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CN109826024A - A kind of dyeing method based on natural pigment of cationically modified flax fabric - Google Patents

A kind of dyeing method based on natural pigment of cationically modified flax fabric Download PDF

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CN109826024A
CN109826024A CN201910183880.3A CN201910183880A CN109826024A CN 109826024 A CN109826024 A CN 109826024A CN 201910183880 A CN201910183880 A CN 201910183880A CN 109826024 A CN109826024 A CN 109826024A
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dyeing
natural pigment
solution
fabric
dye
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王立娟
崔畅
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Northeast Forestry University
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Northeast Forestry University
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Abstract

一种基于阳离子改性的亚麻织物的天然色素的染色方法,它涉及亚麻织物的染色方法。它是要解决现有的天然色素应用于亚麻织物染色时存在着色率低、色牢度低的问题。本方法:一、将亚麻织物浸进入到纤维素酶溶液用纤维素酶溶液预处理;二、用阳离子改性剂溶液对亚麻织物进行二次处理;三、用天然色素染料配制染料溶液;四、将完成二次处理的亚麻织物浸入到染料溶液中染色,完成亚麻织物的染色。本发明的方法的上染百分率达到25%~50%,色牢度达到4~5级。适用于印染领域。

A dyeing method based on the natural pigment of cationically modified linen fabric, which relates to the dyeing method of linen fabric. It is to solve the problems of low coloring rate and low color fastness when the existing natural pigment is applied to linen fabric dyeing. The method: 1. immersing the flax fabric into the cellulase solution and pre-treating it with the cellulase solution; 2. performing the secondary treatment on the linen fabric with the cationic modifier solution; 3. preparing the dye solution with natural pigment dyes; 4. . Dipping the linen fabric after secondary treatment into the dye solution to dye the linen fabric. The dyeing percentage of the method of the invention reaches 25% to 50%, and the color fastness reaches 4 to 5 grades. Suitable for printing and dyeing field.

Description

A kind of colouring method of the natural pigment based on cation-modified sodolin
Technical field
The present invention relates to the colouring methods of sodolin.
Background technique
Flax fiber is extremely important raw material in entire production in light industry as a kind of natural reproducible resource. Sodolin has good water imbibition, static electricity resistance, thermal conductivity and gas permeability, is widely used in various textile fabrics.Flax The main composition of fiber is cellulose, and containing impurity such as more lignin and hemicellulose, due to its special structure group At leading to primary flax fiber textile there are feels coarse, dyeability is poor, the shortcomings that easily decoloration after washing.Therefore it is promoted Level of comfort that flax fiber is taken, the dyeability for improving sodolin and to improve fastness after its dyeing be that current flax is spun Knit one of industry urgent problem to be solved.
In recent years, as the green and healthy idea of the public is constantly promoted, it has been found that the synthesis that textile industry largely uses There is irremediable defects for dyestuff: toxic, carcinogenicity and environment harmfulness.Synthetic dyestuffs are substituted using natural pigment It can solve above-mentioned problem.Vegatable tannin is that one kind is widely present in the intracorporal polyatomic phenol natural pigment of plant, and resource is rich Richness, it is extremely stable in aqueous solution and environment friendly and pollution-free, but as natural pigment be applied to Dyeing of Linen Fabric when exist coloring The problem that rate is low, color fastness is low, performance is unstable.
Summary of the invention
That there are tinctorial yields is low, color fastness is low when being applied to Dyeing of Linen Fabric the present invention is to solve existing natural pigment The problem of, and a kind of colouring method of natural pigment based on cation-modified sodolin is provided.
The colouring method of natural pigment based on cation-modified sodolin of the invention, sequentially includes the following steps:
It one, is that configuration concentration is 10~20g/L's as solvent using the NaAc_HAc buffer solution that pH is 4.5~5.5 Cellulase solution;Sodolin leaching is entered in cellulase solution, bath raio is 1:(15~16), it is warming up to 45~55 DEG C 3~5h is kept, sodolin is taken out, is washed with water to neutrality, pretreatment is completed in drying;
Two, be 20g/L~40g/L by the concentration of cation modifier, the concentration of sodium hydroxide is 10g/L~15g/L, will Cation modifier and sodium hydroxide are added to water, are uniformly mixed, obtain modifier solution;Wherein cation modifier is (3- Chloro- 2- hydroxypropyl) trimethyl ammonium chloride (CHPTMAC);It will complete pretreated sodolin to be immersed in modifier solution, bathe Than for 1:(30~50), 65~75 DEG C of 50~70min of holding are warming up to, fabric is taken out, are washed with water to neutrality, drying completes two Secondary processing;
Three, it is 20~40g/L of concentration of 10~40g/L, accelerant by the concentration of natural colouring substance, by dyestuff and promotees to contaminate Agent is added in distilled water, stirs evenly, obtains dye solution;
Four, dye solution is warming up to 40~45 DEG C, it is molten that the sodolin for completing secondary treatment is then immersed in dyestuff It is dyed in liquid, after dyeing, takes out sodolin, with soaping, then after being rinsed with water, the dyeing of sodolin is completed in drying.
The microstructure of flax fiber determines dyeing and finishing process engineering, and it is pre- that sodolin is first used cellulase by the present invention Processing, is then reprocessed with CHPTMAC under alkaline condition again, and two-step method is cooperateed with glucose in flax fiber element Ring is opened, and the active force between fiber macromolecular is weakened, and the structure between fiber macromolecular becomes loose, and fiber morphology changes Become, surface generates den and stripping damage streak, increases the noncrystalline domain of flax fiber, to make to contaminate in subsequent dyeing course Material is easily accessible, and improves accessibility and reactivity, achievees the purpose that improve dyeing percentage and color fastness.Method of the invention For dyeing percentage up to 25%~50%, color fastness reaches 4~5 grades.Method of the invention can be used for field of printing and dyeing.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of sodolin before modified in embodiment 1;
Fig. 2 is the stereoscan photograph through the pretreated sodolin of step 1 in embodiment 1;
Fig. 3 is the stereoscan photograph of the sodolin in embodiment 1 after step 2 completes secondary treatment;
Fig. 4 is the energy spectrum diagram of unmodified sodolin in embodiment 1;
Fig. 5 is the energy spectrum diagram of the sodolin in embodiment 1 after step 2 completes secondary treatment;
Fig. 6 is the XRD spectra of the fabric and the sodolin after secondary treatment of unmodified flax in embodiment 1.
Specific embodiment
Specific embodiment 1: the dyeing side of the natural pigment based on cation-modified sodolin of present embodiment Method sequentially includes the following steps:
It one, is that configuration concentration is 10~20g/L's as solvent using the NaAc_HAc buffer solution that pH is 4.5~5.5 Cellulase solution;Sodolin leaching is entered in cellulase solution, bath raio is 1:(15~16), it is warming up to 45~55 DEG C 3~5h is kept, sodolin is taken out, is washed with water to neutrality, pretreatment is completed in drying;
Two, be 20g/L~40g/L by the concentration of cation modifier, the concentration of sodium hydroxide is 10g/L~15g/L, will Cation modifier and sodium hydroxide are added to water, are uniformly mixed, obtain modifier solution;Wherein cation modifier is (3- Chloro- 2- hydroxypropyl) trimethyl ammonium chloride (CHPTMAC);It will complete pretreated sodolin to be immersed in modifier solution, bathe Than for 1:(30~50), 65~75 DEG C of 50~70min of holding are warming up to, fabric is taken out, are washed with water to neutrality, drying completes two Secondary processing;
Three, it is 20~40g/L of concentration of 10~40g/L, accelerant by the concentration of natural colouring substance, by dyestuff and promotees to contaminate Agent is added in distilled water, stirs evenly, obtains dye solution;
Four, dye solution is warming up to 40~45 DEG C, it is molten that the sodolin for completing secondary treatment is then immersed in dyestuff It is dyed in liquid, after dyeing, takes out sodolin, with soaping, then after being rinsed with water, the dyeing of sodolin is completed in drying.
Specific embodiment 2: the present embodiment is different from the first embodiment in that accelerant described in step 3 For sodium chloride;It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that day described in step 4 Right colouring substance is rubber Bowl tannin or Baybery tannin;It is other the same as one or two specific embodiments.
Specific embodiment 4: being dyed in step 4 unlike one of present embodiment and specific embodiment one to three When, bath raio is 1:(20~40);It is other identical as one of specific embodiment one to three.
Specific embodiment 5: being dyed in step 4 unlike one of present embodiment and specific embodiment one to four When, dye bath is warming up to 80~95 DEG C of 50~90min of holding with 2~5 DEG C/min;Other phases one of with specific embodiment one to four Together.
Specific embodiment 6: being dyed in step 4 unlike one of present embodiment and specific embodiment one to four When, dye bath is warming up to 90 DEG C of holding 70min with 3 DEG C/min;It is other identical as one of specific embodiment one to four.
With the following examples verifying this it is bright the utility model has the advantages that
Embodiment 1: the colouring method of the natural pigment based on cation-modified sodolin of the present embodiment, by following Step carries out:
It one, be 4.5 using pH is NaAc_HAc buffer solution as solvent, configuration concentration is that the cellulase of 15g/L is molten Liquid;Sodolin is immersed in cellulase solution, bath raio 1:15, is warming up to 45 DEG C of holding 3h, taken out fabric, be washed with water It to neutrality, is dried 3 hours under conditions of temperature is 40 DEG C, completes pretreatment;
Two, be 30g/L by the concentration of cation modifier, the concentration of sodium hydroxide is 12.5g/L, by cation modifier It is added to water with sodium hydroxide, is uniformly mixed, obtains modifier solution;Wherein cation modifier is (the chloro- 2- hydroxypropyl of 3-) Trimethyl ammonium chloride (CHPTMAC);It will complete pretreated sodolin to be immersed in modifier solution, bath raio 1:30, rise Temperature is taken out fabric, is washed with water to neutrality, dry 3 hours under conditions of temperature is 40 DEG C, complete two to 70 DEG C of holding 60min Secondary processing;
Three, it is the concentration 20g/L of 30g/L, sodium chloride by the concentration of dyestuff, dyestuff and accelerant is added in distilled water, It stirs evenly, obtains dye solution;Wherein dyestuff is rubber Bowl tannin;
Four, dye solution is warming up to 40 DEG C, then pretreated sodolin is immersed in dye solution, bath raio For 1:20, dye bath is warming up to 90 DEG C of holdings dyeing 70min with 3 DEG C/min, after dyeing, takes out sodolin, with soaping, then After being rinsed with water, the dyeing of sodolin is completed in drying.
The stereoscan photograph of the unmodified sodolin of step 1 through step 1 as shown in Figure 1, complete pre- in embodiment 1 The stereoscan photograph of the sodolin of processing is as shown in Fig. 2, complete the scanning electricity of the sodolin of secondary treatment through step 2 Mirror photo is as shown in Figure 3.Can be seen that out untreated flax fiber surface from Fig. 1, Fig. 2 and Fig. 3 has fiber fines tightly Attachment has burr, and feel is poor, and the comfort of dress is poor.After enzyme pretreatment, fiber surface is relatively smooth, fiber table The fiber fines in face remove completely substantially, will not generate prodding and itching feeling again, improve the wearing comfort of sodolin;By secondary The flax fiber surface of processing is with den and stripping damage streak.After pretreatment and secondary treatment, the intensive dyestuff of marshalling Structure change has occurred in the low cellulose crystallite area of the accessibility being difficult to enter, and cellulose glucose ring is opened, and fiber divides greatly Active force between son is weakened, and the structure between fiber macromolecular becomes loose, thus fiber morphology changes, and surface generates nest Point and stripping damage streak, the noncrystalline domain of flax fiber increase.The surface topography of flax fiber is set to change by modification, Den and stripping damage streak are produced, and then improves the dyeability of flax fiber.
In embodiment 1 in step 1 the energy spectrum diagram of unmodified sodolin as shown in figure 4, Elemental analysis data such as table 1 Shown, the energy spectrum diagram for completing the sodolin of secondary treatment through step 2 is led to as shown in figure 5, Elemental analysis data is as shown in table 2 The energy spectrum analysis to rear flax fiber before modified is crossed, it is found that the percentage composition of N element in modified flax fiber is 18.46%, The percentage composition of N element is 16.30% in flax fiber before modified, and the N element content in modified flax fiber, which is higher than, to be modified Preceding flax fiber, sodolin are handled through CHPTMAC under enzyme pretreatment and alkaline condition, and CHPTMAC forms band epoxy group Quaternary ammonium salt cationic compound, and with cellulose macromolecule 6 on hydroxy combining, keep the crystallization of macromolecular cellulose broken It is bad.
The Elemental analysis data of the unmodified sodolin of table 1
Element Wt% At%
CK 43.76 49.86
NK 16.68 16.30
OK 39.56 33.84
Table 2 completes the Elemental analysis data of the sodolin of secondary treatment through step 2
Element t Wt% At At%
CK 43.19 49.16
NK 18.91 18.46
OK 37.90 32.38
In embodiment 1 in step 1 the fabric of unmodified flax with through step 2 complete secondary treatment flax fabric XRD spectra as shown in fig. 6, from fig. 6, it can be seen that flax fiber has sharp diffraction maximum, modified flax before modified Fiber diffraction peak acuity reduces, and illustrates to destroy flax fiber when modifying agent is reacted with cellulose fibre to a certain extent The ordered structure of middle cellulose arrangement, declines its crystallinity.This is because modifier molecules amount is small, cellulose chain can be penetrated Gap between piece causes the hydrogen bond between chain piece to be broken, therefore crystallinity declines.It is possible thereby at inferring flax fiber by being modified Noncrystalline domain is managed to increase.In noncrystalline domain, macromolecular arrangement is disorderly and unsystematic, there is more cavity and seam between molecule and molecule Gap improves the accessibility of dyestuff, so that fiber has good dyeability.
Embodiment 2: the colouring method of the natural pigment based on cation-modified sodolin of the present embodiment, by following Step carries out:
It one, be 4.5 using pH is NaAc_HAc buffer solution as solvent, configuration concentration is that the cellulase of 20g/L is molten Liquid;Sodolin is immersed in cellulase solution, bath raio 1:15, is warming up to 45 DEG C of holding 3h, taken out fabric, be washed with water It to neutrality, is dried 3 hours under conditions of temperature is 40 DEG C, completes pretreatment;
Two, be 40g/L by the concentration of cation modifier, the concentration of sodium hydroxide is 12.5g/L, by cation modifier It is added to water with sodium hydroxide, is uniformly mixed, obtains modifier solution;Wherein cation modifier is (the chloro- 2- hydroxypropyl of 3-) Trimethyl ammonium chloride (CHPTMAC);It will complete pretreated sodolin to be immersed in modifier solution, bath raio 1:30, rise Temperature is taken out fabric, is washed with water to neutrality, dry 3 hours under conditions of temperature is 40 DEG C, complete two to 72 DEG C of holding 70min Secondary processing;
Three, it is the concentration 30g/L of 15g/L, accelerant by the concentration of dyestuff, dyestuff and accelerant is added in distilled water, It stirs evenly, obtains dye solution;Wherein dyestuff is rubber Bowl tannin;Accelerant is sodium chloride;
Four, dye solution is warming up to 40 DEG C, then pretreated sodolin is immersed in dye solution, bath raio For 1:20, dye bath is warming up to 85 DEG C of holdings dyeing 60min with 5 DEG C/min, after dyeing, takes out sodolin, with soaping, then After being rinsed with water, the dyeing of sodolin is completed in drying.
Embodiment 3: the dyestuff in step 3 is Baybery tannin to the present embodiment unlike the first embodiment, other and implementation Example 1 is identical.
Embodiment 4: the dyestuff in step 3 is Baybery tannin to the present embodiment as different from Example 2, other and implementation Example 2 is identical.
The measurement that Lab value and dye-uptake are carried out to sodolin after the dyeing of Examples 1 to 4 preparation, as a result such as 3 institute of table Show:
Sodolin carries out Lab value and dye-uptake result after the dyeing of 3 Examples 1 to 4 of table preparation
Sample Dyestuff L* a* b* Color difference Dye-uptake (%)
Embodiment 1 Rubber Bowl tannin 37.58 7.52 33.79 70.92 34.87
Embodiment 2 Rubber Bowl tannin 44.23 5.73 21.52 59.56 26.49
Embodiment 3 Baybery tannin 50.16 15.47 24.54 57.24 49.96
Embodiment 4 Baybery tannin 54.98 12.69 18.34 49.78 39.12
Fastness analysis is carried out to the dyeing sodolin of Examples 1 to 4 preparation, wherein the measurement of washing fastness is according to state Sample is handled under the conditions of as defined in family standard GB/T14575-2009, after processing with " dyefastness fading sample card " or " dyefastness grey scale for staining " is compared grading.Washing fastness is divided into 5 grades, and 1 grade worst, and 5 grades best.Fastness to rubbing is divided into Dry fastness and two kinds of fastness to wet rubbing are tested enterprising in rubfastness test instrument according to standard GB/T/T14575-2009 Row, compares grading with " crock fastness staining gray scale ".Crock fastness is divided into 5 grades, and 1 grade worst, and 5 grades best.Light Measurement be international standard AATCC Test Method 16-2004 according to american chemical textile association, with YG (B) 611- After type III solarization weathering fastness machine illumination for 24 hours, light grade is obtained with " blue wool colorimetric card " comparison.Washing fastness Measurement result it is as shown in table 4, the measurement result of fastness to rubbing and light is as shown in table 5.
4 washing fastness test result of table
From table 4, it can be seen that the washing fastness of the sodolin after Examples 1 to 4 dyeing all reaches industrial and wants It asks.
The test result of 5 crock fastness of table and light
As can be seen from Table 5, the dry and wet crock fastness of the sodolin after Examples 1 to 4 dyeing belongs to light Higher level meets industrial standard.Flax fiber dyer can be shortened to a certain extent by further relating to method of the invention Skill process improves production efficiency.

Claims (6)

1.一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于该方法按以下步骤进行:1. a dyeing method based on the natural pigment of cation-modified flax fabric, is characterized in that this method is carried out according to the following steps: 一、以pH为4.5~5.5的醋酸-醋酸钠缓冲溶液为溶剂是,配置浓度为10~20g/L的纤维素酶溶液;将亚麻织物浸进入到纤维素酶溶液中,浴比为1:(15~16),升温至45~55℃保持3~5h,取出亚麻织物,用水洗至中性,烘干,完成预处理;1. Use acetic acid-sodium acetate buffer solution with pH of 4.5 to 5.5 as solvent, configure cellulase solution with concentration of 10 to 20g/L; dip the linen fabric into the cellulase solution, and the bath ratio is 1: (15-16), heat up to 45-55°C for 3-5h, take out the linen fabric, wash with water until neutral, dry to complete the pretreatment; 二、按阳离子改性剂的浓度为20g/L~40g/L、氢氧化钠的浓度为10g/L~15g/L,将阳离子改性剂和氢氧化钠加入到水,混合均匀,得到改性剂溶液;其中阳离子改性剂为(3-氯-2-羟丙基)三甲基氯化铵;将完成预处理的亚麻织物浸入到改性剂溶液中,浴比为1:(30~50),升温至65~75℃保持50~70min,取出织物,用水洗至中性,烘干,完成二次处理;2. According to the concentration of the cationic modifier is 20g/L~40g/L and the concentration of sodium hydroxide is 10g/L~15g/L, add the cationic modifier and sodium hydroxide into the water and mix them evenly to obtain the modified solution. The cationic modifier is (3-chloro-2-hydroxypropyl) trimethylammonium chloride; the pretreated linen fabric is immersed in the modifier solution, and the bath ratio is 1:(30 ~50), heat up to 65 ~ 75 ℃ for 50 ~ 70min, take out the fabric, wash with water to neutrality, dry, and complete the secondary treatment; 三、按天然色素染料的浓度为10~40g/L、促染剂的浓度20~40g/L,将染料与促染剂加入蒸馏水中,搅拌均匀,得到染料溶液;3. According to the concentration of natural pigment dyes of 10-40g/L and the concentration of dye accelerators of 20-40g/L, add dyes and dye accelerators into distilled water, stir evenly to obtain dye solution; 四、将染料溶液升温至40~45℃,然后将完成二次处理的亚麻织物浸入到染料溶液中染色,染色完毕后,取出亚麻织物,用皂洗,再用水冲洗后,烘干,完成亚麻织物的染色。4. Heat the dye solution to 40-45°C, then immerse the secondary treated linen fabric in the dye solution for dyeing. After dyeing, take out the linen fabric, wash with soap, rinse with water, and dry to complete the linen Dyeing of fabrics. 2.根据权利要求1所述的一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于步骤三中所述的促染剂为氯化钠。2. a kind of dyeing method based on the natural pigment of the cationic modified flax fabric according to claim 1 is characterized in that the dye accelerator described in the step 3 is sodium chloride. 3.根据权利要求1或2所述的一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于步骤四中所述的天然色素染料为橡椀单宁或杨梅单宁。3. a kind of dyeing method based on the natural pigment of the cationic modified flax fabric according to claim 1 and 2, is characterized in that the natural pigment dyestuff described in the step 4 is oak tannin or bayberry tannin. 4.根据权利要求1或2所述的一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于步骤四中染色时,浴比为1:(20~40)。4. The method for dyeing a natural pigment based on cationically modified linen fabric according to claim 1 or 2, characterized in that during dyeing in step 4, the bath ratio is 1:(20-40). 5.根据权利要求1或2所述的一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于步骤四中染色时,染浴以2~5℃/min升温至80~95℃保持50~90min。5. a kind of dyeing method based on the natural pigment of cationic modified linen fabric according to claim 1 and 2, it is characterized in that when dyeing in step 4, the dyeing bath is heated up to 80~95 ℃ at 2~5 ℃/min ℃ to maintain 50 ~ 90min. 6.根据权利要求1或2所述的一种基于阳离子改性的亚麻织物的天然色素的染色方法,其特征在于步骤四中染色时,染浴以3℃/min升温至90℃保持70min。6. a kind of dyeing method based on the natural pigment of cation-modified flax fabric according to claim 1 or 2, is characterized in that when dyeing in step 4, the dyeing bath is heated to 90 ℃ at 3 ℃/min and keeps 70min.
CN201910183880.3A 2019-03-12 2019-03-12 A kind of dyeing method based on natural pigment of cationically modified flax fabric Pending CN109826024A (en)

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CN111705510A (en) * 2020-06-11 2020-09-25 台州恒彩纺织科技有限公司 Modified cellulose fiber and dyeing pretreatment method of knitted fabric woven by using same
CN111705510B (en) * 2020-06-11 2022-11-01 台州恒彩纺织科技有限公司 Modified cellulose fiber and dyeing pretreatment method of knitted fabric woven by using same
CN114606783A (en) * 2022-03-18 2022-06-10 德州学院 A process of dyeing hemp with ebony

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