the quercetin and propylene glycol are firstly condensed to modify the water solubility of quercetin, and then the polyethylene glycol is changed differently (oxyethylene ether) EO chain length and maleic anhydride are synthesized to form an etheric amphiphilic block. The copolymer is finally synthesized by synthesizing the two-stage reaction product and introducing hydrophilic hyaluronic acid to prepare a series of quercetin-type surfactants. The codes and compositions of the products synthesized by the present invention are shown in Table 1.

Structural Identification and Analysis of Quercetin-type Surfactant of the Invention

The structure of the quercetin-type surfactant molecule synthesized by the present invention is confirmed by (FT-IR), and the infrared spectrum analysis chart mainly determines the molecular structure because all molecules have some fixed amount of energy, resulting in bond stretching. And bending, while the atoms oscillate and shake, causing other molecules to vibrate, and a fixed molecule can only bend or vibrate at a specific frequency equivalent to a specific energy level. When a molecule is irradiated with infrared light, the vibrating key absorbs energy only when the frequency of the light is the same as the vibration frequency of the key.

Figure 1 shows the results of infrared FT-IR spectroscopy analysis of the products of the quercetin-type surfactant of the present invention, and Table 2 shows the characteristic absorption peaks corresponding to various functional groups of the synthetic quercetin-type surfactant product, and the results can be seen - The asymmetric stretching vibration of OH and -NH is in the position of 3708~3010cm ^-1 . The stretching vibration of NH group appears in this range. It overlaps with the stretching vibration of OH group, but the peak shape is sharp, and the number of absorption peaks is on the nitrogen. For the number of hydrogen atoms; -CH ₂ asymmetric stretching vibration of 2912 ~ 2882cm ^-1; C = O stretching vibration of the 1770,1680cm ^-1 position; C = C a benzene ring skeleton vibration of 1540 cm ^-1 in a position The position of the asymmetric bending vibration of -CH _{3 is} 2894~3066cm ^-1 ; the symmetric stretching vibration absorption of CO is at the positions of 1141cm ^-1 , 1288cm ^-1 and 1291cm ^{-1 respectively} ; the out-of-plane bending vibration of CH is absorbed in 978cm ^-1 , 854cm ^-1 place.

Comparing examples of the present invention with commercially available other anionic, nonionic surfactants, the quercetin-type surfactants of the present invention exhibit superior properties over conventional surfactants, whether Emulsifying stability, dispersibility, or biodegradability have excellent performance, and can be used as a good surfactant for green and environmental protection.

Nylon fiber is formed by condensation polymerization of amino (-NH-) acid or decylamine. The acid dye is an acidic group containing acid dye. The chemical structure contains -OH group, -SO ₃ H group, -COOH. Dyes in acidic and weakly acidic or neutral dye baths, so wool and silk dyeable acid dyes can also be dyed with nylon fibers.

Most of the acidic groups are -OH group, -SO ₃ H group, -COOH group, sulfonate group, easily soluble in water, dissociated into water cations in water to be anionic, and need to be assisted by acid, so that ionic bond bonding is possible. dyeing. The dyeing operation is simple, the color is bright, and the washing fastness is medium.

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

For dyeing, CIB LAB is based on the theory that a color cannot be both green and red, and neither blue nor yellow. Therefore, a single value can be used to describe the red/green, yellow/blue features. The CIB LAB tolerance formula is centered on the standard and then given individual L*a*b* values, positive and negative (+/-) error ranges.

△L*=L* sample-L* standard (lightness difference, + shallow)

△a*=a* sample-a* standard (+ reddish, - greenish)

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

In the experiment of the invention, the dye acid dye (CI acid blue 113 and CI acid red 114) is used, and the pH is adjusted to 4.5 with acetic acid, and the vanadium force and the hydrogen bond can be made in a weakly acidic environment to obtain better coloring. Rate and color, but acid dyed nylon, not easy to dye, so the use of new surfactants to increase the level of dyeing and dyeing.

The dyeing procedure of the fiber material of the present invention is respectively formulated with a dye concentration of 1% owf (mass percentage, the dye used is 1% of the total dye solution) and an auxiliary agent (quercetin-type surfactant, anionic surfactant, non- Ionic surfactant) a dyeing composition composed of a concentration of 0.05% by weight (% by mass) and a carrier (water) for dyeing nylon fiber cloth, and then using a RUBI dyeing proofing machine and a spectrophotometer The instrument analyzes the relevant properties and discusses the effect of the addition of dyes or additives on the dyeing of nylon fabrics.

Dyeing: When dyeing nylon fabrics, the biggest problem is uneven dyeing. Like, it is necessary to use a leveling agent to achieve a 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 molecules first adsorb the dye molecules, so that the dye molecules become larger, and the dye molecules and fiber dyeing rate slow down, and reach the average Dyeing effect. In the later stage of dyeing, it is necessary to promote the dyeing speed, reduce the dye residue, and achieve the hue concentration of the desired dyeing. Dyed with Drum Dyeing Testing Matching and tested with the Color Matching System (CS-5).

Experimental drugs and materials

Nylon fiber cloth

Acetic Acid Acetate, Glacial CH ₃ COOH, molecular weight 60.05, reagent level, purchased from Japan Pharmaceutical Company

Additives: quercetin type surfactant, commercially available anionic surfactant, nonionic surfactant acid dye: C.I. Acid Blue 113 and C.I. Acid Red 114

Experimental procedure

1, weighing nylon fiber cloth 2 grams

2, preparation of dyeing composition 100ml

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

B. Formulating a concentration of 0.05% (mass%) of additives, the auxiliary agent is selected from: different quercetin type surfactants (including polyoxyethyl ether segments, molecular weights of 2000, 4000, 6000, 8000, respectively) g/mol) polyethylene glycol (PEG)); additives of the comparative examples: commercially available anionic surfactants, nonionic surfactants.

C, adjusted to pH=4.5 with acetic acid, bath ratio: 1:40

3. Dip dyeing step: The nylon fiber material and the dyeing composition are respectively placed in a steel cylinder at room temperature.

4. The retarding step, the dyeing composition and the nylon fiber material immersed therein are heated to 75, 80, 85, 90, 95 ° C at a heating rate of 1 ° C / min by the dyeing conditions of the RUBI dyeing proofing machine.

5. Dyeing step The dyeing composition and the nylon fiber material soaked therein were held at 75, 80, 85, 90, 95 ° C for 30 minutes.

6. The step of cooling the cylinder is carried out, and the dyeing composition and the nylon fiber material immersed therein are lowered to 50 ° C at a cooling rate of 1 ° C / min, and then the nylon fiber material is taken out from the dyeing composition.

7, washed and dried

8, colorimetry

The dye bath formula is prepared according to the dyeing conditions. No auxiliary agent is added to the cylinder of the first cylinder, and the other cylinders are added with different auxiliary agents. The nylon fabric was placed in a steel cylinder, and the cap was tightened to set the initial temperature to 50 ° C, and the temperature was increased by 1 ° C per minute. When reaching 70 ° C, the cylinder is placed in the cylinder holder of the computer dyeing machine. After 5 minutes, one of the cylinders is taken out, and the fabric in the cylinder is fully washed and then naturally dried. At 75, 80, 85, 90, 95 ° C, the remaining cylinders were taken out separately and washed naturally after washing. Use the Applied Color System to make it calibrated and then enter the test.

Dyeing strength and evaluation results

When the dyeing and finishing industry uses dyes for dyeing, it is necessary to add a dyeing agent to the dyeing liquid to make the dye easily enter the fiber interior to achieve the purpose of deep dyeing and low residual liquid. The dyeing agent must have a good dispersion Sex, it helps the dye to diffuse into the fiber, prevent the dye from agglutinating, does not inhibit the final dyeing, and has moderate retarding and leveling properties. In addition, foaming is required to be small, and there is no influence on the dyeing fastness. One of the important indicators for evaluating the dyeing performance of dyes is the depth of dyeing. The Kubelka-Munk staining depth equation establishes a certain functional relationship between the absorption coefficient K and the scattering coefficient S of the measured object and the concentration C of the colored substance in the solid sample. The larger the K/S value obtained by calculation, the deeper the surface color of the solid sample, that is, the higher the concentration of the colored substance, the better the dyeing performance of the dye.

The dyeing properties of the nylon fiber cloth after dyeing using the dye composition containing the quercetin type surfactant of the present invention are as follows:

Spectrophotometric colorimeter analysis

Using the Gretag Macbeth Color-Eye 2180 UV/2180 spectrophotometer, the dyed nylon fiber cloth obtained by the comparative example (without adding the quercetin-type surfactant of the present invention) was used as a standard sample, respectively. The dyeing coloring strength and chromatic aberration of the dyed nylon fiber cloth obtained by each dye composition in the experimental examples were evaluated, and the results are reported in Tables 3 to 8.

The coloring intensity was calculated according to Kubelka-Munk Theory. In the following Tables 3 to 8, the coloring strength of the comparative example (standard sample) is set to 100.0.

The quercetin-type surfactant of the present invention is added in an amount of 0.05%, and the coloring strength color difference analysis results are shown in Tables 3 to 8 below, which are a series of different PEG chain length quercetin-type surfactant adjuvants and are carried out at different temperatures. Dyeing, the results show that the dye dispersibility is better due to the addition of quercetin-type surfactant. The quercetin-type surfactant can partially dissolve the agglutinated dye, and the dye is less likely to agglomerate. Has better dispersion.

Table 3 is the results of the dyeing color difference (ΔE) of acid red 114 dyed on nylon fabric, acid red 114 and the dyeing color difference result of the quercetin type surfactant adjuvant of the invention series, showing the addition of the auxiliary agent of the invention The dyeing degree is better, especially in the QP6H (PGE6000) product dyeing at 75 ° C is smaller than the △ E value of other PEG chain length products, showing that the leveling effect is superior. Comparing the dyeing at different temperatures, it can be seen that 75 ° C has a large (K / S) value, indicating that the dyeing strength is better at low temperature, and the dyeing result at 75 ° C shows that the quercetin type synthesized by the present invention is added. The additive of the surfactant is smaller than the ΔE value of the commercially available anionic and nonionic surfactant, indicating that the synthetic product of the present invention has better leveling property, and the saturated adsorption amount of the dye and the fiber at pH 4.5 The content of the terminal amine group is equivalent, so the dye dyeing speed is faster, and the unevenness is likely to occur. However, the addition of the quercetin-type surfactant can form a complex with the acid dye to reduce the dye solubility. Slow release of molecules, inducing retardation.

The optimum temperature for dyeing nylon fibers is 90 ° C. Generally, the lower the temperature, the lower the dye dyeing intensity. Table 4 shows the acid red color 114 and the dyeing coloring effect of the quercetin-type surfactant additive of the present invention. It can be seen from the table that at 75 ° C, it is shown that the addition of the auxiliary product of the present invention has a high K/S value, and the dyeing effect is best at low temperatures. Comparing the quercetin-type surfactants with different PEG chain lengths in the present invention, the K/S value of 33.923 of QP8H (PEG8000) is the highest, and the dyeing effect is compared. Other PEG chain length products are good, and dyeing at 75 ° C shows that the addition of the product adjuvant of the invention has a higher K/S value than the addition of commercially available anionic and nonionic surfactants, indicating that the dyeing effect is higher than that of the city. The auxin-type surfactant is good in natural decomposable type, and the pollution to the environment can be reduced. The comprehensive data show that the addition of the auxiliary agent of the invention contributes to the dye uptake rate and selects an appropriate auxiliary agent. Add up to the optimal dyeing effect. Table 5 shows an acid red 114 dyed nylon fabric color cloth card, which shows the effect of promoting dyeing and dyeing by using the quercetin type surfactant of the present invention as an auxiliary agent.

Table 6 is a table showing the results of the dyeing (ΔE) of Acid Blue 113 dyed on Nieneng fabric, Acid Blue 113, and the dyeing color difference result of the quercetin-type surfactant adjuvant of the present invention. The QP4H (PEG4000) product has a small ΔE value at 85 °C, and its dyeing effect is the best. Table 7 shows the dyeing strength (K/S) results of acid blue 113 dyed on nylon fabric, from Table 7 Acid Blue. 113. The staining and coloring results of the quercetin-type surfactant auxiliary agent of the different chain length PEG of the present invention show that the quercetin-type surfactant of the present invention has a high K/ when QP8H (PEG8000) is used as an auxiliary agent. The S value indicates that the longer the PEG chain length is, the better the dyeing effect is, but the dyeing property is poor. The dye dyeing speed is faster and the unevenness is easy to occur. The relevant data comprehensively show that the quercetin-type surfactant is added to The product of QP4H (PEG4000) is a complex which can form a complex with an acid dye at 85 °C, which reduces the dye solubility, produces a retarding effect, contributes to the dye dyeing rate, and selects the dye structure and fiber properties. Appropriate additives can be added to optimize the dyeing effect. Table 8 shows an acid blue 113 dyed nylon fabric color card showing the effect of promoting dyeing and dyeing when using the quercetin type surfactant of the present invention as an auxiliary agent.

The quercetin-type surfactant used in the present invention is a condensed quercetin derivative which is biodegradable and non-toxic to the human body and is condensed under an acidic catalyst, and is selected from different molecular weights. Polyethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene (PoE) polyoxyethylene ether segment and diacid, or anhydride compound are ring-opened to obtain a block with ether groups The polymer acts as a spacer to esterify the quercetin derivative with the block copolymer having an ether group, and then hydrolyzes the hyaluronic acid to prepare a series of natural products through condensation reaction. Quercetin-type surfactant. According to the research team of the present invention, the water-soluble quercetin type surfactant has low foaming property, reduced surface tension, wettability, emulsification and dispersion, and the interface property will follow the molecular weight of the polyethylene glycol. Change; synthetic water-soluble quercetin-type surfactant, with good interfacial activity, can be applied to many processing, textile dyeing and mixing and dispersing agents; from the experimental results, a series of quercetin-type surfactants have been obtained. It has the characteristics of reducing surface tension, wettability and low foaming, and is biodegradable. It is applied to fiber dyeing. The quercetin-type surfactant product dyeing effect is good, and it can also be non-toxic and biological. Decomposability, reduce environmental pollution, and greatly improve its economic and practical performance.

The features, aspects, advantages and advantages of the invention are set forth in the description of the embodiments of the present invention, and the descriptions of the embodiments used herein are merely for the purpose of illustration and description. The scope of patents in the actual implementation of the present invention should be limited to the proportions listed in the attached table.

Claims (10)

A dyeing composition of a fibrous material, comprising: a quercetin-type surfactant, the quercetin-type surfactant is contained in an amount of 0.001% by weight to 10% by weight based on the total weight of the dyeing composition; The dye is contained in an amount of 0.001% by weight to 10% by weight based on the total weight of the dyeing composition; and the carrier is 80% by weight based on the total weight of the dyeing composition. % to 99.998% by weight, wherein the quercetin-type surfactant has the chemical structure of the following general formula (I): Wherein L is a diol compound residue, G is a quercetin residue, and x is an acid anhydride or a repeating amount of a -CH ₂ - segment of the diacid compound, and has a value of from 1 to 20, wherein the diol compound is selected from the group consisting of A diol compound having 2 to 20 carbon atoms, and n represents a polyoxyethyl ether segment repeating unit number, and has a value of 10 to 5,000, wherein m represents a repeating unit number of hyaluronic acid segments, and the value is 10 to 10,000. The dyeing composition according to claim 1, wherein the carrier is selected from the group consisting of water, ethanol, acetone or a mixed solution thereof. The dyeing composition according to claim 1, wherein the quercetin-type surfactant is 0.01% by weight based on the total weight of the dyeing composition. Up to 5% by weight; the dye is present in an amount of from 0.01% by weight to 5% by weight. The dyeing composition of claim 1, wherein the dyeing composition has a pH in the range of 2 to 6 at room temperature. The dyeing composition according to claim 1, wherein the preparation of the quercetin-type surfactant is a product A, an acid anhydride or a diacid compound which is reacted with quercetin and a diol compound. From: polyethylene glycol, polyethylene oxide, polyoxyethylene ether polyoxyethylene ether reaction product B, and then product A and product B condensation reaction to obtain product C, product C and then reacted with hyaluronic acid compound product. The dyeing composition according to claim 5, wherein the hyaluronic acid is derived from any one of a microbial fermentation method, a chemical synthesis method, and an animal extraction method. The dyeing composition according to claim 5, wherein the preparation of the quercetin-type surfactant comprises the steps of (a) to (d): (a) quercetin and The diol compound is reacted, the catalyst is slowly heated to 80-200 ° C, the reaction is carried out for 1-8 hours, and then cooled to 50-110 ° C. The reaction is terminated by adding a base, and the temperature is raised to 120-200 ° C to extract and decompress the excess. The diol and water are maintained for 2 to 6 hours to obtain product A; (b) an esterification reaction selected from the group consisting of polyethylene glycol, polyethylene oxide, polyoxyethylene ether of polyoxyethylene, and an acid anhydride compound, and placed in a bottle After heating to 30~80 °C, the acid anhydride compound and the polyoxyethylene ether are uniformly mixed, and then the catalyst is slowly heated to 110 to 200 ° C, and the reaction is carried out for 2 to 8 hours to obtain the product B; (c) the product A and the product are obtained. B, placed in a reaction flask to raise the temperature to 80 ~ 200 ° C, and use water flow evacuation to remove water to obtain product C; (d) product C and hyaluronic acid compound, reaction at 60 ° C ~ 100 ° C 3 ~ 10 In an hour, a crude quercetin-type surfactant was obtained, and the unreacted material was removed by suction filtration using ethanol as a solvent. The upper layer of the filtrate was re-extracted and the solvent was removed using a vacuum concentrator to obtain the final product. A dyeing process for a fibrous material, comprising: providing a fibrous material; providing a dyeing composition according to any one of claims 1 to 7, wherein the fibrous material is dyed with the dyeing composition. A dyeing procedure for a fibrous material according to claim 8, wherein the fibrous material is dyed by the dyeing composition, comprising: a dip dyeing step of immersing the fibrous material in the dyeing composition at room temperature The dyeing step heats the dye composition and the fiber material immersed therein to a temperature of 60 ° C to 110 ° C at a heating rate of 0.5 ° C / min to 5 ° C / min; the dyeing step is 60 ° C ~ 110 °C holding the dyeing composition and the fibrous material immersed therein for 20 minutes to 60 minutes; and cooling the cylinder step, and the dyeing composition is cooled at a temperature decreasing rate of 0.5 ° C / min to 5 ° C / min After the fibrous material soaked therein is lowered to 40 ° C to 80 ° C, the fibrous material is taken out from the dyeing composition. A fibrous product obtained by dyeing a fibrous material by the dyeing composition of any one of claims 1 to 7 or by a dyeing procedure according to any one of claims 8 to 9.