TW201800448A - Dyeing composition for nylon fiber material and dyeing process using the same capable of improving water solubility and interfacial characteristics, as well as providing advantages of good dyeing effect, excellent dyeing rate, dyeing uniformity biological decomposition, and nature and environment protection - Google Patents

Abstract

The present invention discloses a dyeing composition for a nylon fiber material and a dyeing process using the same. A betaine-siloxane surfactant is used as a facilitating agent to dye nylon fiber and is very good in dyeing effect and excellent in dyeing rate or dyeing uniformity. According to this invention, the dyeing process using the betaine-siloxane surfactant involves the following steps: firstly, water-insoluble polysiloxane is modified by combining polysiloxane with a polyoxyethylene ether chain segment, so that the dyeing composition has excellent chemical stability and low skin irritation; and then, a condensation raction technology is employed to combine the modified polysiloxane with hydrophilic betaines, so that the water solubility and interfacial characteristics are greatly improved, and meanwhile, the dyeing composition also has the characteristics of biological decomposition, nature and environment protection and can be widely applied in industries related to dyeing and finishing.

Description

Dyeing composition of nylon fiber material and dyeing program using same

The present invention is a dyeing composition of nylon fiber material and a dyeing program using the same. The composition contains a betaine-siloxane type surfactant as a dyeing and finishing auxiliary agent. The present invention uses a betaine-siloxane type surfactant. As an adjuvant to dye nylon fibers, it was found that the dyeing effect was very good, regardless of dyeing rate or leveling property. The betaine-siloxane type surfactant described in the present invention is a combination of a polysiloxane and a polyoxyethylene ether segment first, and the water-insoluble polysiloxane is modified to have more excellent chemical stability. And low skin irritation, and then the modified polysiloxane is combined with hydrophilic betaines through condensation reaction technology, which greatly improves the water solubility and interface characteristics, and simultaneously has the characteristics of biodegradable natural environment protection , Can be widely used in related industrial uses such as dyeing and finishing.

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

Biological surfactant (Biosurfactant) is a secondary metabolite with certain biological activity secreted by microorganisms during metabolism. It is the same as general surfactants. Sexual surfactants are also composed of hydrophilic and hydrophobic groups, but biological surfactants have potential advantages over synthetic surfactants, including: biodegradable, non-toxic or low-toxic, and have a good environmental phase It can be used as an additive for cosmetics and pharmaceuticals; it can be produced by industrial waste to reduce industrial three wastes; it has better foaming properties under certain environmental conditions (such as high, low temperature, pH, salt concentration) ) Has higher selectivity and specificity; the structure is diversified, and it can be applied to special fields. At present, the application of biological surfactants has involved many fields such as petroleum, chemical industry and environment.

Decomposable surfactants are also called transient surfactants or controlled half-live surfactants (surfactants with controlled half-live). The initial definition is: after completing its application function, through acid, alkali, A type of surfactant that can be decomposed into non-surface-active substances or converted into new surface-active compounds by the action of salt, heat or light. This type of surfactant molecule often contains weak bonds with limited stability between the polar end and the hydrophobic chain. The cleavage of this weak bond can directly destroy the interfacial activity of the molecule, also known as the primary decomposition of the surfactant. Decomposable surfactants are generally classified into acetal type and ketal type according to the different decomposable functional groups. Compared with general surfactants, decomposable surfactants have better environmental protection concepts. Such 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 environmental impact and the speed of biodegradability have gradually become an important indicator for judging the quality of surfactants.

A reactive surfactant refers to a surfactant with a reactive group. It not only has interfacial activity, but also has a chemical reaction with the adsorbed substrate. It is permanently bonded to the surface of the substrate and becomes part of the substrate. Reactive surfactants typically have two characteristics: 1. they have interfacial activity, can participate in chemical reactions, and do not lose their interfacial activity after the reaction; 2. their molecular structure in addition to hydrophilic and hydrophobic groups, but also There should be reactive groups. In many cases, the use of reactive emulsifiers can solve various problems brought about by traditional chemical agents, and prepare polymers with clean surfaces and functional groups. The emergence of reactive surfactants has opened up new fields of surfactant synthesis and application. It can be widely used in emulsion polymerization, solution polymerization, dispersion polymerization, functional polymers, and the preparation of nanomaterials.

Because of its low cost and high application value, siloxane surfactants are widely used as wetting and emulsifying agents in the industry, and because of their smooth, oil-controlling, long-lasting, waterproof and gloss effects, The application of pharmaceuticals and cosmetics has become increasingly important. Siloxane also has a wide range of uses in the textile industry, including defoamers, lubricants and water repellency, softness and other properties. Siloxane has a high degree of flexibility and Having multiple methyl groups causes it to have lower cohesive energy, but the siloxane itself is water-insoluble, and it is still inconvenient in practical applications. The team of the present invention has passed this water-insoluble siloxane through maleic anhydride (maleic anhydride) and polyethylene glycols have been modified to become polyester-containing water-soluble polymers. These polymers have excellent interfacial properties, including surface tension, foamability, and wettability. In terms of application properties, this series of water-soluble polymers can be applied to acid dyed nylon fibers as leveling agents, increasing the affinity with dyes and reducing the diffusion rate of dye-surfactant complexes.

Betaine is an alkaloid found in sugar beet, and its molecular formula is C ₅ H ₁₁ NO ₂ . Can be used as amphoteric surfactants in detergents. It has good compatibility with various types of dyes, surfactants and cosmetic raw materials. It has excellent stability under acidic and alkaline conditions and is good for skin. Low irritation, good biodegradability, and excellent wettability. In addition, as a surfactant, it can effectively reduce surface tension. Siloxane is a semi-organic polymer and a heterogeneous polymer compound composed of silicon and oxygen. It can be used for antibacterial of fabric materials and is often used as a lubricant.

In order to improve the multifunctional use of polysiloxane and meet the requirements of environmental protection, the present invention combines the above two different substrates and has the advantages of various parties to synthesize and prepare the novel betaine-siloxane surfactant of the present invention. In the present invention, natural betaines are used as hydrophilic groups and polyoxyethylene ether segments to modify the siloxane. The betaine-silicone type surfactant obtained has the effect of interfacial activity of excellent emulsification and dispersion. And has low toxicity, biodegradability, and harmless to the human body.

Nylon fiber is made by condensation polymerization of amino (-NH-) acid or lactam. Acid dye contains acid group. Acid dye chemical structure contains -OH group, -SO ₃ H group, -COOH. The dyes in acidic or neutral dye baths are mostly sulfonic acid groups, easily soluble in water, and dissociated into dye cations in water. Under weakly acidic environment, Van der Waals and hydrogen bonding can be effected to obtain a good coloring rate and coloring, but acid dyes are not easy to dye nylon.

Nylon fibers and acid dyes have many applications in the industry. The betaine-silicone type surfactant of the present invention can be effectively used for this acid leveling agent, increasing the leveling and dyeing rate, and reducing the acid dye level. Usage amount. Therefore, the betaine-siloxane surfactant developed by the present invention is a nylon fiber dyeing and finishing additive, which can be effectively used in related fields. In addition, understanding the reaction conditions and actual process production can reduce process costs and factory machine work. The efficiency is improved, and the utilization rate of the equipment can be increased after the process is modified to reduce the cost. The betaine-silicone surfactant of the present invention has been confirmed by experiments to have a leveling effect, which can evenly dye the dye on the fiber, making The leveling phenomenon is reduced and the yield is greatly improved. The raw material used is natural betaine, which can improve the pollution caused by industrial additives and contribute to environmental protection.

The betaine-siloxane surfactant of the present invention has excellent dispersing ability, emulsifying ability, wettability, lubricity, gloss, and texture characteristics, and simultaneously has the characteristics of biodegradable natural environment protection. It is an excellent dyeing and finishing additive for textile dyeing and finishing industry. The fabric is not harmful to the skin after being dyed and fixed by synthetic products. The wastewater after dyeing and finishing can be decomposed by microorganisms and has no environmental impact. Pollution; The results of the betaine-siloxane type interfacial activity research of the present invention can be applied as industrial emulsification and dye dispersion technology for textile dyeing and finishing industry.

The present invention is a dyeing composition of nylon fiber material and a dyeing program using the same. The composition contains a betaine-siloxane type surfactant as a dyeing and finishing auxiliary agent. The present invention uses a betaine-siloxane type surfactant. As an adjuvant to dye nylon fibers, it was found that the dyeing effect was very good, regardless of dyeing rate or leveling property. The betaine-siloxane type surfactant described in the present invention is a combination of a polysiloxane and a polyoxyethylene ether segment first, and the water-insoluble polysiloxane is modified to have more excellent chemical stability. And low skin irritation, and then the modified polysiloxane is combined with hydrophilic betaines through condensation reaction technology to greatly improve water solubility. And interface characteristics, and at the same time have the characteristics of biodegradable natural environmental protection, can be widely used in related industrial uses such as dyeing and finishing.

The invention relates to a dyeing composition of nylon fiber material and a dyeing program using the same. The betaine-silicone type surfactant is used to improve the water insolubility of polysiloxane first. Modification of oxyethylene ether (EO) chain segments with different lengths, after modification, can have better chemical stability and low skin irritation, and is obtained by adding a biodegradable betaine raw material condensation reaction. The present invention uses a betaine-modified siloxane-type surfactant as an auxiliary agent for dyeing nylon fibers, and finds that the dyeing effect is very good, regardless of dyeing rate or leveling property, and has excellent industrial applicability and market substitution.

The invention relates to a dyeing composition of a nylon fiber material and a dyeing program using the same. The dyeing composition comprises a betaine-silicone type surfactant, a dye and a carrier having a specific structure. The content of the betaine-silicone type surfactant is 0.01% to 10% by weight based on the total weight of the dyeing composition; the content of dye is 0.01% to 10% by weight; and the content of the carrier is 80% to 10% by weight. 99.98% by weight. The dyeing composition of the present invention uses the betaine-silicone type surfactant as a dyeing assistant to help dye nylon fibers during the dyeing process. The betaine-siloxane type surfactant according to the present invention has the structure of the general formula (I), which is a modification of the water-insoluble polysiloxane through the combination of the polysiloxane and the polyoxyethylene ether segment first. So that it has more excellent chemical stability and low skin irritation, and then the modified polysiloxane is combined with hydrophilic betaines through condensation reaction technology, which greatly improves water solubility and interface characteristics, and simultaneously has both With the characteristics of biodegradable natural environment protection, it can be widely used in related industrial uses such as dyeing and finishing. In addition, it further improves the biodegradable efficiency.

其中R代表有機基團，包含相同或相異之選自氫原子、羥基(-OH)、烷基(C₁~C₁₀)、苯基之至少一種，y為1~20、z為1~20之整數，n為聚氧乙烯鏈重複單位數，其值為5~5000，w為聚矽氧烷重複單位數，其值為1~200，其中X^-選自羧酸根、磺酸根、硫酸根、磷酸根、-OH根之至少一種。 A dyeing composition of nylon fiber material, comprising: betaine-silicone type surfactant, based on the total weight of the dyeing composition, the content of the betaine-silicone type surfactant is 0.01 weight % To 10% by weight; dye, based on the total weight of the dyeing composition, the content of the dye is 0.01% to 10% by weight; and vehicle, based on the total weight of the dyeing composition, the The content of the carrier is 80% by weight to 99.98% by weight. The betaine-siloxane surfactant has a chemical structure of the following general formula:

Wherein R represents an organic group and contains at least one selected from the group consisting of a hydrogen atom, a hydroxyl group (-OH), an alkyl group (C ₁ to C ₁₀ ), and a phenyl group, and y is 1 to 20 and z is 1 to An integer of 20, n is the number of repeating units of the polyoxyethylene chain, the value of which is 5 to 5000, and w is the number of repeating units of the polysiloxane, the value of which is 1 to 200, where X ^-is selected from the group consisting of carboxylate, sulfonate, and sulfuric acid At least one of root, phosphate, and -OH.

According to the dyeing composition of the nylon fiber material of the present invention, the betaine-siloxane type surfactant is a combination of a polysiloxane hydrophobic group (Hydrophobic group) and a betaine-based hydrophilic group (Hydrophilic group). Due to its special chemical structure, it is easy to be adsorbed on the surface or interface of the solution at a very low concentration, thereby changing the surface or interface free energy of the solution, reducing its surface tension, and producing wetting, penetration, foaming, emulsification, dispersion and dissolution. And other characteristics.

In the dyeing composition of the nylon fiber material of the present invention, the betaine-silicone type surfactant is compounded with polysiloxane by using betaines, polyoxyethylene ether (EO) segments A series of water-soluble surfactants with good biodegradability, no pollution to the environment, and excellent properties are prepared. The betaine-siloxane type surfactant of the present invention combines polysiloxane and polyoxyethylene ether (EO) segments through polysiloxane to modify water-insoluble polysiloxane to provide more excellent chemical stability. And low skin irritation, and then reacted with betaine which is a biodegradable raw material. Betaine is an alkaloid found in beet. It can be used with various types of dyes, surfactants and cosmetic raw materials. Compatibility, excellent stability under acidic and alkaline conditions, low skin irritation, good biodegradability, and excellent wetting properties, combining the advantages of these two materials. Combining water-insoluble polysiloxane with hydrophilic betaines through condensation reaction technology to form a group containing hydrophilic and hydrophobic properties, greatly improving water solubility and exhibiting its own excellent characteristics, making it useful in use Wider industrial applicability. In addition, the biodegradable efficiency is further improved. The betaine-silicone type surfactant described in the present invention has excellent dispersing and emulsifying ability, wetting and lubricating, and improving gloss texture characteristics, and simultaneously has the characteristics of biodegradable natural environment protection, and can be widely used in dyeing It has excellent industrial applicability and market substitution in related industrial uses such as cosmetics, cleaning products, food emulsification, pharmaceutical emulsification, and drug release. It is an excellent dyeing and finishing additive for textile dyeing and finishing industry. The fabric is not harmful to the skin after being dyed and fixed by synthetic products. The wastewater after dyeing and finishing can be decomposed by microorganisms and has no environmental impact. Pollution; The results of the betaine-siloxane type interfacial activity research of the present invention can be used as industrial emulsification and dye dispersion technology for textile dyeing and finishing industry.

其中R代表有機基團，包含相同或相異之選自氫原子、羥基(-OH)、烷基(C₁~C₁₀)、苯基之至少一種，y為1~20、z為1~20之整數，n為聚氧乙烯醚鏈段重複單位數，其值為5~5000，w為聚矽氧烷重複單位數，其值為1~200，其中X^-選自羧酸根、磺酸根、硫酸根、磷酸根、-OH根之至少一種離子。 The dyeing composition of the nylon fiber material of the present invention, the betaine-silicone type surfactant, using betaine, polyoxyethylene ether (EO) segment and polysiloxane compound to prepare a series of It is biodegradable, does not cause pollution to the environment, and has excellent properties of water-soluble surfactants, which are composed of polyoxyethylene ether segments (selected from: polyethylene glycol, polyethylene oxide, polyoxyethylene) It is formed by linking polysiloxane compounds and reacting with betaine compounds. Structure with general formula (I) as shown below

Wherein R represents an organic group and contains at least one selected from the group consisting of a hydrogen atom, a hydroxyl group (-OH), an alkyl group (C ₁ to C ₁₀ ), and a phenyl group, and y is 1 to 20 and z is 1 to An integer of 20, n is the number of repeating units of the polyoxyethylene ether segment, the value of which is 5 to 5000, and w is the number of repeating units of the polysiloxane, the value of which is 1 to 200, where X ^-is selected from the group consisting of carboxylate and sulfonate At least one ion of sulfate, phosphate, -OH.

The method for preparing the betaine-siloxane surfactant according to the present invention comprises the following steps: (a) reacting a polysiloxane compound with polyoxyethylene, and reacting at 10 to 220 ° C for 1 to 24 hours to obtain a reaction Compound A; (b) Reactant A reacts with an alkylene chloride compound and reacts at 10 to 80 ° C for 1 to 10 hours to obtain reactant B; (c) Reactant B and dimethylamine at 40 to 100 Reaction at 2 ° C for 8 hours to obtain reactant C; (d) Reactant C reacts with haloalkanoate and reacts at 60 to 110 ° C for 5 to 20 hours to obtain betaine-siloxane type surfactant product.

The method for preparing a betaine-siloxane type surfactant according to the present invention, wherein the siloxane compound is selected from the group consisting of a polymer having a repeating Si-O as a main chain and an organic group connected to a silicon atom. The general formula is [R _s SiO _{4-s / 2} ] _w , where R represents an organic group containing the same or different and is selected from the group consisting of a hydrogen atom, an alcohol group (OH), an alkyl group (C ₁ to C ₁₀ ), and a phenyl group. , S is 0 to 4, and w is the number of repeating units of the organic group connected to the silicon atom, and is an integer of 1 to 200, preferably an integer of 20 to 100.

The preparation method of betaine-siloxane type surfactant according to the present invention, wherein The alkylene chloride compound is selected from epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, epichloroheptane, epichlorohydrin to epichlorohydrin. Decane.

In the method for preparing a betaine-siloxane surfactant according to the present invention, the polyoxyethylene ether segment is selected from the group consisting of polyethylene glycol (PEG), polyethylene oxide (PEO), or polyoxyethylene (POE).

，其中H選自氟、氯、溴、碘之鹵素，X^-選自羧酸根、磺酸根、硫酸根、磷酸根、-OH根之至少一種離子，z為1~20之整數。 The method for preparing the betaine-siloxane type surfactant according to the present invention, wherein the haloalkanoate has the following chemical structure:

Wherein H is selected from fluoro, chloro, bromo, halo iodine, X ^- is selected from carboxylate, sulfonate, sulfate, phosphate, -OH roots of at least one ionic, z is an integer of from 1 to 20.

In the method for preparing betaine-siloxane surfactant according to the present invention, the steps (a) to (d) have a synthesis temperature of 10 to 220 ° C, a synthesis time of 1 to 24 hours, and a catalyst selection step (a). From: at least one or a combination of titanium isopropoxide (IV), titanium isopropoxide (Sulfuric acid), hydrochloric acid (Hydrochloric acid), step (b) reactant A epoxy alkylene chloride compound reaction In alkaline (1 ~ 10% sodium hydroxide, potassium hydroxide solution), the catalyst is selected from the group consisting of: Tetrabutylammonium bromide (TBAB), benzyltriethylammonium chloride, trioctyl Reaction under the conditions of methylmethylammonium chloride and tetramethylammonium bromide.

Structural analysis of betaine-siloxane surfactant according to the present invention IR: Perkin-Elmer Spectrum One (Perkin Elmer Cetus Instruments, Norwalk, CT). The sample was concentrated, dried under vacuum to remove moisture, and then coated with KBr Test on salt tablets.

Infrared spectrometer (FT-IR) is the absorption of radiation in the infrared region by molecules to cause vibration and conversion. Infrared absorption spectrum generated by the migration of kinetic energy levels to identify compounds is mostly used for functional group identification. All molecules have a fixed energy, which causes the bonds to stretch and bend, while 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 relatively specific energy level, and when the molecule is illuminated by infrared light, the vibrational bond can be absorbed only when the frequency of the light is the same as the vibration frequency of the part energy.

The analysis results of the betaine-siloxane type surfactant synthesized by the present invention are shown in Fig. 1. The characteristic absorption peaks of OH at 3449 ~ 3647cm ^-1 , -CH ₂ symmetrical stretching vibration and asymmetric stretching vibration absorption wave front are respectively At the positions of 2864cm ^-1 and 2918cm ^-1 , 1650 ~ 1670cm-1 is the C = C characteristic absorption peak, 1460cm ^-1 is the -CH-asymmetric stretching vibration absorption peak, 1230cm ^-1 is the CN characteristic absorption peak, 1050 ~ 1200cm ^-1 is -SO ₃ characteristic absorption peak, 1040 ~ 1110cm ^-1 is CO characteristic absorption peak, 800 ~ 1000cm ^-1 is CC characteristic absorption peak, showing the function of the betaine-silicone type surfactant structure according to the present invention. The characteristic absorption peak of the radical.

Performance analysis of betaine-siloxane type surfactant of the present invention:

Basic properties

(1) Surface tension: Japan Kaimenkaguka CBVP-A3 Surface Tensiometer (Kyowa interface Science Co., Japan), measured with a digital hanging platinum sheet (type) surface tension tester. The instrument completes the calibration procedure, burns the platinum film with alcohol, hangs it on the hook after cooling, cleans and dries the glass dish, and then injects the test solution. (Approximately eight minutes full), start the instrument switch, the lifting platform will slowly rise. When the platinum sheet touches the liquid surface, the lifting platform will automatically stop and record the measured value when it is stable. Repeat the above steps several times to find the average. The analysis result of the betaine-siloxane type surfactant synthesized by the present invention is shown in FIG. 2.

(2) Contact angle: FACE CA-5 Contact Angle meter, place a standard plate on the material table to be tested, suck the sample solution with an injection syringe, and control the size of the droplet to about 20mm. Ascend the sample table to make the standard plate come into contact with the droplets. At this time, the droplets will drop on the standard plate (start timing), adjust the instrument according to the correct operation steps, and read the angle (θ) directly by the eyepiece after 1 minute, and 2θ is the contact angle. The analysis result of the betaine-siloxane type surfactant synthesized by the present invention is shown in FIG. 3.

(3) Foaming property: As measured by the Ross and Miles method, 500 ml of a 0.1 wt% betaine-silicone type surfactant aqueous solution was prepared and placed in a sample tank. The flow rate of the fixed motor is 400ml / min. After 1 hour, the foam height in the measuring cylinder is recorded, which is the maximum foam height. Turn off the pump and record the foam height after 3 minutes. This is the foam stability. The analysis result of the betaine-siloxane type surfactant synthesized by the present invention is shown in Fig. 4.

(4) Fluorescence properties: Fluorescence spectrometers have the advantages of high sensitivity and low sample usage. Fluorescent reagent pyrene is used to confirm the affinity of molecular cohesion and describe the characteristics of cell aggregation, which can be used to obtain betaine. -The critical microcellular concentration range of the siloxane surfactant. The main spectroscopic instrument parameters include excitation and emission spectrum types, fine vibration structure, quantum ratio, and polarity in aqueous solution. These properties are related to the microenvironment and can be used to predict hydrophobicity. Aminco-Bowman Series 2 Luminescence Spectrometer, take 0.2ml pyrene alcohol solution in a 100ml beaker, put it in a 40 ° C oven and dry the alcohol. Betaine-silicone type surfactant aqueous solution was formulated at 0.1%, and stirred well. Weigh out 20g of amino acid surfactant solution into the dried beaker. The ultrasound oscillated for 15 minutes. Excitation wavelength is 335nm and emission wavelength is 350 ~ 450nm. The analysis result of the betaine-siloxane type surfactant synthesized by the present invention is shown in Figure 5.

(5) Electrical conductivity: In the dyeing process, the dyeing solution is a mixture of dyes and various surfactants. In the dyeing bath, various types of cells are formed due to molecular attraction, which affects the formation of cells. Electrical conductivity. Too high conductivity will cause uneven dyeing, and the dye powder cannot be uniformly dispersed, resulting in agglomeration of the powder. Therefore, the conductivity of the dye and the surfactant must be controlled to achieve the effect of leveling. The conductivity meter must be calibrated and the detection electrode cleaned. A 1 wt% betaine-siloxane surfactant solution was prepared, the temperature was fixed at 25 ° C, and it was recorded. Sequentially add pure water to dilute, and measure its conductivity at different concentrations. The analysis result of the betaine-siloxane type surfactant synthesized by the present invention is shown in FIG. 6.

(6) Biodegradable rate (BOD ₅ / COD Index): BOD ₅ biochemical oxygen demand represents the organic matter that can be biodegraded in the wastewater, and COD chemical oxygen demand can represent all the organic substances in the wastewater. The larger the BOD ₅ / COD value in (1), the larger the proportion of pollutants contained in wastewater that can be decomposed by microorganisms, that is, the better the biodegradability of wastewater. Therefore, the determination of the ratio of BOD ₅ to COD is the easiest method to identify the biodegradability of wastewater.

In the following, BOD ₅ / COD × 100% is divided into three cases:

(1) BOD ₅ / COD × 100% ≧ 60%: Most of the organic matter contained in wastewater can be decomposed by organisms.

(2) BOD ₅ / COD × 100% ≒ 20%: Organic matter contained in wastewater is not easily biodegradable, and microorganisms need to be domesticated.

(3) BOD ₅ / COD × 100% ≒ 0%: Wastewater contains toxic substances, which is not easy to be treated by biological treatment.

COD Chemical Oxygen Demand Spectrophotometer, HACH, Model DR / 2800 Chemical Oxygen Demand Reactor, Rocker, Model CR25

(1) Prepare 2.00ml of sample solutions of different concentrations and place them in a colorimetric tube.

(2) Place the colorimetric tube in the COD heater and wait for the temperature to rise to 120 ℃

(3) After cooling to room temperature, read the value with the instrument of the COD chemical oxygen demand spectrophotometer.

BOD ₅ BOD

(1) Prepare 420ml of sample solutions of different concentrations and place them in a brown serum bottle.

(2) Add 1ml of nutrient source capsules and activated sludge to the brown serum bottle.

(3) Apply the sealing paste to the bottle mouth, cover the bottle stopper device in the incubator (constant temperature 20 ° C).

(4) After five days, use BOD ₅ BOD instrument to read its value.

The test results are shown in Tables 1 and 2.

2. Emulsifying properties

Emulsions is a colloidal solution. Its composition is two liquids that are mixed or partially mixed with each other. One phase in the state of small particles is called a dispersed phase, that is, a discontinuous phase. In general, the particle diameter of the dispersed phase is about 0.1 to 10 μm. In addition, the other phase present in the emulsion is called the dispersion medium, which is the continuous phase. It is stabilized by external force (mechanical force) or natural change. This method is called the forced dispersion emulsification method of emulsification machinery.

When the emulsion is formed, the contact area of the two phases is increased. The droplets need to be stably dispersed in the medium for non-spontaneous behavior. This dispersed state will proceed in the direction of reducing the contact area, that is, it will be divided into complete two phases, and delamination will occur. . Therefore, a third substance needs to be added to form and stabilize the emulsion, and this substance is an emulsifier, so-called surfactant. In addition, the charge of the emulsion also affects the formation and stability of the emulsion. When the particles have a charged state, it has an important effect on the stability of the emulsion. There are two sources of charge around the particles:

(1) If the surfactant is ionic, it will dissociate itself to generate a charge, and the charge dissociated due to its different properties will also be different.

(2) If the surfactant is non-ionic, a charge is generated by friction between particles in the emulsion and the dispersion medium. When the particles are charged, there will be electrostatic repulsion between the particles, so that the particles will not contact and aggregate with each other, so that the emulsion can exist stably.

Method for measuring emulsification properties:

(1) Formulating a 1 wt% solution of the betaine-siloxane surfactant of the present invention and other different surfactants.

(2) Weigh out 10wt% (O / W) of jojoba oil and various surfactant solutions.

(3) Stir with a homogenizer (Ultra Turrax T25 Homogenizer) at a rotation speed of 11,000 rpm for 10 minutes, and let stand for 10 minutes to form various emulsions.

(IV) Viscosity test of various emulsions

(5) Measure the interfacial potential (zeta potential) of each emulsion with an interfacial potential meter (Colloidal Dynamics, Zeta Probe Analyzer).

(6) Measure the particle size and distribution of each emulsion droplet with a Particle Size Distribution Analyzer.

(7) Measuring cylinder test.

(8) Centrifugal analysis.

The test results are shown in Figures 7-16.

The betaine-siloxane surfactant of the present invention has excellent dispersing and emulsifying ability, wetting and lubricating, and improving gloss texture characteristics, and simultaneously has the characteristics of biodegradable natural environment protection, and can be widely used in dyeing and finishing, Cosmetics, cleaning products, food emulsification and other related industrial uses have excellent industrial applicability and market substitution.

The inventors of this case successfully synthesized betaine-silicone type surfactants. Mingnai uses this betaine-siloxane type surfactant for nylon fiber materials with different color acid dye concentration and different additive concentration to get deep dyeing and uniform effect.

In a dyeing process according to an embodiment of the present invention, dyeing a nylon fiber material using a dyeing composition includes the following steps. In the dipping step, the nylon fiber material is dipped into the dyeing composition at room temperature. In the slow dyeing step, the dyeing composition and the nylon fiber material soaked therein are heated to a temperature of 60 ° C to 110 ° C at a temperature rising rate of 0.5 ° C / min to 5 ° C / min. In the dyeing step, the dyeing composition and the nylon fiber material soaked therein are maintained at a temperature of 60 ° C to 110 ° C for 20 minutes to 60 minutes. After the temperature is lowered, the dyeing composition and the nylon fiber material soaked therein are reduced to a temperature of 40 ° C to 80 ° C at a cooling rate of 0.5 ° C / min ~ 5 ° C / min, and then the nylon fiber material is removed from the dyeing composition. .

In the dyeing composition according to an embodiment of the present invention, the content of the betaine-siloxane-type surfactant is, for example, 0.05% 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, 0.05 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 fiber material of the present invention includes the following steps: providing the fiber material and providing a dyeing composition, wherein the dyeing composition includes betaine-silicone in an amount of 0.01% to 10% by weight based on the total weight of the dyeing composition. Alkane type surfactant, the content of the dye is 0.01% to 10% by weight, and the content is 80% to 99%. 98% by weight of vehicle. The fiber material is dyed with the dyeing composition.

In an embodiment of the present invention, the dye may be adsorbed on the surface of the nylon fiber material through a dyeing process by a molecular force (such as hydrogen bonding or van der Waals force). The dye is an acid dye, which is, for example, Red 114 dye (C.I. Acid Red 114, Dianix Rubine SE-B, manufactured by Dystar).

The content of the dye is from 0.01% by weight to 10% by weight, and preferably from 0.05% by weight to 5% by weight, based on the total weight of the dyeing composition. The content of the dye can be adjusted according to the actual dyeing conditions. When the content of the dye is less than 0.01% by weight, the nylon fiber material cannot be effectively dyed to the desired color; and when the content of the dye is more than 10% by weight, excess dye may remain on the nylon fiber material, causing further damage. Problems with dye waste or environmental pollution.

In the embodiment of the present invention, the role of the carrier is to provide an environment in which the dye and betaine-silicone 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. The content of the carrier is from 80% by weight to 99.98% by weight based on the total weight of the dyeing composition.

In addition, in the embodiment of the present invention, the dyeing composition may further include a pH adjuster for adjusting the pH of the dyeing composition. At room temperature, the pH of the dyeing composition may be, for example, 2 to 6, and the pH adjusting agent may be, 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 charge of the nylon fiber material, and also increase the degree of dye dispersion and the speed with which it is combined with the nylon fiber material.

Based on the above, it is known that betaine-silica is included in the dyeing composition. Alkane type surfactant, so when using the dyeing composition to dye the fiber material, the dyeing composition can have a good dyeing rate and leveling property on the fiber material, thereby achieving deep dyeing and easy dyeing of the fiber material The effect, especially the nylon fiber material, also makes the dyed nylon fiber material have good washing fastness and light fastness.

Another embodiment of the present invention provides a fiber material dyeing program, which uses the dyeing composition of the present invention to dye a fiber material. Compared with the conventional dyeing process, the nylon fiber material dyed through the dyeing process of the present invention can have good fastness to washing and fastness to light.

In the dyeing procedure provided in this embodiment, a nylon fiber material and the dyeing composition described in the above embodiment are first provided, and then the nylon fiber material is dyed using the dyeing composition. In the dyeing procedure, the bath ratio of the nylon fiber material to the dyeing composition is, for example, about 1:10. For example, if a nylon fiber material weighing 10 grams is to be dyed, it can be immersed in a dyeing composition weighing 100 grams.

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

In the embodiment of the present invention, the dipping step is, for example, immersing the nylon fiber material in the dyeing composition at room temperature. After the dipping step, a retarding step is performed. The slow-dyeing step is, for example, heating the dyeing composition and the nylon fiber material immersed therein to a temperature of 60 ° C. to 110 ° C. at a temperature rising rate of 0.5 ° C./min to 5 ° C./min. During the impregnation step In the slow-dyeing step, the dye in the dyeing composition can be initially adsorbed on the surface of the nylon fiber material, and the nylon fiber material can be dyed to a color corresponding to the dye.

After the dipping step and the retarding step, a dyeing step is performed. The dyeing step is, for example, maintaining the dyeing composition and the nylon fiber material soaked therein at 60 ° C to 110 ° C for 20 minutes to 60 minutes. In the above-mentioned dip dyeing step, slow dyeing step, and dyeing step, since the dyeing composition of the present invention contains betaine-silicone type surfactant, the dyeing composition is suitable for nylon fibers at a temperature of 60 ° C to 110 ° C. The material has good dyeing rate and leveling property, so that the dyed nylon fiber material has good fastness to washing and fastness to light.

After the dyeing step, a cooling-out step is performed. The step of cooling out of the vat, for example, reduces the dyeing composition and the nylon fiber material soaked in the dyeing composition to a temperature of about 40 ° C. to 80 ° C. at a cooling rate of 0.5 ° C./min to 5 ° C./min. take out. In addition, after the temperature-reducing step, the dyed fiber material can be washed, dehydrated, and air-dried.

Based on the above dyeing results, as shown in Tables 3 to 11, in the dyeing process of the present invention, since the nylon fiber material is dyed using a dyeing composition containing a betaine-silicone type surfactant, the dyed nylon The fiber material has good coloring rate and leveling property.

Figure 1. Infrared spectrum of betaine-siloxane surfactant of the present invention

Figure 2. Surface tension test chart of betaine-siloxane surfactant of the present invention

Figure 3. Contact angle test chart of betaine-siloxane type surfactant of the present invention

Figure 4. Foaming and Foam Stability Diagram of Betaine-Silane Surfactant of the Present Invention

Figure 5. Fluorescence spectrum of betaine-siloxane surfactant of the present invention

Figure 6. Electrical conductivity test chart of betaine-siloxane type surfactant of the present invention

Figure 7. Test potential diagram of the interfacial potential of the betaine-siloxane surfactant of the present invention

Figure 8. The average particle size distribution of betaine-silicone type surfactant of the present invention

Figure IX. Viscosity comparison chart of betaine-silicone surfactant (PEG2000) and other surfactant emulsified 10wt% jojoba oil emulsion (O / W) of the present invention

Fig. 10 Centrifugal diagram of emulsified 10wt% jojoba oil emulsion (O / W) of betaine-silicone surfactant (PEG2000) and other surfactants of the present invention

Figure 11: Measuring chart of a graduated cylinder of betaine-silicone type surfactant (PEG2000) and other surfactants of the present invention emulsified 10wt% jojoba oil emulsion (O / W)

Figure 12.Interfacial potential (zeta potential) of non-ionic surfactant (C ₁₄ H ₂₂ O (C ₂ H ₄ O) n) emulsified 10wt% jojoba oil emulsion (O / W)

Figure 13. Interfacial potential (zeta potential) of the betaine-siloxane surfactant (PEG2000) emulsified 10wt% jojoba oil emulsion (O / W) of the present invention

Figure 14.Interfacial potential (zeta potential) of an emulsion of 10 wt% jojoba oil (O / W) emulsified by anionic surfactant (SDS)

Figure 15.Interfacial potential (zeta potential) of a cationic surfactant (CTAB) emulsified 10wt% jojoba oil emulsion (O / W)

Figure 16. Comparison chart of the interfacial potential (zeta potential) of the betaine-silicone type surfactant (PEG2000) of the present invention and other surfactants emulsified 10wt% jojoba oil emulsion (O / W)

Figure XVII. Nylon Fiber Cloth Dyed with Acid Dyes as Betaine-Siloxanes Surfactant of the Invention as an Auxiliary

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

Preparation and property determination of betaine-siloxane type surfactant according to the present invention

Materials used:

(1) Siloxane, the general formula x = 1 ~ 200, x = 42 in the embodiment

(2) Polyoxyethylene ether segments with molecular weights of 2000, 4000, 6000, and 8000 (g / mol) polyethylene glycol (PEG)

(3) Dimethylamine

(4) epichlorohydrin

(5) ClCH ₂ CH ₂ CH ₂ SO ₃ Na

(6) Sodium hydroxide

(7) Titanium isopropoxide (IV)

(8) Tetrabutyl ammonium bromide (TBAB)

(9) Jojoba oil

(10) Non-ionic surfactant: C ₁₄ H ₂₂ O (C ₂ H ₄ O) n, n is 9 or 10, (TritonX-100)

(11) Anionic surfactant: Sodium dodecyl sulfate (SDS)

(12) Cationic surfactant: Cetyl trimethyl ammonium bromide (CTAB)

The synthesis of the betaine-siloxane surfactant of the present invention is as follows:

(1) Reaction of 1 mol of polyethylene glycol (2000, 4000, 6000, 8000, 10000), 1 mol of polysiloxane and 1 g of titanium isopropoxide (IV) (Titanium isopropoxide (IV)) catalyst at 150 ° C 6 hours, reactant A was obtained.

(2) Add reactant A to epichlorohydrin, and react in the presence of 3% sodium hydroxide and Tetrabutyl ammonium bromide (TBAB) catalyst at about 55 ° C for about 5 hours to obtain a reactant. B.

(3) Dimethylamine is added to the reactant B and reacted at about 70 ° C. for about 4 hours to obtain a reactant C.

(4) The reaction product C is added with ClCH ₂ CH ₂ CH ₂ SO ₃ Na, and then reacted at about 85 ° C. for about 10 hours to obtain a betaine-silicone type surfactant product.

Basic properties of betaine-siloxane type surfactant according to the present invention

(1) Surface tension

Surfactant added to the aqueous solution will reduce the surface tension, because the surfactant itself contains hydrophilic and hydrophobic groups in the structure, the hydrophilic part of the solution will remain in the water, and the hydrophobic part will be adsorbed to protrude the water surface. To. This arrangement will reduce the asymmetric hydrogen bonding force of water molecules on the surface, resulting in a decrease in surface free energy, and thus a decrease in surface tension. At 25 ° C, the surface tension of pure water is about 72.8mN / m. However, as the surfactant concentration increases, the surface tension value varies with Its reduction. When the concentration increase reaches a certain level, the surfactant molecules in the solution begin to attract and aggregate with each other with hydrophobic groups to form so-called microcells. The concentration at which microcells begin to form is called critical microcellular concentration (Critical Micelle Concentration; cmc).

Figure 2 is a surface tension test chart of the betaine-siloxane surfactant of the present invention. The results show that as the molecular weight of PEG increases, the surface tension decreases, and the molecular weight of PEG increases with a higher proportion of EO in the structure. Chain, so that the oxygen atom and water molecules in the chain segment have a higher hydrogen bonding ratio, resulting in increased hydrophilicity of the product in water, and the state of adsorption on the surface is jagged, and when the concentration increases, its molecules are densely arranged on the surface and disorder Therefore, when the concentration increases, the surface tension value does not decrease sequentially.

(2) Contact angle

Wetting is the phenomenon in which a fluid phase on a solid or liquid surface is replaced by another fluid phase. Generally, the situation where the air on a solid surface is replaced by a liquid phase such as water or oil is called wetting. The molecules on the surface of the liquid are affected by the gravitational forces of the internal molecules to form a gravitational force to reduce the surface area, so the droplets are all spherical. If a surfactant is added, it can help water wet a solid surface to achieve a wetting effect. The size of the wetness and permeability is generally expressed by the contact angle.

Figure 3 is the contact angle test results of betaine-silicone type surfactant of the present invention on different test boards at a concentration of 1% by weight. The angles measured by water on various test boards are Acrylic about 80, PVC about 70, Teflon is about 100, and the data measured by the contact angle of the betaine-silicone type surfactant of the present invention are less than water, so it has a moisturizing effect.

(3) Foaming

Foaming is one of the characteristics of surfactants. Bubbles are substances formed by liquid films surrounding gas. Such films are easy to form but difficult to rupture. After stirring, many bubbles will be generated. A thin film is a foam. Surfactants are added to the aqueous solution to mechanically stir the air into the solution to form bubbles formed by the solution. At this moment, the hydrophobic groups are generated toward the inside of the bubbles, and the hydrophilic groups are adsorbed toward the solution phase. The bubbles rise in the solution by buoyancy and impact. The surface of the solution forms a two-molecule film with the surfactant molecules adsorbed on the surface of the solution. If the appropriate conditions are met, bubbles will rise from the surface to the outside air, and the two molecules will surround the bubbles and escape in the air. It is often necessary to add a surfactant during the dyeing process to improve the dyeing quality. During the operation, the machine turns and the gas enters the dyeing solution, which causes foam. Too much foam will hinder the contact between the dye solution and the fibers and cause uneven dyeing. Therefore, the surfactant used in the dyeing and finishing process must have low foaming properties.

Figure 4 is a comparison chart of the product with the highest and lowest proportion of EO chain in the betaine-siloxane type surfactant of the present invention. Generally speaking, the foaming power of the anionic series surfactant is above 20 cm, and the betaine of the present invention -The structure of Si containing surfactant in the structure containing Si, has the function of defoaming, so a series of products are low foaming. In this series of products, the higher the EO chain hydrophilic ratio is, the higher the foaming power is, but the foam stability is not changed much.

(4) Fluorescence properties

In microcell and microenvironment systems, the application of physical chemical technology has become a very important tool in research. Pyrene, a fluorescent reagent, was used to recognize the unique affinity of the molecular agglomerates, and the interaction between the surfactant and the molecules was used to explore the characteristics of its radioactive mass and cell aggregation. The main spectroscopic instrument parameters include Excitation and Emission spectrum forms, fine vibration structure, quantum ratio, and polarity in solution.

Figure 5 shows the fluorescence spectrum of the betaine-siloxane surfactant of the present invention. The hydrophilicity of the product can be determined by the intensity of the fluorescence. As shown in the results, the fluorescence of the EO chain increases with the proportion of hydrophilicity of the EO chain. The intensity of the PEG8000 is increased, which indicates that the PEG8000 has the highest fluorescence intensity, which indicates that the EO chain can properly interact with the Pyrene molecule, and the excessively hydrophilic ratio of the EO chain results in disordered adsorption, which affects the fluorescence characteristics .

(5) Conductivity

Conductance refers to the ability of a substance to pass an electric current. A solution generates an electric current by the movement of anions and cations. Since the rate of ion movement becomes faster with increasing temperature, the conductance increases with increasing temperature. The conductivity in water is standardized as the conductivity after the unit is standardized. The electrolyte in water will dissociate into ions and has the function of conductivity. Therefore, the conductivity is an indicator of the amount of electrolyte in the water. The measured conductance of the solution is directly proportional to the area of the electrode and inversely proportional to the distance of the electrode, so it is generally converted to the value of area 1cm ² and distance 1cm, which is the conductivity. The conductivity of water is very small, and it is generally expressed in micromho / cm (μmho / cm, μS / cm).

FIG. 6 is a conductivity test chart of the betaine-siloxane surfactant of the present invention. From the results of the conductivity test, a series of products with a concentration of 0.1wt% has a significantly increased conductivity. When the concentration reaches 1wt%, the EO chain is hydrophilic As the ratio increases, the conductivity increases.

(6) Biodegradable rate

Biochemical oxygen demand (BOD ₅ for short) is the amount of dissolved oxygen required for aerobic microorganisms in water to decompose organic matter in water to inorganic matter at a certain temperature during this specific time. Chemical Oxygen Demand (COD) is a chemical method to measure the amount of oxygen consumed by organic matter in a water sample when it is oxidized by a strong oxidant. It is used to indicate the amount of organic matter in water. Under certain conditions, the amount of oxidant consumed by oxidizing reducing substances in 1 liter of water sample is used as an indicator, and converted into the number of milligrams of oxygen required per liter of water sample, expressed in mg / L. It reflects the extent to which water is contaminated by reducing substances. This index is also used as one of the comprehensive indicators of the relative content of organic matter. The ratio of biochemical oxygen demand to chemical oxygen demand (COD) can explain the proportion of organic matter that is difficult to biodegrade in water, and organic pollutants that are difficult to decompose by microorganisms are more harmful to the environment. The ratio of BOD ₅ / COD reflects the biodegradability of wastewater. BOD ₅ is close to or more significant than COD (typically 60% or more within 28 days), then the substance can be said to be biodegradable.

Table 1 is a decomposability index table of the betaine-siloxane type surfactant of the present invention at a concentration of 0.01% by weight. The results show that the percentage of BOD ₅ / COD of a series of products is greater than 60%, and only PEG10000 Less than 60%, so the betaine-siloxane surfactant of the present invention has biodegradability.

Emulsifying performance of betaine-siloxane type surfactant of the present invention

(1) Interfacial potential

Emulsions is a colloidal solution. Its composition is two liquids that are mixed or partially mixed with each other. One phase in the state of small particles is called a dispersed phase, that is, a discontinuous phase. In general, the particle diameter of the dispersed phase is about 0.1 to 10 μm. In addition, the other phase present in the emulsion is called the dispersion medium, which is the continuous phase. In colloid chemistry, it is believed that solid colloidal particles have an electric double layer on the surface of the solution, the surface of the solid particles has a positive charge, and the negatively charged ions in the solution attract each other so that the solid surface is distributed in a layered form. Stern layer. In the electric field, the solid particles will move relative to the water along the surface of the shear. The ions in the surface of the shear and the solid surface are tightly coupled, and will move relative to the surface of the shear, leaving the surface of the shear outside. The ions are distributed in the solution in a diffused state, and the potential difference between the shear surface and the solution body is the interface potential (ζ, zeta potential, Zeta Potential).

FIG. 7 is an interface potential test chart of the betaine-siloxane surfactant of the present invention. The results show that PEG10000 in the product has a larger absolute potential value, and therefore has a larger charge repulsive force between the particles to facilitate the dispersion of the emulsion. stability.

(2) Particle size and distribution

Emulsification is two insoluble liquids, one of which is a state of fine particles with a diameter of about 0.1 to 5 μm, which is evenly dispersed in another liquid. The operation is called emulsification. The size of the particles in the emulsion can identify the degree of emulsification ability. Generally speaking, the narrower the particle size distribution range, the smaller the particle size, and the better the stability of emulsification, but the particles of the emulsion do not undergo fusion with time. That is, it has excellent stability.

The quality of the emulsion is related to the droplet size of the dispersed phase. The purpose of general emulsification is to maintain the state of the droplets. The size of the droplets cannot increase sharply with time. The stability of the droplets depends on the surfactant The emulsification ability is different, and the emulsification process includes two steps: (1) the droplets are broken and deformed when the specific surface area of the emulsion is increased, and (2) the stability of the new interface formed by the surfactant.

There are three effects of adding emulsifiers: (a) reducing the interfacial tension, (b) promoting the mechanical protection of the particle surface through the process of adsorption, and (c) promoting the repulsion between particles through the use of ionicity. .

Figure 8 is the average particle size distribution of betaine-silicone surfactant of the present invention on olive oil as an emulsion. The measured particle size is between 1 and 4 μm . It can be observed that when the average particle size of PEG2000 is small, and the particle size range of the droplets is narrow, it shows a curve of a single peak, showing that most emulsion droplets have a uniform particle size and high stability, while others The emulsion of the product produces Brownian motion to agglomerate the molecules and present a wide range of particle sizes.

The betaine-siloxane surfactant (of which polyethylene glycol PEG2000 is selected), the conventional nonionic surfactant (C ₁₄ H ₂₂ O (C ₂ H ₄ O) n), and the anionic interface activity of the present invention Comparison of emulsifying performance of the additives (Sodium dodecyl sulfate (SDS)) and cationic surfactant (Cetyl trimethyl ammonium bromide (CTAB)), as shown in Figures 9 ~ 10 Six as shown.

Figure 9 shows the viscosity of four different types of surfactants emulsified with jojoba oil. It can be seen that the four emulsions are Newtonian fluids.

Figure 10 is a centrifugal diagram of the emulsion of four different types of surfactants and 10wt% jojoba oil after emulsification. It can be seen from the beginning that the cationic surfactant has poor emulsification effect and the oil-water separation is more serious. After 5 minutes of centrifugation All four surfactants have been separated. It can be seen that after 30 minutes of centrifugation, the emulsification and separation of non-ionic, betaine-siloxane, and anionic surfactants of the present invention has been stabilized, while cationic interface activity The separation of the emulsifier is more obvious.

The measurement of the graduated cylinder can discuss the stability of the emulsion. It can be seen from Figure 11 that with time, the height of the non-ionic and anionic surfactant emulsified graduated cylinders does not change much and is more stable. The cationic surfactant emulsion and beet Alkali-siloxane surfactant emulsions are separated and separated from oil and water, but cationic surfactant emulsions are more severe than betaine-siloxane surfactants, and they change significantly over time, showing that the invention Emulsion of betaine-silicone surfactant is more stable than cationic surfactant.

The larger the absolute value of the interfacial potential (zeta potential), the greater the repulsive force between the colloidal particles, the better the dispersibility, the less prone to agglutination, and the higher the emulsion stability. Figures twelve to fifteen are the individual interface potentials (zeta potentials) of the four surfactants. The horizontal axis is pH and the vertical axis is the interface potential (zeta potential) value. The interface potential (zeta potential) value is increased with the increase of pH. It has also increased. Among them, the use of non-ionic surfactant emulsifiers, when the acid-base value reaches pH 7, the change in the interfacial potential (zeta potential) tends to a stable state; betaine-siloxane surfactant emulsifiers tend to be partial. The interfacial potential (zeta potential) in the acidic environment changes slowly, while the interfacial potential (zeta potential) in the alkaline environment decreases from pH7 to pH10; the anionic surfactant emulsification solution changes with the pH value of pH3 ~ Under the change of pH10, the interfacial potential (zeta potential) tends to decrease; while the cationic surfactant emulsion changes slowly in acidic and alkaline environments, but the value of the interfacial potential (zeta potential) decreases when the pH value becomes neutral obvious.

And by comparing the interfacial potential (zeta potential) of various surfactant emulsions in Fig. 16, we can know that betaine-silicone type surfactant has the maximum absolute interfacial potential (zeta potential) at pH10 ~ pH11 , Showing the emulsification of the betaine-siloxane type surfactant of the present invention in an alkaline environment The stabilization effect is the best, and it is even better than the anionic surfactant. The absolute value of the interfacial potential (zeta potential) of the anionic surfactant is larger, indicating that the emulsion stability is higher than other surfactants.

Comparison of the biodegradability of the betaine-siloxane surfactants of the present invention with conventional nonionic, anionic, and cationic surfactants, as shown in Table 2.

When the biodegradable rate is greater than 60%, it means that most of the organic matter contained in the wastewater can be decomposed by the organism. Table 1 shows the biodegradable index table of four different types of surfactants at a concentration of 0.1wt%. The results show that betaine-silicon surfactant is greater than 60%, the decomposition rate is the highest, and it can achieve environmentally friendly effects.

The comparison between the examples of the present invention and the comparative examples shows that the betaine-siloxane surfactants of the present invention have more excellent properties than other conventional surfactants, whether it is emulsification stability, dispersibility, Or it has excellent performance in biodegradability, and it can be used as a good green and environmentally friendly surfactant.

Nylon fiber is made by condensation polymerization of amino (-NH-) acid or lactam. The acid dye is an acid dye containing acid group. The chemical structure contains -OH group, -SO ₃ H group, -COOH. Acidic and weakly acidic or neutral dyes in the dyeing bath, so wool, silk can be dyed acid dyes can also dye nylon fibers.

Most of the acidic groups are -OH group, -SO ₃ H group, -COOH group, sulfonate group, easily soluble in water, dissociation into dye cations in water is anionic, and the help of acid is needed to achieve ionic bond bonding. dyeing. The dyeing operation is simple, the color is bright, and the washing fastness is medium.

Dyeability test, one of the important indicators for evaluating dyeing performance 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 through calculation, 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 play the role of wetting agent, leveling agent, solubilizer, precipitation preventive agent, etc. Therefore, the interaction between dye and surfactant is very important in many dyeing processes, such as the use in fabric dyeing, photo printing , Inkjet technology and other processes.

Leveling, CIB LAB is based on the theory that a color cannot be both green and red at the same time, and cannot be both blue and yellow at the same time. Therefore, a single value can be used to describe the red / green and yellow / blue characteristics. The CIB LAB tolerance formula is centered on the standard, and then the individual L * a * b * values are given, with an error range of plus or minus (+/-).

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

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

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

In the experiment of the present invention, the dye acid dye (CIAcid Red 114) is used, and the pH is adjusted to 4.5 with acetic acid. In a weakly acidic environment, Van der Waals and hydrogen bonding can be caused to obtain a good coloring rate and color. However, acid dyes are not easy to level nylon, so the use of new betaine silicon surfactants increases leveling and dyeing rate.

The dyeing procedure of the nylon fiber material of the present invention is to prepare a dye concentration of 1%, respectively. owf (mass percentage, the dye used is 1% of the total dyeing solution) and betaine-siloxane surfactants with different ratios of 0.2wt%, 0.4wt%, 0.5wt% (weight percentage) A dye composition composed of a carrier (water), used to dye nylon fiber cloth, and then analyze various related properties with a Ruby dyeing proofing machine, a spectrophotometer, and other instruments, and explore the dye or auxiliary The effect of addition on the dyeing of nylon fabrics.

Dyeability: When dyeing nylon fabrics, the biggest problem is the phenomenon of uneven dyeing, so a leveling agent is required to achieve the dyeing effect. The speed of dyeing is affected by the complex formed by the dye and the surfactant in the dyeing solution. During the dyeing, the surfactant molecules first adsorb the dye molecules, so that the dye molecules become larger, and the dyeing rate of the dye molecules and fibers is slowed down.染 结果。 Effect. In the later stage of dyeing, it is necessary to promote the dyeing speed, reduce the dye residue, and reach the hue concentration of the desired dyeing. Use a computer dyeing machine (Drum Dyeing Testing Matching) for dyeing, and then use a computer color matching system (CS-5) for testing.

Experimental drugs and materials

Nylon fiber cloth

Acetic Acid, Glacial CH ₃ COOH, molecular weight 60.05, first test reagent, purchased from Japan Test Drug Company

Auxiliary: betaine-silicone type surfactant

Acid Dyes: (C.I.Acid Red 114)

Experimental steps

1.Weigh 2 grams of nylon fiber cloth

2. Make up 100ml of dyeing composition

A. The concentration of formulated dye (C.I. Acid Red 114) is: 1% o.w.f (mass percentage, so that The dye used is 1% of the total dye solution).

B. Preparation of betaine-silicone type surfactants (including polyoxyethyl ether segments with molecular weights of 2000, 4000, 6000, and 8000 (g / mol) polyethylene glycol (PEG)) The concentrations of the additives are 0.2% and 0.4% (mass percentage).

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

3. In the dipping step, the nylon fiber material and the dyeing composition are respectively placed in a steel bottle at room temperature.

4. In the slow dyeing step, the dyeing composition and the nylon fiber material soaked therein are heated to 75, 85, and 95 ° C. at a temperature rise rate of 1 ° C./min through the dyeing conditions of a Ruby dye proofing machine.

5. In the dyeing step, the dyeing composition and the nylon fiber material soaked therein are held at 75, 85, and 95 ° C for 30 minutes.

6. The step of cooling out of the vat, after the dyeing composition and the nylon fiber material soaked therein are reduced to 50 ° C at a cooling rate of 1 ° C / min, the nylon fiber material is taken out of the vat of the dyeing composition.

7, wash and dry

8, colorimetric

The dyeing bath formula is prepared according to the dyeing conditions. The cylinders of the first tank are not added with any auxiliary agent, and the cylinders of the other tanks are added with different synthetic auxiliary agents. Put the nylon fabric into the steel bottle, fasten the cap tightly, set the starting temperature to 50 ° C, and increase it by 1 ° C every minute. When it reaches 70 ° C, put the steel cylinder on the cylinder base of the computer dyeing machine. After 5 minutes, take out one of the steel cylinders, wash the fabric in the steel cylinder thoroughly, and then dry it naturally. Remove the remaining steel cylinders at 75, 85, and 95 ° C. Dry naturally after washing. With a computer-applied Color System, it is calibrated and tested before it enters the test in a stable state.

Dyeing strength and evaluation results

When the dyeing and finishing industry uses dyes for dyeing, it is necessary to add a dye guide to the dyeing solution, so that the dyes can easily enter the inside of the fiber, and the purpose of deep dyeing and less residual liquid is achieved. The dye guide must have good dispersibility to help the dye diffuse into the fiber, prevent dye agglomeration, do not inhibit the final dyeing, and have moderate retardation and leveling properties. In addition, it is required to have low foaming property and has no effect on the fastness of dyeing. One of the important indicators for evaluating dyeing performance 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 through calculation, 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.

Using the dyeing composition containing the betaine-silicone type surfactant of the present invention, the dyeing properties of nylon fiber cloth after dyeing are tested as follows:

Analysis of spectrophotometric colorimeter

A Gretag Macbeth Color-Eye 2180UV / 2180 spectrophotometer was used as the standard. The dyed nylon fiber cloth obtained in the comparative example (without the additive of the betaine-silicone surfactant of the present invention) was used as a standard. The samples were used to evaluate the strength and color difference of the dyed nylon fiber cloth obtained from each dye composition in the experimental example, and the results are recorded in Tables 3 to 5.

The strength is calculated according to Kubelka-Munk Theory. In the following Tables 3 to 5, the intensity of the comparative example (standard sample) will be set to 100.0.

The betaine-siloxane type surfactant is added in an amount of 0.2%, For 0.4%, the results of dynamic color difference analysis are shown in Tables 3 to 5 below. A series of products were dyed at different concentrations and at different temperatures. The results showed that the dispersibility of the dyes increased with the betaine-silicone surfactant chain. As the molecular weight of oxyethylene (EO) increases, the better its dispersibility. As the EO chain length of the betaine-siloxane type surfactant increases, the hydrophilicity of the microcellular peripheral structure increases, and the agglomerated dye can be partially dissolved. Less agglutination, that is, better dispersibility to the dye. As the dyeing temperature is higher, the K / S value is larger, that is, the deeper the dyeing degree of the fabric is, the better. However, as the EO chain length increases, the dye-assistance effect is better.

The present invention uses non-toxic, biodegradable betaine to change water-insoluble silicone It is a water-soluble betaine-silicone type surfactant, with different molecular weights of polyethylene glycol (PEG = 2000, 4000, 6000, 8000, 10000) and betaine as the main raw materials. The synthesized product is amphiphilic Type (Amphiphilic) surfactant. This water-soluble betaine-silicone type surfactant has low foaming properties, reduced surface tension, wettability, emulsification and dispersion and other interfacial activities. The interfacial properties will change with the molecular weight of polyethylene glycol. Water-soluble betaine-silicone type surfactant with good interfacial activity can be used in many processing, textile dyeing and mixing and dispersing agents; a series of betaine-silicone type surfactants are obtained from the experimental results The agent has the characteristics of reducing surface tension, wettability, and low foaming properties, and has biodegradability. It is used in fiber dyeing. The higher the betaine-silicone surfactant product EO chain ratio, the higher the dyeing effect. The better the effect. Replacing the existing petroleum raw materials with betaine as the main body can not only reduce the cost, but also make it non-toxic, biodegradable, reduce environmental pollution, and greatly improve its economic benefits and practical performance.

Dyeing comparison of the betaine-siloxane surfactant of the present invention as a dyeing assistant for nylon fibers compared with other commercially available cationic, anionic, and nonionic surfactants

Dyeing conditions

(1) Prepare a 1% owf acid dye (CIAcid Red 114) solution, and add 0.5wt% of different auxiliaries (cationic surfactant, anionic surfactant, nonionic surfactant, betaine-siloxane interface) Active agent), stir uniformly, adjust the pH to 4.5 using acetic acid.

(2) Pour 40ml of the prepared sample into a steel bottle.

(3) Put 2.00g nylon fiber cloth into the steel bottle and fasten the steel bottle.

(4) When the bath ratio is 1:40, the temperature is raised to 75 ° C, 85 ° C, and 95 ° C at 1 ° C per minute using a Ruby dyeing machine. Can be tapped and cooled.

(5) Wash the fabric sufficiently, and allow it to dry naturally. Finally, use a spectrophotometer to discuss the data such as the dyeing rate and color difference value.

It can be seen from FIG. 17 and Tables 6 to 11 that the betaine-siloxane surfactants synthesized by the present invention have better leveling properties than the commercially available cationic, anionic, and nonionic surfactants, and with increasing temperature, Dyeing rate will also increase. The coloring effect of cationic surfactants is better than that of anionic surfactants and nonionic surfactants, but it is prone to uneven coloring.

Spectrophotometric detection

Table 8 Dyeing rate at 95 ℃

Tables 6 to 8 show the results of spectrophotometric detection. From the results, it can be seen that the K / S values range from 0.9 to 2.8 in Table 6 to Table 8 and the K / S values are: betaine> cation> anion> non-ion The larger the K / S value, the better the dyeing effect. The results show that the new betaine silicon surfactant has the best dyeing rate.

表9至表11為分光測色檢測染料色差值的結果，可由圖十七來探討各染色效果的明度及彩度的差異、色偏值等。 Table 11 Dye color difference values at 95 ° C

Table 9 to Table 11 are the results of spectrophotometric detection of the color difference values of the dyes, and the differences in lightness and chroma of each dyeing effect, color deviation values, etc. can be discussed from FIG. 17.

Look at the excellent difference from the DE value, and the smaller the DE value is, the more uniform dyeing is, and it is not easy to dye the flowers. The value of DE in Table 9 is nonionic> anion> cation> Sibetaine; Ion> cation> Sibetaine> anion; the DE value in Table 11 is anion> cation> nonionic> Sibetaine. The results show that the new betaine silicon surfactant has better leveling property.

It is known from the experimental results that the synthesized product has better leveling properties than the commercially available cations, anions, and non-ions, and the dyeing rate will increase with increasing temperature. good.

The coloring effect of cationic surfactants is better than that of anionic surfactants and non-ionic surfactants, but it is prone to uneven coloring. Based on the experimental results of K / S value and DE value, the new betaine silicon-type interface activity is shown. The agent has the best dyeing rate and better leveling property.

The experimental results show that the synthesized betaine-silicone surfactants have better leveling properties than other commercially available cationic, anionic, and nonionic surfactants as dyeing aids for nylon fibers. As the temperature increases, the dyeing rate will also increase, and the dyeing rate and dyeing rate are best at a temperature of 95 ° C.

General cationic surfactant dyeing aids have better coloring effects than anionic and non-ionic, but are prone to uneven coloring. From the K / S value and DE value experimental results, the betaine used in the present invention- The siloxane-type surfactant has the best dyeing rate and better leveling property.

The features, contents and advantages of the present invention and the effects achieved by the present invention are described in detail in the form of examples of the present invention as described above, and the list used in the text is only for the purpose of illustration and supplementary description. The scope of the patent for practical implementation of the present invention should be limited with respect to the proportions in the attached table, which should be described together.

Claims (10)

A dyeing composition of nylon fiber material, comprising: betaine-silicone type surfactant, based on the total weight of the dyeing composition, the content of the betaine-silicone type surfactant is 0.01 weight % To 10% by weight; dye, based on the total weight of the dyeing composition, the content of the dye is 0.01% to 10% by weight; and vehicle, based on the total weight of the dyeing composition, the The content of the carrier is 80% by weight to 99.98% by weight. The betaine-siloxane surfactant has a chemical structure of the following general formula:

Wherein R represents an organic group and contains at least one selected from the group consisting of a hydrogen atom, a hydroxyl group (-OH), an alkyl group (C ₁ to C ₁₀ ), and a phenyl group, and y is 1 to 20 and z is 1 to An integer of 20, n is the number of repeating units of the polyoxyethylene chain, the value of which is 5 to 5000, and w is the number of repeating units of the polysiloxane, the value of which is 1 to 200, where X ^-is selected from the group consisting of carboxylate, sulfonate, and sulfuric acid At least one ion of a root, a phosphate, and -OH. The dyeing composition according to item 1 of the patent application scope, wherein the carrier is selected from the group consisting of water, ethanol, acetone, or a mixed solution thereof. The dyeing composition according to item 1 of the scope of the patent application, wherein the content of the betaine-silicone type surfactant is 0.05% to 5% by weight based on the total weight of the dyeing composition; The content of the dye is from 0.05% by weight to 5% by weight. The dyeing composition according to item 1 of the scope of patent application, wherein the pH value of the dyeing composition is 2 to 6 at room temperature. The dyeing composition according to item 1 of the scope of patent application, wherein the preparation of the betaine-silicone type surfactant comprises the following steps: (a) reaction of a polysiloxane compound with a polyoxyethylene chain To obtain reactant A; (b) reactant A with alkylene chloride compound to obtain reactant B; (c) reactant B and dimethylamine to obtain reactant C; (d) reactant C and halogen The alkanoate reacts to obtain the product of betaine-siloxane type surfactant. The dyeing composition according to item 5 of the scope of the patent application, wherein the polysiloxane compound is selected from a polymer having a repeating Si-O as the main chain and an organic group connected to a silicon atom. The general formula is [R _s SiO _{4-s / 2} ] _w , wherein R represents an organic group and contains the same or different and is selected from a hydrogen atom, an alcohol group (OH), an alkyl group (C ₁ to C ₁₀ ), a phenyl group, s 0 to 4; wherein the alkylene chloride compound is selected from epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorochloroheptane, epichlorohydrin To epichlorohydrin; where the polyoxyethylene chain is selected from the group consisting of polyethylene glycol, polyethylene oxide (PEO), or polyoxyethylene (POE); the haloalkanoates have the following chemical structure:

Wherein H is selected from fluoro, chloro, bromo, halo iodine, X ^- is selected from carboxylate, sulfonate, sulfate, phosphate, -OH roots of at least one ionic, z is an integer of from 1 to 20. The dyeing composition according to item 5 of the scope of the patent application, wherein in the preparation of the betaine-siloxane surfactant, the synthesis temperature of steps (a) to (d) is 10 to 220 ° C, and the synthesis time is From 1 to 24 hours, step (a) further includes a catalyst selected from at least one or a combination of titanium (IV) tetraisopropoxide, sulfuric acid, and hydrochloric acid, and step (b) the reaction between reactant A and the alkylene chloride compound. Should be further reacted in the presence of basic (1 ~ 10% sodium hydroxide, potassium hydroxide) and a catalyst, the catalyst is selected from the group consisting of tetrabutylammonium bromide, benzyltriethylammonium chloride, At least one of trioctylmethylammonium chloride, tetramethylammonium bromide, or a combination thereof. A dyeing program for a nylon fiber material, comprising: providing a nylon fiber material; providing the dyeing composition according to any one of claims 1 to 7 of the patent application scope; and using the dyeing composition to dye the nylon fiber material . According to the dyeing procedure of the nylon fiber material according to item 8 in the scope of the patent application, wherein the fiber material is dyed by using the dyeing composition, including: a dipping 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 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; Hold the dyeing composition and the fiber material soaked therein at 110 ° C for 20 minutes to 60 minutes; and step of cooling out of the vat, the dyeing composition is cooled at a cooling rate of 0.5 ° C / min to 5 ° C / min. After the fiber material soaked therein is lowered to 40 ° C to 80 ° C, the fiber material is taken out of the dyeing composition. A nylon fiber product, which is obtained by dyeing a nylon fiber material with a dyeing composition according to any one of claims 1 to 7, or a dyeing procedure according to any one of claims 8 to 9, .