CN103015224B - Method for dyeing fabric with natural mineral dye - Google Patents

Abstract

The invention relates to a method for dyeing natural mineral dyes on fabrics, comprising: (1) modifying the fabric with a modifying agent by dipping or padding and then preparing for use; (2) using a dispersant to nanometerize the natural mineral dyes Finally, the nano-mineral dye is prepared into a dye solution, and the above-mentioned modified fabric is dyed by a dyeing method of two dipping and two padding. After dyeing, it is dried, baked, soaped, washed with water, and then dried. The dyeing method of the invention is simple and feasible; it improves the color fastness of natural dye dyeing, increases its functionality, and realizes the dual purposes of natural dye high color fastness ecological dyeing and functional finishing.

Description

A kind of dyeing method of natural mineral dyestuff on fabric

technical field

The invention belongs to the field of fabric dyeing methods, in particular to a method for dyeing natural mineral dyes on fabrics.

Background technique

Textiles are easily irritated to human skin after being dyed with some chemically synthesized dyes. On the other hand, chemically synthesized dyes will have a certain impact on the environment during production and use. With the enhancement of ecological and environmental awareness, more and more consumers prefer green and safe textiles and pay attention to the safety of textile dyes.

In terms of dyeing with natural dyes, as some varieties of synthetic dyes are banned, people's interest in natural dyes has increased again. The main reason is that natural dyes are obtained from plants, animals, minerals or microorganisms such as bacteria, fungi, molds, and some other natural raw materials, with little or no chemically processed dyes. Most natural dyes are ecologically compatible with the environment, biodegradable, and have low toxicity. In addition, the consumption of petroleum resources has shown that the raw materials of synthetic dyes are insufficient, and it also promotes the development of natural dyes to supplement synthetic dyes. Although natural dyes still have many shortcomings, such as poor color fastness, incomplete chromatogram, and expensive prices of most varieties, it is impossible to completely replace synthetic dyes, but it is valuable as a partial replacement or supplement for synthetic dyes, especially with The development of some high value-added textiles with natural dyes has broad prospects for development.

Natural mineral dyes, as natural inorganic dyes, have a long history of application. Natural mineral dyes are a kind of natural inorganic dyes with different colors, such as brownish red, green, gray, yellow, white and so on. Among them: the green ores mainly include: malachite [Cu ₂ (CO ₃ ) (OH) ₂ ], green copperite [Cu ₂ (OH) ₃ Cl], bile alum [Cu ₄ (OH) ₄ SO ₄ ] and brown Ores (mainly oxides containing iron and manganese). Blue ores include: azurite [Cu ₂ (CO ₃ ) ₂ (OH) ₂ ], lapis lazuli [(Na,Ca) ₃ (AlSiO ₄ )(SO ₄ ,S,Cl) ₂ ], cobalt soil [m (Co,Ni)O.MnO ₂ .nH ₂ O]. Red ores are: hematite (Fe ₂ O ₃ ) and specularite, various shades of red earthy substances containing iron oxide. Yellow ores include: orpiment (As ₂ S ₃ ), lead yellow (PbO), phlogopite, and various yellow earthy substances containing iron hydroxide. These natural mineral dyes have no affinity for fibers, so their dyeing is different from dye dyeing. Through research, natural mineral dyes can be nano-sized in the presence of dispersants. In the case of fiber swelling, on the one hand, the mineral dyes penetrate into the fiber with fine particles to achieve the purpose of dyeing; on the other hand, the nano-sized minerals The dye is carried to the surface of the fiber through the padding of the fabric, and deposited in the fiber capillary space or tissue space. As the fabric is heated during the drying and baking process, the distance between the molecular aggregates of the dispersant shrinks to form a strong, wear-resistant, colorless and transparent linear polymer film, which is tightly bonded to the surface of the fiber. In addition, under high-temperature baking, the "dye seat" on the fabric and the active functional group in the dispersant molecule form a cross-link between the fiber and the dispersant, and between the dispersant molecules, forming a three-dimensional network structure, so that Mineral dyes are embedded in the dispersant film and firmly attached to the fabric, so as to achieve the purpose of "dyeing". Therefore, to complete the dyeing of natural mineral dyes on fabrics, the structure of the dispersant and the "dye seat" on the fabric are the key to improving the color fastness.

In addition, because some mineral dyes have some specific functions, such as anti-ultraviolet, far-infrared, blood circulation and blood stasis, etc., the added value of textiles can be increased by dyeing natural mineral dyes on fabrics, thereby achieving the improvement of natural dyes. Improve the color fastness, increase its functionality, realize the dual purpose of ecological dyeing with high color fastness of natural dyes and functional finishing.

Contents of the invention

The technical problem to be solved by the present invention is to provide a dyeing method of natural mineral dyes on fabrics. The dyeing method of the present invention is simple and feasible, can improve the color fastness of natural dye dyeing, increase its functionality, and realize high color fastness of natural dyes. The dual purpose of ecological dyeing and functional finishing.

A kind of dyeing method of natural mineral dyestuff of the present invention on fabric, comprises:

(1) Modifying the fabric with a fabric modifier by dipping or padding;

(2) After the natural mineral dye is nano-sized with a dispersant, the nano-mineral dye is prepared into a dye solution, and the above-mentioned modified fabric is dyed by the dyeing method of two dipping and two padding. After dyeing, it is dried, baked, Soap, rinse and tumble dry.

In the step (1), the molecular structure of the fabric modifier contains at least a bifunctional group, which is epichlorohydrin, glyoxal, glutaraldehyde, ethylenediamine or diisocyanate.

The fabric in the step (1) is one of cotton fabric, linen fabric, polyester fabric, cotton-linen blended fabric, cotton-polyester blended fabric, wool fabric, and rabbit fur fabric.

The structural formula of the dispersant in the step (2) is:

Among them, R ₁ is H or CH ₃ ; R ₂ is one or more of C ₁ to C ₁₀ alkyl groups and hydroxyl-containing C ₁ to C ₁₀ alkyl groups; R ₃ is H or CH ₃ ; R ₄ is H or CH ₃ ; R ₅ is one or more of C ₁ -C ₁₀ alkyl, hydroxyl-containing C ₁ -C ₁₀ alkyl; a:b:c:d=0.3-0.5: 0-0.4: 0.4-0.7: 0-0.2, the weight average molecular weight of the dispersant is 8000-30000 g/mol.

The preparation method of the dispersant is as follows: at room temperature, add reaction monomers and solvents into the reaction vessel, pass nitrogen gas for 20-60 minutes, heat up to 60-85°C while stirring, add a part of the initiator dropwise, and then keep warm for 0.5-4 hours , then add the remaining initiator dropwise, and then keep the temperature for 5-12 hours. After the product is cooled, add the crude product dropwise into the poor solvent of the copolymer for reprecipitation, then wash and dry the copolymer to obtain the copolymer. After the sodium hydroxide solution is mixed, saponify at 30-50°C for 1-3 hours, then add the obtained product dropwise into acetone for re-precipitation, filter with suction, wash and dry to obtain a dispersant.

The reactive monomer is one or more of maleic anhydride, R ₂ COOC(R ₁ )CH ₂ , CH ₂ C(R ₄ )COOR ₅ , wherein R ₁ in R ₂ COOC(R ₁ )CH ₂ is H or CH ₃ , and R ₂ is one or more of C ₁ to C ₁₀ alkyl groups and C ₁ to C ₁₀ alkyl groups containing hydroxyl groups; R ₄ in CH ₂ C(R ₄ )COOR ₅ is H or CH ₃ , R ₅ is one or more of a C ₁ -C ₁₀ alkyl group and a hydroxyl group-containing C ₁ -C ₁₀ alkyl group.

Described solvent is methyl alcohol, ethanol, acetone, butanone, ethyl acetate, dimethyl sulfoxide or carbon tetrachloride; Initiator is azo compound initiator or organic peroxide initiator; The poor solvent of copolymer is Acetone, chloroform, dichloromethane, methanol or petroleum ether, the poor solvent of the copolymer depends on the solvent used in the reaction system and the reaction monomer.

The azo compound initiator is azobisisobutyronitrile or azobisisoheptanonitrile, and the organic peroxide initiator is benzoyl peroxide, dicumyl peroxide, lauryl peroxide or peroxide Diisopropyl dicarbonate.

By titration method, the actual molar content of maleic anhydride is 20-45%.

According to the amount of NaOH added, the actual degree of saponification is determined to be 15-80%.

The mineral dye in the step (2) is green ore, brown ore, blue ore, red ore or yellow ore.

For example: green ores mainly include: malachite [Cu ₂ (CO ₃ )(OH) ₂ ], green copperite [Cu ₂ (OH) ₃ Cl], bile alum [Cu ₄ (OH) ₄ SO ₄ ] and brown Ores (mainly oxides containing iron and manganese). Blue ores include: azurite [Cu ₂ (CO ₃ ) ₂ (OH) ₂ ], lapis lazuli [(Na,Ca) ₃ (AlSiO ₄ )(SO ₄ ,S,Cl) ₂ ], cobalt soil [m (Co,Ni)O.MnO ₂ .nH ₂ O]. Red ores are: hematite (Fe ₂ O ₃ ) and specularite, various shades of red earthy substances containing iron oxide. Yellow ores include: orpiment (As ₂ S ₃ ), lead yellow (PbO), phlogopite, and various yellow earthy substances containing iron hydroxide.

Natural mineral dyes have certain functionalities, such as anti-ultraviolet properties, far-infrared properties, and properties of promoting blood circulation and removing blood stasis.

In the step (2), it is nanometerized by adopting a mechanical method, especially by crushing and grinding, and the particle size of the ground natural mineral dye is 90-300 nm.

In the step (2), the drying temperature is 80-100° C., the drying time is 1-3 minutes, the baking temperature is 130-150° C., and the baking time is 3 minutes.

Determination of the K/S value of the dyed fabric before and after soaping is used to calculate the color fastness of the dyed fabric. The calculation formula of the color fastness is:

In the formula, _before K/S is the color depth of the dyed fabric before soaping of the dyed fabric, and _after K/S is the color depth of the dyed fabric before soaping of the dyed fabric.

Measure the K/S value of the dyed fabric before and after soaping, measure the K/S value of 13 different points, and use it to calculate the color unevenness of the dyed fabric. The calculation formula of the color unevenness is:

In the formula, K/S _i is the color depth of each point among the 13 points taken on the front of the dyed fabric, It is the average value of 13 points K/S.

The method for dyeing natural mineral dyes on fabrics of the present invention firstly involves a fabric modifying agent, by modifying fabrics, abundant "dye seats" are introduced into the fabrics. Secondly, the natural mineral dyes are nano-sized under a dispersant with a specific structure. By adding the dispersant, the natural mineral dyes can be wetted and dispersed very quickly in the water-based system, shortening the time of sand milling or ball milling, and the dispersant has good Natural mineral dyes have very good dispersion stability. Again, the padding method is used to dye the fabric. When the dyed fabric is baked at 130-150°C for 3 minutes, the dispersant reacts with the "dye seat" on the fabric to improve the color fastness after dyeing, thereby improving the Color fastness of natural mineral dyes on fabrics.

Beneficial effect

(1) The dyeing method of the present invention is simple and feasible;

(2) The dyeing method of the present invention improves the color fastness of natural dye dyeing, increases its functionality, and realizes the dual purposes of ecological dyeing with high color fastness of natural dyes and functional finishing.

Description of drawings

Fig. 1 is the SEM picture before pure cotton fabric dyeing among the embodiment 1;

Fig. 2 is the SEM picture of natural mineral dyestuff in embodiment 1 after dyeing the pure cotton fabric after modification.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

(1) Modification of pure cotton fabric: Add 0.5g of anionic emulsifier sodium lauryl sulfate powder into 200g of water, stir, and after the sodium lauryl sulfate is completely dissolved, add dropwise to the above 0.25% solution Add 4g of epichlorohydrin (fabric modifier) dropwise and stir until a stable and uniform emulsion of epichlorohydrin is prepared.

The pure cotton fabric (warp and weft yarn density 14.575tex×14.575tex, warp density 133 threads/10cm, weft density 72 threads/10cm) was treated by the modified method of two dipping and two rolling, and the excess rate was 70%. Dry at 110°C; treat the dried fabric in 12g/L NaOH solution at 60°C for 30 minutes, then take it out and wash it with water to make the pH of the cloth surface 7. After drying, measure the epoxy value on the cotton fabric ,stand-by.

The method of measuring the epoxy value is: configure a certain concentration of HClO ₄ and NaOH solution, and the concentration of the calibrated NaOH is 0.2456mol/L. Then the modified pure cotton fabric was cut into fragments of about 2mm × 2mm in size, 0.5g of the chopped cotton fabric was put into a round bottom flask, 10ml of calibrated HClO ₄ was added, and 40ml of deionized water was added. Stir at 30°C for 1 hour, then titrate with the calibrated NaOH concentration, and titrate the blank at the same time, and calculate the epoxy value on the cotton fabric by the following formula:

In the formula, V ₀ is the volume of NaOH consumed by the blank sample, mL; V _t is the volume of NaOH consumed by the sample sample, mL; C _NaOH is the concentration of NaOH, mol/L; m _fabric is the mass of cotton fabric, g.

By measuring the epoxy value on the modified fabric, the epoxy value on the fabric is 0.007mol/g fabric.

(2) Preparation of dispersant for nano-sized mineral dyes:

At room temperature, add monomer vinyl acetate (12.09g, 0.14mol) and maleic anhydride (5.882g, 0.06mol) into a 250mL four-neck flask, add solvent ethyl acetate (100g), and blow nitrogen for about 30min , and then mechanically stirred at 300r/min, while stirring, the temperature was raised to 70-72°C, and then a part of the initiator azobisisobutyronitrile (0.085g, 0.517mmol) was added dropwise. Insulate and react at 72°C for 2 hours, then add the remaining initiator azobisisobutyronitrile (0.085g, 0.517mmol) dropwise, then keep warm at 70-72°C, continue to react for 10h, then stop the reaction. After the product was cooled, the crude product was added dropwise into chloroform for reprecipitation, filtered with suction, washed with chloroform several times, and then baked in a vacuum oven at 40°C for 10 hours to obtain a copolymer. The actual molar ratio of maleic anhydride in the copolymer was 30.6%, and the yield was 70%.

Take 10g of copolymer into a 100mL three-necked flask, weigh a certain amount of NaOH (8.89g, 0.22mol) and dissolve it in 60mL of water, then add the NaOH aqueous solution into the three-necked flask, stir and react at 30°C for 2h, and react After stopping, the product was added dropwise into acetone for reprecipitation, suction filtered, washed several times, and then dried in a vacuum oven at 40°C for 10 hours to obtain the final dispersant product with a saponification degree of 40.9%.

(3) Nanoization of mineral dyes

Take 2g of mineral dye iron yellow, add 60ml of water to the sand mill, and add 250g of zirconium beads with a particle size of 2mm and 0.5mm, the compounding ratio of zirconium beads is 2mm:0.5mm=30:20, the prepared dispersant The dosage is 0.5g/g iron yellow. After all preparations are ready, turn on the sand mill at room temperature and grind for 3 hours. The particle diameter of iron yellow obtained under this condition is 150nm, and Zata is -35.2mV, and it is used for dyeing.

(4) Dyeing of mineral dyes on fabrics

The iron yellow with a particle size of 150nm is prepared into a dye solution with a concentration of 10g/L, and the modified cotton fabric is dyed by the dyeing method of two dipping and two padding. The padding rate is 80%. Dry at ℃×3min, bake at 130～150℃×3min, then soap at 95℃ for 10min with 3% soap powder, wash with water, and dry.

The dyeing results are shown in Table 1:

Iron yellow after the grinding of table 1 is to the dyeing result of fabric

As can be seen from Table 1, the color depth K/S value of the fabric after dyeing the cotton fabric modified in Example 1 is relatively high with iron yellow after grinding, and the color depth K/S value after soaping is still the same. Relatively high, that is, the dyeing fastness is relatively high; and the dyeing depth of the modified fabric is obviously higher than that of the unmodified fabric, and the color unevenness of the modified fabric is less than 10, which meets the standard.

Example 2

(1) Modification of pure cotton fabric: Add 0.5g of anionic emulsifier sodium lauryl sulfate powder into 200g of water, stir, and after the sodium lauryl sulfate is completely dissolved, add dropwise to the above 0.25% solution Add 4g of epichlorohydrin (fabric modifier) dropwise and stir until a stable and uniform emulsion of epichlorohydrin is prepared.

The pure cotton fabric (warp and weft yarn density 14.575tex×14.575tex, warp density 133 threads/10cm, weft density 72 threads/10cm) was modified by dipping modification method. /L NaOH solution at 60°C for 30 minutes, then take it out and wash it with water to make the pH value of the cloth surface 7, and dry it for later use. By measuring the epoxy value on the modified fabric, the epoxy value on the fabric is 0.009mol/g fabric.

(2) Dyeing of mineral dyes on fabrics

The iron yellow with a particle size of 150nm in Example 1 is prepared into a dye solution with a concentration of 10g/L, and the above-mentioned modified pure cotton fabric is dyed by the dyeing method of two dipping and two padding, and the scraping rate is 80%. Finally, the fabric is dried at 80°C for 3 minutes, baked at 130-150°C for 3 minutes, then soaped at 95°C for 10 minutes with 3% soap powder, washed with water, and dried.

The dyeing results are shown in Table 2:

Iron yellow after table 2 grinds to the dyeing result of fabric

It can be seen from Table 2 that the color depth K/S value of the cotton fabric dyed fabric modified by Example 2 with the ground iron yellow is relatively high, but the color unevenness of the modified fabric is relatively high.

Example 3

(1) Modification of pure cotton fabric: Add 0.5g of nonionic emulsifier AEO ₁₀ into 200g of water, stir, then add 4g of epichlorohydrin (fabric modifier) dropwise to the above 0.25% solution, drop Stir while adding until a stable and uniform epichlorohydrin emulsion is prepared.

The pure cotton fabric (warp and weft yarn density 14.575tex×14.575tex, warp density 133 threads/10cm, weft density 72 threads/10cm) was treated by the modified method of two dipping and two rolling, and the excess rate was 70%. Dry at 110°C; treat the dried fabric in 12g/L NaOH solution at 60°C for 30 minutes, then take it out and wash it with water to make the pH of the cloth surface 7. After drying, measure the epoxy value on the cotton fabric ,stand-by.

By measuring the epoxy value on the modified fabric, the epoxy value on the fabric is 0.004mol/g fabric.

(2) Dyeing of mineral dyes on fabrics

The iron yellow with a particle size of 150nm in Example 1 is prepared into a dye solution with a concentration of 10g/L, and the above-mentioned modified pure cotton fabric is dyed by the dyeing method of two dipping and two padding, and the scraping rate is 80%. Finally, the fabric is dried at 80°C for 3 minutes, baked at 130-150°C for 3 minutes, then soaped at 95°C for 10 minutes with 3% soap powder, washed with water, and dried.

The dyeing results are shown in Table 3:

Iron yellow after table 3 grinds to the dyeing result of fabric

As can be seen from Table 3, the color depth K/S value of the cotton fabric dyed fabric modified in Example 3 is relatively high with the iron yellow after grinding, and the dyeing depth of the modified fabric is higher than that of the unmodified fabric The dyeing depth, the color unevenness of the modified fabric is less than 10, which meets the standard.

Comparing the color fastness and color unevenness after dyeing of Example 1 and Example 2 modified fabrics in Table 1 and Table 2, it can be seen that the modification effect of the padding modification method for the modifier epichlorohydrin is compared Good; Comparing the color fastness and color unevenness after dyeing of the modified fabrics of Example 1 and Example 3 in Table 1 and Table 3, it can be seen that the modification effect of using anionic emulsifier to emulsify epichlorohydrin is better.

Claims (9)

1. the colouring method of natural minerals dyestuff on fabric, comprising:

(1) by dipping or pad method, with fabric-modifying agent, modification is carried out to fabric; Wherein in fabric-modifying agent molecule structure containing at least double functional group, for epoxychloropropane, glyoxal, glutaraldehyde, ethylenediamine or vulcabond;

(2) with dispersant by after natural minerals dyestuff nanometer, nano-mineral dyestuff is mixed with dye liquor, adopts two colouring methods that roll of leaching two to dye to above-mentioned modified fabric, carry out after dyeing drying, bake, soap, wash post-drying; Wherein dispersant structure formula is:

wherein, R ₁for H or CH ₃; R ₂for C ₁~ C ₁₀alkyl, hydroxyl C ₁~ C ₁₀alkyl in one or more; R ₃for H or CH ₃; R ₄for H or CH ₃; R ₅for C ₁~ C ₁₀alkyl, hydroxyl C ₁~ C ₁₀alkyl in one or more; A:b:c:d=0.3 ~ 0.5:0 ~ 0.4:0.4 ~ 0.7:0 ~ 0.2, the weight average molecular weight of dispersant is 8000-30000 gram/mol.

2. the colouring method of a kind of natural minerals dyestuff according to claim 1 on fabric, is characterized in that: the fabric in described step (1) is the one in COTTON FABRIC, linen, dacron, cotton ramie blended spinning fabric, cotton-polyester blend fabric, wool fabric, rabbit hair fabric.

3. the colouring method of a kind of natural minerals dyestuff according to claim 1 on fabric, it is characterized in that: the preparation method of described dispersant is: under room temperature, reaction monomers is added in reaction vessel, solvent, logical nitrogen 20 ~ 60min, warming while stirring is to 60-85 DEG C, drip insulation reaction 0.5 ~ 4h after a part of initator, drip residue initator again, then insulation reaction 5 ~ 12h, after product cooling, crude product is added drop-wise in the poor solvent of copolymer and precipitates again, then wash, dry to obtain copolymer, by gained copolymer with after sodium hydroxide solution mixing, saponification 1 ~ 3h at 30 ~ 50 DEG C, then products therefrom is added dropwise in acetone and precipitates again, suction filtration, washing, dry to obtain dispersant.

4. the colouring method of a kind of natural minerals dyestuff according to claim 3 on fabric, is characterized in that: described reaction monomers is maleic anhydride, R ₂cOOC (R ₁) CH ₂, CH ₂c (R ₄) COOR ₅in one or more, wherein R ₂cOOC (R ₁) CH ₂middle R ₁for H or CH ₃, R ₂for C ₁~ C ₁₀alkyl, hydroxyl C ₁~ C ₁₀alkyl in one or more; CH ₂c (R ₄) COOR ₅middle R ₄for H or CH ₃, R ₅for C ₁~ C ₁₀alkyl, hydroxyl C ₁~ C ₁₀alkyl in one or more.

5. the colouring method of a kind of natural minerals dyestuff according to claim 3 on fabric, is characterized in that: described solvent is methyl alcohol, ethanol, acetone, butanone, ethyl acetate, dimethyl sulfoxide (DMSO) or carbon tetrachloride; Initator is: azoic compound initiator or organic peroxide evocating agent; The poor solvent of copolymer is: acetone, chloroform, carrene, methyl alcohol or benzinum, and the poor solvent of copolymer depends on the solvent that reaction system is used and reaction monomers.

6. the colouring method of a kind of natural minerals dyestuff according to claim 5 on fabric; it is characterized in that: described azoic compound initiator is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile), organic peroxide evocating agent is benzoyl peroxide, cumyl peroxide, dilauroyl peroxide or di-isopropyl peroxydicarbonate.

7. the colouring method of a kind of natural minerals dyestuff according to claim 1 on fabric, is characterized in that: the mineral dye in described step (2) is green ore, brown ore, blue ore, red ore or yellow ore.

8. the colouring method of a kind of natural minerals dyestuff according to claim 1 on fabric, is characterized in that: in described step (2), the particle diameter of nano-mineral dyestuff is 90 ~ 300nm.

9. the colouring method of a kind of natural minerals dyestuff according to claim 1 on fabric, it is characterized in that: in described step (2), bake out temperature is 80 ~ 100 DEG C, drying time is 1 ~ 3min, and baking temperature is 130 ~ 150 DEG C, and the time of baking is 3min.