阅读说明：本技术 一种炭黑色浆及其制备方法和应用 (Carbon black color paste and preparation method and application thereof ) 是由 吕仕铭 徐利伟 宋文强 吕品 于 2020-08-05 设计创作，主要内容包括：本发明公开了一种炭黑色浆及其制备方法和应用,将占改性炭黑质量3～6wt.％的表面活性剂、占炭黑色浆总质量5～10wt.％的保湿剂、占炭黑色浆总质量0.05～0.5wt.％的防霉杀菌剂和水混合均匀,将pH值调节到8.0～10.0,添加占炭黑色浆总质量20～50wt.％的改性炭黑,经分散、研磨、过滤后得到炭黑色浆。本发明提供的炭黑色浆及其制备方法和应用,首先用液相氧化法利用氧化剂对炭黑氧化,得到氧化炭黑,然后将壳聚糖包覆在炭黑表面上,最后再对壳聚糖进行羧甲基化,制备得到的改性炭黑与具有特殊结构的表面活性剂、保湿剂、防霉杀菌剂、水等经混匀、分散、研磨、过滤后得到炭黑色浆,炭黑色浆具有粒径小、稳定性高、与粘胶原液的相容性好、制备的纤维耐水洗性能好等特点。(The invention discloses a carbon black color paste and a preparation method and application thereof, wherein a surfactant accounting for 3-6 wt.% of the total mass of modified carbon black, a humectant accounting for 5-10 wt.% of the total mass of the carbon black color paste, an anti-mildew bactericide accounting for 0.05-0.5 wt.% of the total mass of the carbon black color paste and water are uniformly mixed, the pH value is adjusted to 8.0-10.0, the modified carbon black accounting for 20-50 wt.% of the total mass of the carbon black color paste is added, and the carbon black color paste is obtained after dispersion, grinding and filtration. The carbon black color paste and the preparation method and the application thereof provided by the invention are characterized in that firstly, carbon black is oxidized by an oxidant by a liquid phase oxidation method to obtain oxidized carbon black, then chitosan is coated on the surface of the carbon black, and finally carboxymethylation is carried out on the chitosan, so that the prepared modified carbon black, a surfactant with a special structure, a humectant, an anti-mildew bactericide, water and the like are uniformly mixed, dispersed, ground and filtered to obtain the carbon black color paste.)

1. The carbon black color paste is characterized by being prepared by uniformly mixing a surfactant, a humectant, an anti-mildew fungicide and water, adjusting the pH value of the mixture and then mixing the mixture with modified carbon black.

2. The preparation method of the carbon black color paste according to claim 1, which is characterized by comprising the following steps of:

uniformly mixing a surfactant which accounts for 3-6 wt.% of the total mass of the modified carbon black, a humectant which accounts for 5-10 wt.% of the total mass of the carbon black color paste, an anti-mildew fungicide which accounts for 0.05-0.5 wt.% of the total mass of the carbon black color paste and water, adjusting the pH value to 8.0-10.0 by using a pH value regulator, adding the modified carbon black which accounts for 20-50 wt.% of the total mass of the carbon black color paste, and uniformly mixing, dispersing, grinding and filtering to obtain the required carbon black color paste; wherein the total mass of the carbon black color paste is the sum of the mass of the surfactant, the humectant, the mildew-proof bactericide, the water and the modified carbon black.

3. The preparation method of the carbon black color paste according to claim 2, wherein the modified carbon black is prepared by the following steps:

s1: mixing 40 parts by mass of carbon black with 400 parts by mass of an oxidant, reacting at the temperature of 60-90 ℃ for 2-5 hours, cooling, filtering, washing and drying to obtain oxidized carbon black;

s2: dispersing 40 parts by mass of the oxidized carbon black prepared in the step S1 in 100 parts by mass of water, adding 2-5 parts by mass of chitosan for dispersing for 30-60 min, adding 20-40 parts by mass of sodium hydroxide for dispersing for 2-6 h, slowly adding 5-10 parts by mass of chloroacetic acid and 0.5-1.0 part by mass of potassium iodide, reacting at 40-70 ℃ for 2-6 h, cooling, filtering, washing and drying to obtain the modified carbon black.

4. The method for preparing the carbon black color paste according to claim 3, wherein the oxidant is at least one of hydrogen peroxide, sulfuric acid, ammonium persulfate and nitric acid.

5. The method for preparing the carbon black color paste according to claim 2, wherein the surfactant is a compound having a structure of a general formula (I):

wherein R is an alkyl group containing 10-20 carbon atoms, and contains 10 and 20 carbon atoms; y is one of Na and K.

6. The method for preparing the carbon black color paste according to claim 2, wherein the humectant is at least one of polyethylene glycol, polypropylene glycol, triethylene glycol, glycerol, 1,2, 4-butanetriol, diethylene glycol dibutyl ether, tetraethylene glycol and tetraethylene glycol dimethyl ether.

7. The method for preparing the carbon black color paste according to claim 2, wherein the mildewproof bactericide is at least one of 1, 2-benzisothiazolin-3-one, 5-chloro-2-methyl-1-isothiazolin-3-one and 3-iodo-2-propargyl butyl carbamate.

8. The method for preparing the carbon black color paste according to claim 2, wherein the pH value regulator is one of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, disodium hydrogen phosphate and triethanolamine.

9. The use of the carbon black paste according to claim 1 in the coloration of viscose stock solutions.

Technical Field

The invention belongs to the technical field of fine chemical engineering, and particularly relates to carbon black color paste and a preparation method and application thereof.

Background

The viscose fiber is prepared by using natural fibers such as wood fiber/cotton linter and the like as raw materials, preparing soluble cellulose xanthate through the processes of alkalization, aging, sulfonation and the like, dissolving the soluble cellulose xanthate in dilute alkali liquor to prepare viscose, and performing wet spinning. Because the viscose fiber has the characteristics of good air permeability and moisture absorption, meeting the physiological requirements of human skin and the like, the viscose fiber is widely applied to various textiles such as underwear, coats and the like. Dyeing by adopting dye is a main method for dyeing viscose, but the process has the defects of water consumption, energy consumption, large sewage quantity and the like.

The dope coloring process is a technology of directly preparing colored viscose fiber by adding a colorant into a viscose spinning dope and spinning. Because the stock solution coloring process reduces the traditional dyeing process, compared with dyeing, the water consumption and the energy consumption are obviously reduced, and the viscose fiber prepared by the stock solution coloring process has high washing and light fastness and good development prospect. In the field of viscose stock solution coloring, in order to avoid waste caused by transition yarns with different colors, stock solution coloring viscose manufacturers generally select to produce stock solution coloring fibers with larger consumption such as black, and carry out centralized production on production lists, so that the continuous production time is longer. In order to ensure the quality of continuous production, the performance of the black color paste has more rigorous requirements.

Carbon black is a common pigment, and the surface modification of the pigment such as carbon black is carried out to improve the stable dispersion of the pigment in water and the application effect of the pigment in an application system, so that the method is a common method for improving the application performance of the pigment. Chinese patent, patent publication No. CN106634059, discloses a method for preparing water-based self-dispersible nano carbon black, which comprises grafting a silane coupling agent containing carbon-carbon double bonds on the surface of carbon black, copolymerizing polymerizable groups of the silane coupling agent with other water-based monomers, and coating a layer of polymer with dual functions of dispersion and stabilization on the surface of carbon black particles to achieve the purpose of self-dispersion in a water-based solvent. U.S. patent publication No. US6221143 discloses a cationic pigment containing an organic group which is disclosed to be composed of two structures: a) at least one aromatic group, at least one C_1-20Alkyl groups of (a), or both; b) at least one ionic group bearing a cation, at least one group bearing an ionizable cation, or both, and a corresponding counter anion, the cation beingPigments can be used in water or solvent based compositions, particularly in ink compositions, especially inkjet ink compositions.

The chitosan is an alkaline polysaccharide obtained by deacetylating second natural polymer chitin in the world under a strong alkali condition, has a chemical structure similar to that of cellulose, and has the characteristics of no toxicity, bacteriostasis and the like. In the prior art, chitosan or modified chitosan is directly added into a spinning solution to be mixed to prepare viscose, for example, Chinese patent with the patent publication number of CN1424441 discloses a preparation process and a product of a modified chitin-chitosan and viscose spinning solution blending material, and the product of the modified chitin-chitosan and viscose spinning solution blending material has good dyeing property, antibacterial property and compatibility. In the prior art, chitosan or modified chitosan is directly mixed with carbon black, for example, Chinese patent with patent publication No. CN107502071 discloses a carbon black-based water-based paint and a preparation method thereof, wherein components such as carbon black, antibacterial agent modified chitosan and the like are dispersed to obtain the carbon black-based water-based paint which is mainly used for surface coating of outer bag paper of fruit bag. However, no report is known for coating chitosan on carbon black and coloring viscose fiber stock solution to improve the spinnability of viscose fiber and improve the color fastness to washing of colored fiber.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention aims to provide the carbon black color paste and the preparation method and application thereof.

In order to achieve the purpose and achieve the technical effect, the invention adopts the technical scheme that:

a carbon black color paste is prepared by uniformly mixing a surfactant, a humectant, an anti-mildew bactericide and water, adjusting the pH value of the mixture and then mixing the mixture with modified carbon black.

The invention discloses a preparation method of carbon black color paste, which comprises the following steps:

uniformly mixing a surfactant which accounts for 3-6 wt.% of the total mass of the modified carbon black, a humectant which accounts for 5-10 wt.% of the total mass of the carbon black color paste, an anti-mildew fungicide which accounts for 0.05-0.5 wt.% of the total mass of the carbon black color paste and water, adjusting the pH value to 8.0-10.0 by using a pH value regulator, adding the modified carbon black which accounts for 20-50 wt.% of the total mass of the carbon black color paste, and uniformly mixing, dispersing, grinding and filtering to obtain the required carbon black color paste; the surfactant plays an important role in the preparation of the color paste, and the dosage of the surfactant depends on the quality of the pigment carbon black; wherein the total mass of the carbon black color paste is the sum of the mass of the surfactant, the humectant, the mildew-proof bactericide, the water and the modified carbon black.

Further, the modified carbon black is prepared by the following steps:

s1: mixing 40 parts by mass of carbon black with 400 parts by mass of an oxidant, reacting at the temperature of 60-90 ℃ for 2-5 hours, cooling, filtering, washing and drying to obtain oxidized carbon black;

s2: dispersing 40 parts by mass of the oxidized carbon black prepared in the step S1 in 100 parts by mass of water, adding 2-5 parts by mass of chitosan for dispersing for 30-60 min, adding 20-40 parts by mass of sodium hydroxide for dispersing for 2-6 h, slowly adding 5-10 parts by mass of chloroacetic acid and 0.5-1.0 part by mass of potassium iodide, reacting at 40-70 ℃ for 2-6 h, cooling, filtering, washing and drying to obtain the modified carbon black.

Further, in step S1, the oxidant is at least one of hydrogen peroxide, sulfuric acid, ammonium persulfate, and nitric acid.

Further, the surfactant is a compound having a structure of general formula (I):

wherein R is an alkyl group containing 10-20 carbon atoms, and contains 10 and 20 carbon atoms; y is one of Na and K.

Further, the compound with the structure of the general formula (I) is prepared by a plurality of processes, wherein one process takes mordenite as a catalyst and is protected by inert gasThe temperature is controlled to be 60-90 ℃, and the alkanolamide RCONHCH₂CH₂And (3) reacting OH with maleic anhydride for 2-5 h, and then reacting with sulfite to obtain the catalyst.

Further, the humectant is at least one of polyethylene glycol, polypropylene glycol, triethylene glycol, glycerol, 1,2, 4-butanetriol, diethylene glycol dibutyl ether, tetraethylene glycol and tetraethylene glycol dimethyl ether.

Further, the mildew-proof bactericide is at least one of 1, 2-benzisothiazolin-3-one, 5-chloro-2-methyl-1-isothiazolin-3-one and 3-iodo-2-propargyl butyl carbamate.

Further, the pH value regulator is one of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, disodium hydrogen phosphate and triethanolamine.

The invention also discloses an application of the carbon black color paste in viscose stock solution coloring.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides a carbon black color paste and a preparation method and application thereof, wherein a surfactant accounting for 3-6 wt.% of the total mass of modified carbon black, a humectant accounting for 5-10 wt.% of the total mass of the carbon black color paste, an anti-mildew bactericide accounting for 0.05-0.5 wt.% of the total mass of the carbon black color paste and water are uniformly mixed, a pH value is adjusted to 8.0-10.0 by using a pH value adjusting agent, the modified carbon black accounting for 20-50 wt.% of the total mass of the carbon black color paste is added, and the carbon black color paste is obtained after dispersion, grinding and filtration. The carbon black color paste and the preparation method and the application thereof provided by the invention are characterized in that firstly, carbon black is oxidized by an oxidant by a liquid-phase oxidation method to obtain oxidized carbon black, then chitosan is coated on the surface of the carbon black, and finally carboxymethylation is carried out on the chitosan, so that the prepared modified carbon black, a surfactant with a special structure, a humectant, an anti-mildew bactericide, water and the like are uniformly mixed, dispersed, ground and filtered to obtain the carbon black color paste.

Detailed Description

The following detailed description of the embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention.

A carbon black color paste is prepared by uniformly mixing a surfactant, a humectant, an anti-mildew bactericide and water, adjusting the pH value of the mixture and then mixing the mixture with modified carbon black.

A preparation method of carbon black color paste comprises the following steps:

uniformly mixing a surfactant which accounts for 3-6 wt.% of the total mass of the modified carbon black, a humectant which accounts for 5-10 wt.% of the total mass of the carbon black color paste, an anti-mildew bactericide which accounts for 0.05-0.5 wt.% of the total mass of the carbon black color paste and water, adjusting the pH value to 8.0-10.0 by using a pH value regulator, adding the modified carbon black which accounts for 20-50 wt.% of the total mass of the carbon black color paste, uniformly mixing, dispersing, grinding and filtering to obtain the required carbon black color paste, wherein the sum of the mass of the surfactant, the humectant, the anti-mildew bactericide, the water and the modified carbon black is the total mass of the carbon black color paste.

The modified carbon black is prepared by the following steps:

s1: mixing 40 parts by mass of carbon black with 400 parts by mass of an oxidant, reacting at the temperature of 60-90 ℃ for 2-5 hours, cooling, filtering, washing and drying to obtain oxidized carbon black;

s2: dispersing 40 parts by mass of the oxidized carbon black prepared in the step S1 in 100 parts by mass of water, adding 2-5 parts by mass of chitosan for dispersing for 30-60 min, adding 20-40 parts by mass of sodium hydroxide for dispersing for 2-6 h, slowly adding 5-10 parts by mass of chloroacetic acid and 0.5-1.0 part by mass of potassium iodide, reacting at 40-70 ℃ for 2-6 h, cooling, filtering, washing and drying to obtain the modified carbon black.

The oxidant is at least one of hydrogen peroxide, sulfuric acid, ammonium persulfate and nitric acid.

The humectant is at least one of polyethylene glycol, polypropylene glycol, triethylene glycol, glycerol, 1,2, 4-butanetriol, diethylene glycol dibutyl ether, tetraethylene glycol and tetraethylene glycol dimethyl ether.

The mildew-proof bactericide is at least one of 1, 2-benzisothiazolin-3-one, 5-chloro-2-methyl-1-isothiazolin-3-one and 3-iodo-2-propargyl butyl carbamate.

The pH regulator is one of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, disodium hydrogen phosphate and triethanolamine.

The invention also provides application of the carbon black color paste in viscose stock solution coloring.

The following examples and comparative examples employ surfactants that are compounds having the general structure (I):

wherein R is an alkyl group containing 10-20 carbon atoms, and contains 10 and 20 carbon atoms; y is one of Na and K.

In the surfactant A1, R is C₁₅H₃₁Y is 10, n is Na;

in the surfactant A2, R is C₁₀H₂₁M is 30, n is K;

in the surfactant A3, R is C₂₀H₄₁M is 15 and n is Na.