TW201905275A - Dyeing composition for fiber material and dyeing process using the same capable of improving the dyeing uniformity and coloring rate of the fiber material during dyeing - Google Patents

Abstract

The present invention provides a dyeing composition for fiber material and a dyeing process using the same. The dyeing composition for the fiber material includes: providing a surface-treated fiber material, wherein the surface of the fiber material is treated with a chitosan-siloxane type surfactant; and providing a dye bath composition including: an auxiliary, a dye, and a carrier. Based on the total weight of the dye bath composition, the content of the auxiliary agent is from 0.01% by weight to 10% by weight, the content of the dye is from 0.01% by weight to 10% by weight, and the content of the carrier is from 80% by weight to 99.98% by weight. The surface-treated fiber material refers to the surface treatment performed by using the chitosan-siloxane type surfactant of the present invention, and the treated fiber material can improve the dyeing uniformity and coloring rate of the fiber material during dyeing.

Description

 Dyeing composition of fiber material and dyeing program using same  

A dyeing composition of a fibrous material and a dyeing process using the same, the dyeing composition of the fibrous material comprising: providing a surface treated fibrous material, the surface of the fibrous material being a chitosan-vaoxane type surfactant Processing; providing a dye bath composition comprising: an auxiliary, a dye, and a carrier. The content of the auxiliary agent is from 0.01% by weight to 10% by weight based on the total weight of the dye bath composition; the content of the dye is from 0.01% by weight to 10% by weight; and the content of the carrier is from 80% by weight to 99.98% by weight. The fiber material which is surface-treated by the chitosan-methoxyalkane type surfactant of the present invention, and the auxiliary agent may also be selected from the chitosan-oxirane type surfactant of the present invention, according to the present invention. Improve the dyeing uniformity and coloring rate of the fiber material during dyeing. The dyeing composition of the present invention is suitable for various fiber materials, and is particularly suitable for dyeing polylactic acid fibers and polyester fiber materials. The fiber dyeing process of the present invention comprises: providing a surface treated fibrous material, the surface of the fibrous material being treated with a chitosan-vaoxane type surfactant; providing a dye bath composition, the dye bath composition comprising The auxiliary agent, the dye and the carrier; the fiber material surface-treated by the chitosan-vaoxane type surfactant of the invention further comprises a plasma treatment to improve the dyeing uniformity and coloring of the fiber material during dyeing; rate. The chitosan-nonane type surfactant prepared by the invention has the characteristics of biodegradability, non-toxicity and good biocompatibility, and is an excellent fiber surface treatment agent, dyeing and finishing aid for textile dyeing and finishing industry. The woven fabric fiber can be used to treat the dyeing uniformity and coloring rate of the fiber after being treated by the chitosan-oxane type surfactant of the present invention, and is harmless to the skin, and the wastewater after dyeing and finishing can be used. Decomposed by microorganisms, it is not polluting to the environment.

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 is mainly caused by the large consumption of oil. The goods used by human beings are over-reliant on petroleum raw materials, resulting in a shortage of petroleum energy. Because of the petroleum-based products, many of them are not easily decomposed 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 chitosan used in the present invention is a polysaccharide obtained by polymerizing amino-based glucose, and has a multifunctional and environmentally friendly saccharide polymer, which is biocompatible (low toxicity, no antibody production, etc.) , biological activity (lowering cholesterol, lowering blood fat, lowering blood pressure, increasing immune function), biodegradability, film formation, gelation, positive polarity (antibacterial, adsorption, hemostasis) in acidic solution, so it can be used Wound dressings, patches, surgical sutures, antibacterial and deodorant fabrics, health foods, diet foods, immobilized enzymes, and cosmetics, can also be used as juice clarifiers, fruit preservatives, wastewater treatment agents, etc. In today's society where energy is reused, it has great potential for development.

Chitosan is widely used in medicine, textile, chemical, agricultural, and food fields. The main sources are shells of crustaceans such as shrimps, crabs, and insects, and organs of mollusks (such as cartilage of squid), and cell walls of fungi. Wait. Its reserves rank second in the natural polymer on the earth, second only to cellulose. Based on shrimp and crab crustaceans, it is an important fishery processing waste in Taiwan. If it is not used, it is easy to cause environmental pollution. The shrimp and crab processing waste is rich in protein, astaxanthin, chitin, calcium and other valuable components, and can be recycled to produce high value-added substances. Generally, the degree of deacetylation of chitin and chitosan is not clearly defined. It is recommended that the total nitrogen content accounts for more than 7% of the total polymer weight (W/W) (about 60% of the degree of deacetylation). , called chitosan. Chitosan is represented by the following chemical formula (1)

Most of the disperse dyes in the prior art have little affinity, and the dyeing rate of dyes is generally low during dyeing, so that a large amount of dyes remain in the dyeing solution after dyeing, causing problems of dye waste and environmental pollution.

Polylactic acid (PLA) is an environmentally friendly fiber material. The polylactic acid fiber material can be obtained by mixing starch extracted from corn or cassava, sugar extracted from sugar cane or sugar beet, and cellulose extracted from straw, and subjected to fermentation, dehydration, or the like. Further, the polylactic acid fiber material is a linear aliphatic thermoplastic polyester which is resistant to sterilization and easy to process, and is non-toxic, non-irritating, and biodegradable ( Biodegradable) and good biocompatibility. The polylactic acid fiber material has a glass transition temperature of about 60 ° C, a crystallization temperature of about 110 ° C, and a melting point of about 160 ° C. The product made of the polylactic acid fiber material has a smooth surface and is not harmful to the human body, and thus can be applied to the manufacture of clothes.

Conventional dyes have low dye uptake or leveling property on polylactic acid fiber materials, which causes the dyed polylactic acid fiber material to have a problem that the dye remains on the surface, which leads to the resistance of the dyed polylactic acid fiber material. Wash fastness or light fastness is too low, even dye waste and other environmental problems. Therefore, a dye bath composition suitable for a low-temperature dyeing process has been developed which has good dye uptake and leveling properties for polylactic acid fiber materials, and enables the dyed polylactic acid fiber material to have high wash fastness. And light fastness will be a very important topic in this field.

Poly Lactic Acid (PLA) is an environmentally friendly material that can be completely decomposed by microorganisms in nature, and eventually produces carbon dioxide and water, which does not pollute the environment and is very beneficial to environmental protection. Polyester (Polyester) clothing is not affected by acid, acid resistance and alkali resistance, but will be decomposed at high temperatures, not easily broken down by microorganisms. Therefore, the PET fiber material is replaced by a biodegradable PLA. However, the disadvantage of the PLA fiber material is that it is not easily dyed, especially a disperse dye.

In the prior art, the ruthenium compound has excellent excellent properties such as defoaming, lubrication, and gloss enhancement, but its nature itself is mostly water-insoluble, so it is often limited in application, and often used in environmental protection concepts. Causes environmental pollution and other issues.

The inventors of the present invention have successfully synthesized a chitosan-vaoxane type surfactant, which is a chitosan-oxirane type surfactant having a special structure, and the present invention utilizes the chitosan-矽The oxane type surfactant is surface-treated with the fiber material, and the surface-treated fiber material is further subjected to plasma treatment, and then dyed, and dyed under different color disperse dyes and different auxiliary concentrations. The effect of deep dyeing and uniformity can be obtained, and the chitosan-methoxyalkane type surfactant of the present invention can also be used as a dyeing and finishing agent for dyeing.

The present invention provides a dyeing composition of a fibrous material, comprising: providing a surface treated fibrous material, the surface of the fibrous material being treated with a chitosan-vaoxane type surfactant; providing a dye bath composition, the dyeing bath The composition comprises: an auxiliary agent, the auxiliary agent is contained in an amount of 0.01% by weight to 10% by weight based on the total weight of the dyeing bath composition; and the dye is based on the total weight of the dyeing bath composition, The content of the dye is from 0.1% by weight to 10% by weight; and the carrier is contained in an amount of from 80% by weight to 99.89% by weight based on the total weight of the dyeing bath composition; wherein the chitosan a sugar-methoxyalkyl type surfactant having a structure represented by the following formula (I):

Where G represents a chitosan residue , R represents an organic group selected from a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a phenyl group, and m represents a number of repeating units of chitosan, and its value 2~5000; x represents the repeating unit number of the oxoxane 1~200; y represents the number of repeating units of -CH ₂ - in the acid anhydride or diacid compound, and its value is 0-20; n represents the repeating unit of the polyoxyethylene ether segment The number is from 10 to 5000.

The present invention further provides a dyeing bath composition, the dyeing bath composition comprising: an auxiliary agent, the auxiliary agent is contained in an amount of 0.01% by weight to 10% by weight based on the total weight of the dyeing bath composition; The dye is contained in an amount of 0.1% by weight to 10% by weight based on the total weight of the dye bath composition; and the carrier is 80% by weight based on the total weight of the dye bath composition. % to 99.89% by weight; wherein the auxiliary comprises at least one chitosan-nonane type surfactant of the invention, which contributes to deep dyeing and uniform effect upon dyeing.

A dyeing composition of the fibrous material of the present invention, wherein the carrier is selected from the group consisting of water, ethanol, acetone or a mixed solution thereof.

The dyeing composition of the fibrous material of the present invention, wherein the polyoxyethylene ether segment in the chitosan-methoxyalkane type surfactant is selected from the group consisting of polyethylene glycol (PEG) and polyethylene oxide It is composed of alkane (PEO) and polyoxyethylene (POE). Among them, the acid anhydride or the diacid compound is selected from a linear or branched anhydride or diacid compound having a carbon number of 3 to 23.

The chitosan-vaoxane type surfactant according to the present invention, wherein the oxoxane compound is selected from the group consisting of a polymer having a repeating Si-O as a main chain and an organic group bonded to a ruthenium atom. , the general formula is [R _s SiO _4-s/2 ] _x , wherein R represents an organic group selected from a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group The base and the phenyl group, s are 0 to 4, and x is the repeating unit number of the oxirane to which the organic group is bonded to the oxime atom, and the value is an integer of 1 to 200, preferably an integer of 20 to 100.

The present invention provides a dyeing process for a fibrous material, comprising: providing a surface treated fibrous material, the surface of the fibrous material being treated with a chitosan-vaoxane type surfactant; providing a dye bath composition, the dyeing bath The composition comprises: an auxiliary agent, the auxiliary agent is contained in an amount of 0.01% by weight to 10% by weight based on the total weight of the dyeing bath composition; and the dye is based on the total weight of the dyeing bath composition, The content of the dye is from 0.1% by weight to 10% by weight; and the carrier is contained in an amount of from 80% by weight to 99.89% by weight based on the total weight of the dyeing bath composition; a fiber material for surface treatment of a sugar-oxymethane type surfactant, wherein the fiber material is dyed by the dye bath composition, wherein the chitosan-methoxyalkane type surfactant has the above A surfactant of the structure of the formula (I).

A dyeing composition of a fibrous material and a dyeing process using the same, wherein the fiber material is dyed by the dyeing composition, comprising: a fiber material surface treatment step, the surface of the fiber material is subjected to the chitosan of the invention a siloxane-type surfactant treatment; a dip dyeing step of immersing the surface-treated fibrous material in the dye bath composition at room temperature; and a retarding step of heating at a temperature of 0.5 ° C / min to 5 ° C / min Rateing the dye bath composition and the surface-treated fibrous material immersed therein to a temperature of 100 ° C to 200 ° C; a dyeing step of immersing the dye bath composition at 100 ° C to 200 ° C and immersing therein The surface treated fiber material is held for 20 minutes to 60 minutes; and the cooling step is performed, and the dye bath composition and the surface treated therein are treated at a cooling rate of 0.5 ° C / min to 5 ° C / min. After the fiber material is lowered to 50 ° C to 90 ° C, the surface treated fiber material is taken out from the dye bath composition.

A dye bath composition of a fibrous material and a dyeing process using the same, wherein the fiber material is dyed by the dye bath composition, comprising: a dip dyeing step, and the surface treated fiber material is at room temperature Immersing in the dye bath composition; in the retarding step, heating the dye bath composition and the surface treated fiber material immersed therein to a temperature of 0.5 ° C / min to 5 ° C / min to 100 ° C ~ a 200 ° C dyeing step, the dyeing bath composition and the surface-treated fibrous material immersed therein are held at a temperature of 100 ° C to 200 ° C for 20 minutes to 60 minutes; and the step of cooling the cylinder is performed at 0.5 ° C / min A temperature drop rate of 5 ° C / min reduces the dye bath composition and the surface treated fiber material immersed therein to 50 ° C to 90 ° C, and then removes the surface treated fiber material from the dye bath composition.

A dyeing process for a fiber material according to the present invention, wherein the fiber material surface-treated with the chitosan-methoxyalkane type surfactant is further dyed after being processed by the plasma technology, in the dyeing process. It can help fiber dyeing and achieve the effect of deep dyeing and leveling. The dyed fiber material has good washing fastness and light fastness. The fiber material comprises fiber materials of various materials, and has good dye uptake and level dyeability, especially for polylactic acid fiber materials and polyester fiber materials.

The dyeing composition of the fiber material of the invention and the dyeing program using the same are suitable for dyeing various fibers, and are particularly suitable for the biodegradable polylactic acid fiber material and the polyester fiber material, the polylactic acid fiber material material and the polyester fiber material. The disadvantage is that it is not easy to deeply dye, especially the disperse dye, and the chitosan-vaoxane type surfactant of the invention is the fiber surface treatment agent, so that the fiber can be deeply dyed and level dyed when dyed. effect.

The dyeing composition of the fiber material of the present invention and the dyeing process using the same are the use of a specific structure of a chitosan-vaoxane type surfactant as a fiber surface treatment agent, which is a hydrophobic surface of the fiber surface treatment agent ( Hydrophobic group) and Hydrophilic Group are an organic compound. Due to its special symmetrical chemical structure, it is easily adsorbed on the surface or interface of the solution at very low concentrations, thus changing the surface or interface of the solution. Free energy, which reduces surface tension and produces properties such as wetting, penetration, foaming, emulsifying, dispersing and melting.

The dyeing composition of the fiber material of the present invention and the dyeing process using the same, using a specific structure of chitosan-vaoxane type surfactant as a fiber surface treatment agent, the chitosan-oxime type a surfactant having the chemical structure of the following general formula (I) Wherein G represents a chitosan residue, and R represents an organic group selected from the group consisting of a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a phenyl group, and m represents The number of repeating units of chitosan, the value is 2~5000; x represents the number of repeating units of oxime oxide 1~200; y represents the number of repeating units of -CH ₂ - in the acid anhydride or diacid compound, the value is 0-20; n represents the number of repeating units of the polyoxyethylene ether segment, and its value is from 10 to 5,000.

The preparation method of the chitosan-vaoxane type surfactant of the present invention comprises the product A which is reacted with chitosan and an acid anhydride compound or a diacid compound, and is selected from the group consisting of polyethylene glycol and polyethylene oxide A product B of at least one polyoxyethylene ether segment of alkane or polyoxyethylene reacted with a decane, and then a product of product A and product B is condensed to obtain a chitosan-methoxyalkane type surfactant. The structure containing the affinity and hydrophobic group arrangement can be dispersed or emulsified in an aqueous solution, and has the advantages of non-toxicity, no pollution, biodegradability and good biocompatibility, so that it has wider industrial applicability in use. The chitosan-nonane type surfactant of the invention has excellent dispersing emulsifying ability, moisturizing lubrication and improving luster texture characteristics, and has the characteristics of biodegradable natural environment and can be widely used for dyeing. Relevant industrial uses such as emulsification, dispersion and wetting of cosmetics, cleaning products, pharmaceuticals, foods and industrial products.

The preparation of the chitosan-vaoxane type surfactant of the present invention comprises the following synthetic steps (a) to (c):

(a) Synthesis of chitosan-anhydride or diacid compound

The chitosan acetic acid aqueous solution and the acid anhydride or diacid compound are placed in a reactor equipped with a stir bar and a thermometer, and then the catalyst is added and uniformly stirred and slowly heated to 30 to 90 ° C. After the reaction at this temperature for several hours, the gas is pumped. Filtration of the impurities, and drying in vacuo to obtain product A;

(b) Synthesis of polyoxyethylene ether segment-heloxane

Selected from: polyethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene ether (POE) polyoxyethylene ether segment and helium oxide and catalyst, at 100 ~ 200 ° C constant temperature for several hours, Product B;

(c) Synthesis of chitosan-heloxy-type surfactant

The product A of the step (a) and the product B of the step (b) are reacted to obtain a series of chitosan-methoxyalkane type surfactants.

The invention relates to the preparation of a chitosan-vaoxane type surfactant, wherein the catalyst is selected from the group consisting of titanium isopropoxide, sulfuric acid, hydrochloric acid or a group thereof. Wherein the acid anhydride or diacid compound is selected from a linear or branched anhydride or diacid compound having a carbon number of 3 to 22.

The synthesis reaction formula of the chitosan-methoxyalkane type surfactant of the present invention is as follows: wherein the diacid or anhydride compound is exemplified by maleic anhydride, and the polyoxyethylene ether segment is exemplified by polyethylene glycol.

Step (a)

Step (b)

Step (c)

The preparation of the chitosan-vaoxane type surfactant of the present invention, wherein the acid anhydride or diacid compound is selected from a linear or branched anhydride or diacid compound having a carbon number of 3 to 23.

The inventor succeeded in synthesizing a chitosan-vaoxane type surfactant, and the present invention utilizes the chitosan-methoxyalkane type surfactant to treat the surface of the fiber material, and further treats the fiber material by plasma. The surface is then subjected to different color disperse dyes and different additive concentrations to obtain deep dyeing and uniform effects.

Dyeing properties

In fiber dyeing engineering, disperse dyes cause physical or chemical pollution, which is less sensitive than acid dyes. The process of dyeing polyester fabrics with disperse dyes is mainly carried out in four steps:

(1) The dye is dispersed and partially dissolved in the dye solution by the action of a dispersing agent.

(2) The dye particles are transferred from the dyeing to the surface of the fabric and produce adsorption.

(3) The undissolved dye particles in the dispersion are produced on the surface of the fabric which is dissolved and continuously transferred.

(4) Dye molecules adsorbed on the surface of the fabric diffuse into the interior of the fabric.

Leveling

CIB LAB is based on the theory that a color cannot be both green and red, and not both blue and 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 a dyeing procedure according to an embodiment of the present invention, a polyester (PET) fiber material or a polylactic acid (PLA) surface-treated with the chitosan-methoxyalkane type surfactant of the present invention is utilized by a dye bath composition. The fiber material is dyed.

In one embodiment of the present invention, the dyeing process of the fiber material comprises the steps of: a surface treatment step of the fiber material, the surface of the fiber material is treated with a chitosan-vaoxane type surfactant; and the dip dyeing step is performed at room temperature. The surface treated polylactic acid fiber material or polyester fiber material is immersed in the dye bath composition. In the retarding step, the dye bath composition and the surface-treated polylactic acid fiber material or polyester fiber material immersed therein are heated to a temperature of 100 ° C to 200 ° C at a heating rate of 0.5 ° C / min to 5 ° C / min. In the dyeing step, the dye bath composition and the surface-treated polylactic acid fiber material or polyester fiber material immersed therein are kept at a temperature of from 100 ° C to 200 ° C for 20 minutes to 60 minutes. Cooling and discharging step, the dye bath composition and the surface-treated polylactic acid fiber material or polyester fiber material immersed therein are lowered to 50 ° C to 90 ° C at a cooling rate of 0.5 ° C / min to 5 ° C / min, and then The surface treated polylactic acid fiber material or polyester fiber material is taken out from the dye bath composition.

In another embodiment of the present invention, the dyeing process of the fibrous material comprises the steps of: dipping the polylactic acid fiber material or the polyester fiber material into the dye bath composition of the present invention at room temperature; and retarding the step to 0.5 The heating rate of °C/min~5°C/min is used to heat the dye bath composition and the polylactic acid fiber material or polyester fiber material soaked therein to 100 ° C ~ 200 ° C; the dyeing step, the dye bath at 100 ° C ~ 200 ° C The composition and the polylactic acid fiber material or the polyester fiber material immersed therein are held for 20 minutes to 60 minutes; the step of cooling the cylinder is performed, and the dye bath composition is immersed at a cooling rate of 0.5 ° C / min to 5 ° C / min. After the polylactic acid fiber material or the polyester fiber material is lowered to 50 ° C to 90 ° C, the polylactic acid fiber material or the polyester fiber material is taken out from the dye bath composition.

In the dye bath composition according to an embodiment of the present invention, the content of the dye is, for example, 0.05% by weight to 5% by weight based on the total weight of the dye bath composition.

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

In an embodiment of the invention, the dye is adsorbed onto the surface of the polylactic acid fiber material or the polyester fiber material by a molecular dyeing force (for example, hydrogen bonding or van der Waals force) through a dyeing process. The dye may be a disperse dye such as CI blue dye 79, CI red dye 60, yellow dye (Dianix Yellow AM-42, manufactured by DyStar), black dye (Goldenlon Black DXF, by Xiejing Company) Manufactured, HUNTSMAN (TERASIL NAVY GRL-C 200% Blue, TERASIL RED FBN CONC. Red, TERASIL ORANGE 5RL 150% Orange), or a combination thereof.

The content of the dye is from 0.01% by weight to 10% by weight, based on the total weight of the dye bath composition, preferably from 0.05% by weight to 7% by weight, more preferably from 0.05% 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 0.01% by weight, the polylactic acid fiber material and the polyester fiber material cannot be effectively dyed to a desired color; and when the content of the dye is more than 10% by weight, the excess dye may remain in the dye. Polylactic acid fiber materials and polyester fiber materials, which cause problems of dye waste or environmental pollution.

In an embodiment of the invention, the carrier functions to provide an environment in which the dyes and auxiliaries in the dye bath composition can be optionally mixed and/or aggregated. The carrier is, for example, water, ethanol, acetone or a mixed solution thereof. The carrier is present in an amount of from 80% by weight to 99.98% by weight based on the total weight of the dye bath composition.

Further, in an embodiment of the present invention, the dye bath composition may further include a pH adjusting agent for adjusting the pH of the dye bath composition. The pH of the dye bath 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 bath composition is in the above range, it will be able to affect the charge of the polylactic acid fiber material and the polyester fiber material, and also increase the degree of dye dispersion and its combination with the polylactic acid fiber material and the polyester fiber material. speed.

Based on the above, since the dye composition includes a fiber material surface-treated with a chitosan-siloxane type surfactant, the dye bath composition is dyed when the dyeing bath composition is used to dye the fiber material. The fiber material can have better dyeing rate and leveling property, thereby achieving the effect that the fiber material can be deeply dyed and easily dyed, especially the polylactic acid fiber material and the polyester fiber material, and also the dyed polylactic acid fiber. Materials and polyester fiber materials have good wash fastness and light fastness.

In the dyeing procedure provided in this embodiment, a surface-treated polylactic acid fiber material or a polyester fiber material and a dye bath composition described in the above embodiments are first provided, followed by surface treatment with the dye bath composition. The fiber material is dyed. The surface treatment further comprises a plasma treatment. In the dyeing procedure, the bath ratio of the surface treated polylactic acid fiber material or polyester fiber material to the dye bath composition is, for example, about 1:30. For example, if a surface-treated polylactic acid fiber material or a polyester fiber material having a weight of 5 g is to be dyed, it may be immersed in a dye bath composition having a weight of 150 g.

When the surface-treated fibrous material is dyed using the dyeing bath 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 surface treated fibrous material into the dye bath composition at room temperature. After the dip step, a slow dyeing step is performed. The retarding step is, for example, heating the dye bath composition and the surface-treated fibrous material immersed therein to a temperature of from 0.5 ° C / min to 5 ° C / min to 100 ° C to 200 ° C. In the dip dyeing step and the retarding step, the dye in the dye bath composition may be initially adsorbed on the surface of the surface treated fibrous material, thereby dyeing the fibrous 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, holding the dye bath composition and the surface fiber material immersed therein at a temperature of from 100 ° C to 200 ° C 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 the surface-treated fibrous material of the chitosan-siloxane-type surfactant, it is at 100 ° C to 200 ° C. At the temperature, the dye bath composition has good dye uptake and leveling property to the fiber material, so that the dyed 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 bath composition and the fiber material immersed therein to a temperature of about 50° C. to 90° C. at a temperature decreasing rate of 0.5° C./min to 5° C./min, and then removing the fiber material from the dye bath composition. Take out. 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, it is understood that in the dyeing procedure of the present invention, since the surface treatment of the fiber material is followed by dyeing using a chitosan-siloxane-type surfactant, the dyed fiber material has a good coloring ratio. And leveling.

Analysis of dyeing properties of fiber materials surface treated with chitosan-heloxy-type surfactants of the present invention:

Dyeing test

The surfactant can be used as a leveling agent, a precipitation inhibitor, a solubilizer, a wetting agent, a fixing agent, etc., so the interaction between the dye and the surfactant is very important in the dyeing process of the fabric.

The dyeing depth (K/S Values) is one of the important indexes for evaluating the dyeing performance of dyes. A certain function is established between the absorption coefficient and scattering coefficient of the measured object and the concentration of colored substances in the solid sample. The relationship is the Kubelka-Munk dyeing depth equation. The color yield of the dyed sample is higher. The higher the K/S value is calculated by the light reflectance, the higher the concentration of the colored substance, that is, the darker the surface of the solid sample. The dye dyeing performance is better.

K/S=(1-R) ² /(2R)

K absorption coefficient; S scattering coefficient; R reflectivity

The basic color concept is based on three attributes: Hue, Lightness, and Saturation. According to the three attributes of the color, a three-dimensional color stereo can be constructed.

The International Commission on Illumination (CIE) developed basic standards and metrics for lighting and developed international standards in this field. In 1976, two uniform color spaces were developed, respectively L*a*b* color space. (CIELAB) and CIE L*u*v* (CIELUV), CIELAB color difference formula is mainly used in object color, while CIELUV color difference formula is used in light source color (self-luminous source display), the most famous system is CIELAB, The result of the CIE color space presented by the linear transformation CIE L*a*b* is roughly a uniform color space. The relative color scale is established to define the standard, which makes it easier and more accurate to express the color and depict the intensity of the perceived color. .

As shown below, in the three-dimensional color solid structure, the color stereo outer edge portion is a hue, and L* indicates that the brightness is increased or decreased along the vertical axis, and its value extends from 0 (black) to 100 (white), and a* and b* are color directions. :+a* is the red direction, -a* is the green direction, +b* is the yellow direction, and -b* is the blue direction. The center is colorless, and the saturation varies according to the center point. As the values of a* and b* increase and the point moves out from the center, the saturation of the color increases in the color space.

L *, a * and b * values of the XYZ tristimulus values proportional, and X _n, Y _n, Z _n is a special light source and the observation angle within the desired tristimulus values of the reflected light source diffuser by the CIE in Established in 1931, the conversion equation is as follows.

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

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

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

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

The invention utilizes the synthesized chitosan-vaoxane type surfactant to surface treatment of polylactic acid fiber material or polyester fiber material, and then carries out different color disperse dyes and different auxiliary concentration to obtain deep dyeing and The effect of dyeing.

Figure 1. FTIR spectrum of chitosan-methoxypropane type surfactant

Figure 2. SEM image of blank PLA polylactic acid fiber at different magnifications

Figure 3. SEM image of polylactic acid fiber coated with chitosan-methoxyalkane surfactant (PEG2000, PEG4000, PEG6000, PEG8000) at 500X rate

Figure 4. SEM image of polylactic acid fiber coated with chitosan-methoxyalkane surfactant (PEG2000, PEG4000, PEG6000, PEG8000) at 1000x ratio

Figure 5. SEM image of polylactic acid fiber coated with chitosan-methoxyalkane surfactant (PEG2000, PEG4000, PEG6000, PEG8000) at 4000X ratio

Figure 6. High resolution electron spectroscopy test chart

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

Preparation of chitosan-vaoxane type surfactant

Use materials:

(1) chitosan (C ₆ H ₁₁ O ₄ N) _m , m=35-70 in the examples

(2) Acetic acid C ₂ H ₄ O ₂

(3) Maleic Anhydride (MA)

(4) 矽 烷 (C ₂ H ₆ OSi) _x , x=42 in the examples

(5) Polyethylene glycol (PEG)

structure:

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

(6) Titanium Isopropoxide

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

(7) Dyes C.I. Disperse dyes Blue 79

(8) Dye C.I. Disperse dye Red 60

The preparation of the chitosan-methoxyalkane type surfactant of the present invention is exemplified as follows, and is not intended to limit the present invention. The steps of the synthesis step including (a) to (c) are as follows:

(a) Synthesis of chitosan-anhydride or diacid compound

1 mol of a 2% aqueous solution of chitosan acetic acid and 1 mol of an acid anhydride were placed in a reactor equipped with a stir bar and a thermometer, and 1 g of a catalyst (Titanium Isopropoxide) was added thereto and uniformly heated to 50. After ~70 ° C, the temperature is reacted at this temperature for 4 hours, the impurities are filtered by suction, and dried under vacuum at 50 ° C to obtain product A;

(b) Synthesis of polyoxyethylene ether segment-heloxane

1 mol of polyethylene glycol (average molecular weight Mw: 2000, 4000, 6000, 8000) polyoxyethylene ether segment and 1 mol of decane and 1 g of catalyst (Titanium Isopropoxide), at 130~ 150 ° C × 4 ~ 6hr constant temperature, to obtain product B;

(c) Synthesis of chitosan-heloxy-type surfactant

A reaction of 1 mol of the product of the step (a) and 1 mol of the product of the step (b) gives a series of chitosan-oxirane type surfactants.

The chitosan-vaoxane type surfactant of the present invention, in the experimental example, is chitosan, polyethylene glycol (average molecular weight Mw: 2000, 4000, 6000, 8000), maleic anhydride and helium oxygen The alkane is the main raw material, firstly reacting chitosan with an acid anhydride or a diacid compound to obtain a product A, and then synthesizing different polyoxyethylene ether segments of polyglycol ether and a nonoxyl alkane to obtain a product B, and finally the step The product A and the product B are reacted and synthesized to prepare a series of chitosan-vaoxane type surfactants. The codes and compositions of the products synthesized by the present invention are shown in Table 1.

Table 1 is a synthetic component list and product code of the chitosan-nonane type bimolecular surfactant of the present invention.

The structure of the chitosan-methoxyl type surfactant was identified by Infrared Spectrophotometer Perkin-Elmer Spectrum one (Perkin Elmer Cetus Instruments, Norwalk, CT), and the sample was concentrated and vacuum dried to remove the solvent. The test was carried out on a KBr salt plate. As a result, as shown in Fig. 1, characteristic absorption peaks corresponding to various functional groups were observed from the FTIR spectrum. Silicon type surfactant alumoxane product corresponding to the various functional groups characteristic absorption peaks, wherein the results can be seen in 810cm ^-1 with a specific siloxane silica SiO characteristic peaks, there are at 1105cm ^-1 CO - chitosan synthesized the stretching vibration absorption, methyl -CH ₂ asymmetric stretching absorption at 2886cm ^-1, absorption -CH ₃ asymmetric stretching at 2966cm ^-1, 3450cm ^-1 has the -OH stretching vibration of hydroxyl group absorption. Since chitosan is a hydrophilic group, it does not absorb at 2886 cm ^-1 and 2966 cm ^-1 , but the azide is a hydrophobic group at 2966 cm ^-1 -CH ₃ is more, and has a strong absorption.

Analysis of fiber materials surface treated with chitosan-methoxyalkane surfactant

1. Field emission scanning electron microscope (FESEM)

Models: JSM-6330F field emission scanning electron microscope were used to analyze the surface structure changes of the chitosan-methoxyalkane surfactant solution coated on the polylactic acid fiber fabric or after plasma treatment.

(1) Cut the sample to be tested into a square of 0.3 cm in diameter

(2) Apply double-sided adhesive carbon to the metal round sample stage, and then place the sample flat on the carbon glue.

(3) Vacuum plating of platinum with an Ion Coater, and plating of the sample after platinum plating under a scanning electron microscope, scanning and photographing at different magnifications in a vacuum.

Figure 2 is an SEM image of blank PLA polylactic acid fiber with different magnifications. It can be seen from the scanning electron microscope of the third, fourth and fifth field emission scanning that the surface of the polylactic acid fabric coated PEG4000 is unevenly coated. After the modification, the uneven coating phenomenon was not improved. The surface smoothness and uniformity of the polylactic acid fabric after coating with PEG8000 were relatively good after the surface modification of the plasma.

2. High resolution electron spectroscopy (HRXPS)

Model: ULVAC-PHI (XPS: PHI Quantera SXM/Auger: AES 650); X-ray source: Scanning Monochromated A1 anode. Energy Analyzer: 180° Spherical Capacitor Analyzer + 32 Channel Detector. Hot/Cold Stage: -120 ° C ~ +250 ° C. Vacuum degree: <5×10-10 torr.

It is generally used to detect the electron binding energy of an element. It can be used to determine the element of an unknown element by electron binding. The principle is to use high voltage to generate high-speed electrons to attack aluminum or magnesium and release X-RAY. When X-RAY hits the sample. After detecting the photocurrent, the electron binding energy can be known.

It can be seen from the test chart of the high-resolution electron spectroscopy of Fig. 6 that the presence of strontium is found in the polylactic acid fabric coated with PEG2000. After the surface modification of the plasma, the oxygen element is also improved, and the carbon element is decreased.

The biggest problem with the application of disperse dyes to polylactic acid fabrics is that they are not easily dyed deeply, so it is necessary to use a solid color leveling agent to achieve the deep 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. First, dye the polylactic acid fiber fabric after treating the polylactic acid fiber fabric with a chitosan-methoxyalkane type surfactant, or further polymerize the polylactic acid fiber fabric treated with the chitosan-siloxane type surfactant to further the plasma technology. After surface treatment, dyeing was carried out to compare the dyeing efficiency before and after the plasma treatment. Dray Dyeing Testing Matching was used for dyeing and was tested using a ColorMatching System (CS-5).

Dyeing procedure, experimental steps of the fiber material of the present invention

1, weighing polylactic acid (PLA) fiber material 5 grams

2, preparation of dye bath composition 100ml

A, formulated dye (C.I. disperse dye red 60 or C.I. disperse dye blue 79) concentration: 1.0% (mass percentage)

B. Formulation auxiliary concentration: 0.16% chitosan-heloxy-type surfactant

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

D, temperature: 110 ° C (heating rate 2 ° C / min)

3, polylactic acid fiber, or polylactic acid fiber surface coated with chitosan-heloxane type surfactant

4. Dyeing step, 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 additives. The polylactic acid fiber material and the dye bath composition were separately placed in a steel cylinder at room temperature.

5. The retarding step was set to an initial temperature of 50 ° C, and the dye bath composition and the polylactic acid fiber material immersed therein were heated to 110 ° C at a heating rate of 2 ° C / min.

6. A dyeing step of holding the dye bath composition and the polylactic acid fiber material immersed therein at 110 ° C for 30 minutes.

7. The step of cooling the cylinder is carried out, and the composition of the dye bath and the polylactic acid fiber material immersed therein are lowered to 90 ° C at a cooling rate of 2 ° C / min, and then the polylactic acid fiber material is taken out from the dye bath composition. .

8, washed and dried

9. Perform colorimetry. Use the Applied Color System to make it calibrated and then enter the test.

Dyeing property of the chitosan-oxirane type surfactant of the invention

Table 2 shows the dyeing and chromatic aberration results of the dyeing of the polyester fiber using the chitosan-methoxyl type surfactant, the CI disperse dye blue 79, and it is known that the chitosan-矽 of the present invention is added. The oxane type surfactant has a better dyeing rate, and the second row (the PEG2000) of the first column on the left side of the dye coloring rate is the PLA coated chitosan-methoxyalkane type surfactant via the plasma. The name code of the modification process is in order.

To explore the interaction between auxiliaries and dyes, the larger the K/S value is shown in Table 2, the best dyeing rate is obtained. From PEG8000, the K/S value is 1.645, and after plasma modification, PEG8000 is 1.933 judged that the dyeing effect of polylactic acid fabric can be increased after plasma modification. The PEG8000△E value is 3.72, and the △E value is 1.92 after plasma modification. The smaller the △E value, the better the dyeability. There is also a good dyeing effect after the plasma is modified.

Table 3 shows the dyeing and color difference results of the dyeing of polylactic acid fiber using chitosan-vaoxane type surfactant, CI disperse dye red 60, and the K/S value of PEG8000 in Table 3 blue disperse dye. 22.22, after the plasma modification, the K/S value is 22.99, the △E value is 0.94, and the plasma is modified to 2.24. The effect after plasma modification is opposite to that of the red disperse dye.

(1) The present invention utilizes the addition of a hydrophilic group on the OH functional group of chitosan and the addition of a hydrophobic group on the CH ₃ functional group to increase the hydrophobic and hydrophilic ends, thereby preparing a series of chitosan-矽Oxygen-type surfactant.

(2) Using molecular design viewpoints to introduce molecular groups of different functionalities into the molecular structure of chitosan-vaoxane type surfactant and to draw their molecules by hydrophilic groups and hydrophobic groups in polylactic acid fibers. The chain is such that the chitosan is immobilized on the polylactic acid fiber and is not easily peeled off.

(3) The argon plasma treatment method is used to greatly increase the surface area, so that the surface is more hydrophilic, and the polylactic acid fabric is coated and then treated with plasma to raise oxygen.

(4) Dyeing properties, chitosan-oxime type surfactants have the highest K/S value in the +PEG8000 red disperse dye, indicating the best dyeing rate, and the △E value is also small, representing The best dyeing performance.

The fiber treatment by using the chitosan-vaoxane type surfactant of the invention can make the fiber dyeing have good dye uptake, level dyeing and deep dyeing. Further, by using the dyeing composition of the present invention in a dyeing process, the dyed fibers, particularly the polylactic acid fiber material and the polyester fiber material, can have good wash fastness and light fastness.

Industrial utilization of the present invention

The disadvantages of polylactic acid fiber materials and polyester fiber materials are that they are not easy to be deeply dyed, especially disperse dyes, and the present invention uses chitosan-vaoxane type surfactant as an auxiliary agent to help deep dyeing and leveling. The effect is good, and has good washing fastness and light fastness, and is quite industrially useful.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (10)

A dyeing composition of a fibrous material, comprising: providing a surface treated fibrous material, the surface of the fibrous material being treated with a chitosan-vaoxane type surfactant; providing a dye bath composition, the dye bath composition comprising: An auxiliary agent, wherein the auxiliary agent is contained in an amount of 0.01% by weight to 10% by weight based on the total weight of the dyeing bath composition; and the dye is used in an amount of the total weight of the dyeing bath composition. 0.1% by weight to 10% by weight; and a carrier, the carrier is contained in an amount of 80% by weight to 99.89% by weight based on the total weight of the dyeing bath composition; wherein the chitosan-oxime An alkane type surfactant having a structure represented by the following formula (I): Where G represents a chitosan residue , R represents an organic group selected from a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a phenyl group, and m represents a number of repeating units of chitosan, and its value 2~5000; x represents the repeating unit number of the oxoxane 1~200; y represents the number of repeating units of -CH ₂ - in the acid anhydride or diacid compound, and its value is 0-20; n represents the repeating unit of the polyoxyethylene ether segment The number is from 10 to 5000. A dye bath composition comprising: an auxiliary agent, the auxiliary agent is contained in an amount of 0.01% by weight to 10% by weight based on the total weight of the dye bath composition; and the dye is based on the total weight of the dye bath composition The dye is contained in an amount of 0.1% by weight to 10% by weight; and the carrier is contained in an amount of 80% by weight to 99.89% by weight based on the total weight of the dyeing bath composition; The agent comprises at least one chitosan-deoxymethane type surfactant having a structure represented by the following formula (I): Where G represents a chitosan residue , R represents an organic group selected from a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a phenyl group, and m represents a number of repeating units of chitosan, and its value 2~5000; x represents the repeating unit number of the oxoxane 1~200; y represents the number of repeating units of -CH ₂ - in the acid anhydride or diacid compound, and its value is 0-20; n represents the repeating unit of the polyoxyethylene ether segment The number is from 10 to 5000.  The dyeing composition of the fibrous material according to the above aspect of the invention, wherein the carrier is selected from the group consisting of water, ethanol, acetone or a mixed solution thereof.    The dyeing composition of the fibrous material according to the first aspect of the invention, wherein the dye bath composition has a pH of 2 to 6 at room temperature.    The dyeing composition according to the above aspect of the invention, wherein the concentration of the fiber surface treatment agent of the chitosan-vaoxane surfactant is from 0.05% by weight to 10% by weight.   A dyeing process for a fibrous material, comprising: providing a surface treated fibrous material, the surface of the fibrous material being treated with a chitosan-vaoxane type surfactant; providing a dye bath composition, the dye bath composition And comprising: an auxiliary agent in an amount of 0.01% by weight to 10% by weight based on the total weight of the dye bath composition; and a dye based on the total weight of the dye bath composition, the dye The content is from 0.1% by weight to 10% by weight; and the carrier is contained in an amount of from 80% by weight to 99.89% by weight based on the total weight of the dye bath composition; and the chitosan is- a fiber material surface-treated with a siloxane-type surfactant, wherein the fiber material is dyed by the dye bath composition, wherein the chitosan-methoxyalkane type surfactant has the general formula (I) Structure of surfactant, Where G represents a chitosan residue , R represents an organic group selected from a hydrogen atom, a hydroxyl group (-OH), a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a phenyl group, and m represents a number of repeating units of chitosan, and its value 2~5000; x represents the repeating unit number of the oxoxane 1~200; y represents the number of repeating units of -CH ₂ - in the acid anhydride or diacid compound, and its value is 0-20; n represents the repeating unit of the polyoxyethylene ether segment The number is from 10 to 5000.  The dyeing process of the fiber material according to claim 6, wherein the fiber material surface-treated with the chitosan-methoxyalkane type surfactant is processed after the plasma technology, and then dyed. The carrier is selected from the group consisting of water, ethanol, acetone or a mixed solution thereof; the adjuvant comprises at least one chitosan-methoxyalkane type surfactant as described in claim 6 of the patent application.    A dyeing process for a fibrous material comprising: providing a fibrous material, providing a dye bath composition as in claim 2 of the patent application, and dyeing the fibrous material with the dye bath composition.    The dyeing process of the fibrous material according to claim 8, wherein the fiber material is dyed by the dyeing composition, comprising: a dip dyeing step, immersing the fiber material in the dyeing bath at room temperature In the composition; the dyeing step, heating the dye bath composition and the fibrous material immersed therein to a temperature of from 0.5 ° C / min to 5 ° C / min to 100 ° C ~ 200 ° C; dyeing step, at 100 The dye bath composition and the fiber material immersed therein are held at a temperature of 20 ° C to 60 ° C for 20 minutes to 60 minutes; and the cooling step is performed at a temperature drop rate of 0.5 ° C / min to 5 ° C / min. After the dye bath composition and the fibrous material soaked therein are lowered to 50 ° C to 90 ° C, the fibrous material is taken out from the dye bath composition.    A dyeing process for a fibrous material as described in claims 6 and 8, wherein the fibrous material is selected from the group consisting of polylactic acid fibers or polyester fiber materials.