CN110484385B

CN110484385B - Environment-friendly soaping anti-sticking agent composition and preparation method thereof

Info

Publication number: CN110484385B
Application number: CN201910861522.3A
Authority: CN
Inventors: 吴金丹; 金黔宏; 陈智杰; 黄诗莹; 戚栋明; 仇海刚
Original assignee: Yiwu Zhongli Industry & Trade Co ltd; Zhejiang University of Technology ZJUT
Current assignee: Yiwu Zhongli Industry & Trade Co ltd; Zhejiang University of Technology ZJUT
Priority date: 2019-09-11
Filing date: 2019-09-11
Publication date: 2021-02-19
Anticipated expiration: 2039-09-11
Also published as: CN110484385A

Abstract

The invention relates to the field of textile printing and dyeing auxiliaries, and discloses an environment-friendly soaping anti-sticking agent composition and a preparation method thereof. The environment-friendly soaping anti-sticking agent composition comprises: 2-10% of carboxymethyl chitosan-poly (N-vinyl pyrrolidone), 1-5% of sodium carboxymethyl cellulose, 3-10% of nonionic surfactant, 0.5-2% of chelating agent and the balance of water. The components in the formula are natural and green and environment-friendly, and meanwhile, the components can be synergized in the soaping process, so that the efficiency is greatly improved, unfixed dye is efficiently eluted, and the color fastness of the fabric is improved.

Description

Environment-friendly soaping anti-sticking agent composition and preparation method thereof

Technical Field

The invention relates to the field of textile printing and dyeing auxiliaries, in particular to an environment-friendly soaping anti-sticking agent composition and a preparation method thereof.

Background

The reactive dye contains active groups in the molecular structure, can be combined with cellulose fibers through covalent bonds, and has good color fastness. However, the reactive dye can undergo hydrolysis reaction in the dyeing process, active groups disappear, and the reactive dye is adsorbed on the fiber only through secondary forces such as hydrophobic interaction, hydrogen bond interaction and the like. It has been found that about 30-40% of the dye undergoes hydrolysis during dyeing with reactive dyes and loses reactivity. The partially hydrolyzed dye will adsorb onto the fabric with a small amount of reactive dye not fixed, and will also partly diffuse into the fiber interior. In addition, a part of the dye particles can aggregate and settle on the surface of the fabric.

In the soaping process, the dye adsorbed on the surface of the fiber is firstly diluted and exchanged by water to be washed away, the dye which is not fixed in the fiber needs to be firstly diffused out of the fiber and then diluted and exchanged by the water, and meanwhile, the dye particles settled on the surface of the fabric are separated under the action of mechanical force. Therefore, the soaping process is a key step for washing away the loose color, and has a large influence on the color fastness of the fabric. The adsorption and dissociation of the dye is a dynamic equilibrium process, and although the dissociation of the unfixed dye from the fabric into the solution is a main process in the soaping process due to the use of the soaping agent and the dilution of a large amount of aqueous solution, the soaping process is time-consuming, and the dropped dye can be transferred and adsorbed to other parts of the fabric again. The dyeing of the dark areas often requires the use of higher concentrations of dye, with more flooding, and the partially eluted dye may be adsorbed to the light or white parts of the fabric during the soaping process, causing severe staining, i.e. white staining, which seriously affects the quality of the fabric.

The currently marketed soaping agent mostly adopts the technology of compounding surfactants. The anionic surfactant can improve the ionic strength in the system, simultaneously acts with fibers, dye particles and the like to accumulate negative charges on the surface of the fiber and the dye particles, the repulsion between the fiber and the dye particles is increased to weaken deposition, and the nonionic surfactant prevents the dye from being adsorbed again by increasing the steric hindrance. Meanwhile, the surfactant can form relatively stable colloid with the dropped dye through hydrophobic interaction and the like in the system, solubilize the dropped dye into the colloid, and finally take away the dropped dye along with the solution after soaping. However, it is difficult to achieve excellent anti-staining effect on the white ground only by using a surfactant, and many factors such as water hardness, system DH, soaping temperature, ionic strength and the like are affected during the soaping anti-staining process. The surfactant is greatly affected by the above factors, for example, the anionic surfactant and calcium and magnesium ions in the washing liquid form a water-insoluble substance, and the ionic strength is too high to weaken electrostatic interaction and promote staining of the dye.

As described above, it is necessary for an excellent white soil repellent to have good chelating ability, dispersing ability, wet permeability, dye trapping stability, and the like. It is difficult to satisfy the above requirements by the surfactant alone. CN106380534B discloses a method for synthesizing acrylic acid multipolymer and application thereof, which copolymerizes alpha-olefin sulfonate, acrylamide, N-vinyl pyrrolidone and partial polymerizable carboxylic acid to obtain the acrylic acid multipolymer which can be used as a soaping anti-sticking agent after printing and dyeing. CN1302174C discloses a textile white soil anti-staining detergent, which takes organic phosphorus and micromolecular pyrrolidone as an anti-staining agent and a color removing agent and is compounded with a nonionic surfactant and an anionic surfactant. However, the raw materials involved in the above patents are poor in environmental protection, and because a large amount of auxiliaries used in the washing process can be discharged, the environmental pressure can be greatly reduced if environment-friendly and environment-friendly materials are used.

Disclosure of Invention

In order to solve the technical problems, the invention provides an environment-friendly soaping anti-sticking agent composition and a preparation method thereof. The soaping anti-sticking agent composition comprises carboxymethyl chitosan-poly (N-vinyl pyrrolidone), sodium carboxymethyl cellulose, a nonionic surfactant, a green chelating agent and water. The components in the formula are natural and green and environment-friendly, and meanwhile, the components can be synergized in the soaping process, so that the soaping efficiency is greatly improved, unfixed dye is efficiently eluted, and the color fastness of the fabric is improved.

The specific technical scheme of the invention is as follows: an environment-friendly soaping anti-sticking agent composition comprises the following components in percentage by mass:

2 to 10 percent of carboxymethyl chitosan-poly (N-vinyl pyrrolidone),

1 to 5 percent of sodium carboxymethyl cellulose,

3 to 10 percent of nonionic surfactant,

0.5 to 2 percent of chelating agent,

the balance of water.

The mechanism of the invention is as follows: the carboxymethyl chitosan molecular structure contains amino/amide groups, the weak positive property of the carboxymethyl chitosan has certain binding force on anionic reactive dyes, and the pyrrolidone has a five-membered ring structure containing N and strong affinity on the reactive dyes. The inventor finds in the research process that when a certain amount of N-vinyl pyrrolidone is grafted to carboxymethyl chitosan, the binding force of the structure to the dye is greatly enhanced, probably because the flexible folding of the molecular chain of the copolymer allows free electrons on N atoms in the system to be fully and uniformly dispersed; and a certain amount of proper nonionic surfactant is added into the system to play a role in washing and cleaning, and simultaneously, the nonionic surfactant and the copolymer can form a complex with the dye, so that the nonionic surfactant is stably and uniformly dispersed in a solution phase and is not deposited on a cloth sample. Surprisingly, the inventor finds that the sodium carboxymethylcellulose with a certain specification can play a remarkable synergistic effect on the basis of the above, so that the color floating cleaning is thorough, and the color fastness of the treated fabric after washing is obviously improved. Without being bound by theory, the inventor believes that the sodium carboxymethyl cellulose can be well attached to cotton fabrics with similar structures, the floating color on the surfaces of the fabrics is desorbed through electrostatic repulsion, certain interaction can be generated between the sodium carboxymethyl cellulose and carboxymethyl chitosan-poly (N-vinyl pyrrolidone), the polyhydroxy environment on the cellulose is highly hydrated, and the water phase dispersion stability of the copolymer and dye compound is improved. In addition, the addition of a chelating agent removes free polyvalent heavy metal ions in the system to prevent the polyvalent ions from acting as a bridge to fix the free dye to the fabric.

The inventor also finds that the carboxymethyl polysaccharide has certain compatibility with the nonionic surfactant, is poor in compatibility with the ionic surfactant, and is unstable in a system, but the content of the nonionic surfactant is not high enough, otherwise, the stability of the system is also influenced; the specification of carboxymethyl polysaccharide also affects the product properties, if the molecular weight of the polysaccharide is too high, the viscosity of the system is larger, the compatibility with the surface activity is poor, and if the molecular weight of the polysaccharide is too low, the effect is not obvious. For sodium carboxymethylcellulose, the carboxymethylation degree should not be too high, otherwise the carboxymethylation degree and carboxymethyl chitosan-poly (N-vinyl pyrrolidone) generate too strong interaction, and the soaping anti-sticking efficiency is reduced.

Preferably, the carboxymethyl chitosan-poly (N-vinylpyrrolidone) is prepared by the following method: preparing a carboxymethyl chitosan solution, and sequentially adding ammonium ceric nitrate and a functional monomer N-vinyl pyrrolidone under the protection of nitrogen; heating to 55-65 ℃, reacting for 5-7h, putting the reaction system into a dialysis bag, dialyzing in deionized water for 2-4 days, and freeze-drying and collecting to obtain the carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preferably, the carboxymethyl chitosan has a molecular weight of 10,000-50,000, a degree of carboxymethylation of 0.7-1.2, a degree of deacetylation of 50-90%, and a concentration of the carboxymethyl chitosan solution of 3-10 wt%.

Preferably, the dosage of the cerium ammonium nitrate is 35-85% of the mass of the carboxymethyl chitosan, and the mass of the N-vinyl pyrrolidone is 300-600% of the mass of the carboxymethyl chitosan.

Preferably, the cut-off molecular weight of the dialysis bag is 5000-.

Preferably, the molecular weight of the sodium carboxymethylcellulose is 15,000-50,000, and the degree of carboxymethylation is 0.6-0.8.

It should be noted that, in order to further achieve the desired technical effect, the specifications and process parameters of the above raw materials need to be strictly controlled, and if the range effect is exceeded, the effect is greatly reduced (see the data comparison in the detailed implementation section).

Preferably, the nonionic surfactant comprises one or more of alkyl glycoside and fatty alcohol-polyoxyethylene ether.

Preferably, the chelating agent comprises one or more of glutamic acid diacetate, methylglycine diacetate and ethylenediamine disuccinate.

The chelating agents used in the invention are green chelating agents, and have excellent chelating ability and good biodegradability.

Preferably, the water is deionized water with conductivity < 5 mus/cm.

A preparation method of the environment-friendly soaping anti-sticking agent composition comprises the following steps: sequentially adding sodium carboxymethylcellulose and carboxymethyl chitosan-poly (N-vinyl pyrrolidone) into water at room temperature, stirring while adding, after dissolving, heating to 35-40 deg.C, adding fatty alcohol-polyoxyethylene ether and chelating agent, and stirring.

Compared with the prior art, the invention has the beneficial effects that: in the soaping process, the components of the environment-friendly soaping anti-sticking agent composition can realize synergistic interaction, can chelate polyvalent heavy metal ions, can remove a large amount of unfixed dye, and has a good white bottom anti-sticking function. And the used components are green and environment-friendly, and cannot cause pollution to the environment.

Detailed Description

The present invention will be further described with reference to the following examples.

General examples

An environment-friendly soaping anti-sticking agent composition comprises the following components in percentage by mass:

2 to 10 percent of carboxymethyl chitosan-poly (N-vinyl pyrrolidone),

sodium carboxymethylcellulose 1-5% (molecular weight 15,000-50,000, carboxymethylation degree 0.6-0.8),

3-10% of nonionic surfactant (comprising one or more of alkyl glycoside and fatty alcohol-polyoxyethylene ether),

chelating agent (including one or more of glutamic acid diacetate, methyl glycine diacetate and ethylenediamine disuccinate) 0.5-2%,

the balance of water (deionized water with conductivity < 5 mus/cm).

Wherein the preparation method of the carboxymethyl chitosan-poly (N-vinyl pyrrolidone) comprises the following steps: preparing a carboxymethyl chitosan solution, and sequentially adding ammonium ceric nitrate and a functional monomer N-vinyl pyrrolidone under the protection of nitrogen; heating to 55-65 ℃, reacting for 5-7h, putting the reaction system into a dialysis bag, dialyzing in deionized water for 2-4 days, and freeze-drying and collecting to obtain the carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preferably, the carboxymethyl chitosan has a molecular weight of 10,000-50,000, a degree of carboxymethylation of 0.7-1.2, a degree of deacetylation of 50-90%, and a concentration of the carboxymethyl chitosan solution of 3-10 wt%. The dosage of the ammonium ceric nitrate is 35-85% of the mass of the carboxymethyl chitosan, and the mass of the N-vinyl pyrrolidone is 300-600% of the mass of the carboxymethyl chitosan. The cut-off molecular weight of the dialysis bag was 5000-.

Example 1

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of the carboxymethyl chitosan is 30,000, the carboxymethylation degree is 0.9, and the deacetylation degree is 55%; preparing a solution of the carboxymethyl chitosan with deionized water, wherein the concentration is 3 wt%; under the protection of nitrogen, sequentially adding cerium ammonium nitrate accounting for 85% of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone accounting for 600% of the mass of the carboxymethyl chitosan; heating to 60 ℃, reacting for 6h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 15,000, dialyzing in deionized water for 3 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preparing a soaping anti-sticking agent: 50g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 20g of sodium carboxymethyl cellulose (molecular weight is 15,000, and carboxymethylation degree is 0.6) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 40 ℃, 60g of fatty alcohol polyoxyethylene ether (carbon chain length is C12-C18, average repeat unit of polyoxyethylene ether is 9) and 5g of sodium glutamate diacetate are added to 1000g of deionized water, and stirring is carried out.

Example 2

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of carboxymethyl chitosan is 10,000, the carboxymethylation degree is 0.7, and the deacetylation degree is 90%; preparing the solution of the carboxymethyl chitosan with deionized water, wherein the concentration is 10%; under the protection of nitrogen, sequentially adding ammonium ceric nitrate accounting for 35% of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone accounting for 300% of the mass of the carboxymethyl chitosan; heating to 55 ℃, reacting for 7h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 5,000, dialyzing in deionized water for 2 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preparing a soaping anti-sticking agent: 100g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 10g of sodium carboxymethyl cellulose (molecular weight is 50,000, and carboxymethylation degree is 0.8) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, 100g of alkyl glycoside (carbon chain length is C12-C18) and 20g of sodium methylglycinate are added, and the mixture is made up to 1000g by using deionized water and stirred.

Example 3

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of carboxymethyl chitosan is 50,000, the carboxymethylation degree is 1.2, and the deacetylation degree is 85%; preparing the solution of carboxymethyl chitosan with deionized water, wherein the concentration is 8%; under the protection of nitrogen, sequentially adding ammonium ceric nitrate accounting for 65% of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone accounting for 500% of the mass of the carboxymethyl chitosan; heating to 65 ℃, reacting for 5h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 10,000, dialyzing in deionized water for 4 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preparing a soaping anti-sticking agent: 50g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 25g of sodium carboxymethyl cellulose (molecular weight is 30,000, and carboxymethylation degree is 0.7) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 38 ℃, 30g of fatty alcohol polyoxyethylene ether (carbon chain length is C16-C18, average repeating unit of polyoxyethylene ether is 9) and 30g of alkyl glycoside, 10g of ethylenediamine disuccinic acid sodium are added, and the balance is made up to 1000g of deionized water and stirred.

Example 4

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of the carboxymethyl chitosan is 40,000, the carboxymethylation degree is 0.85, and the deacetylation degree is 60%; preparing the solution of carboxymethyl chitosan with deionized water, wherein the concentration is 5%; under the protection of nitrogen, cerium ammonium nitrate with the mass of 55 percent of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone with the mass of 400 percent of the mass of the carboxymethyl chitosan are sequentially added; heating to 60 ℃, reacting for 6h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 15,000, dialyzing in deionized water for 3 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preparing a soaping anti-sticking agent: 20g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 50g of sodium carboxymethyl cellulose (molecular weight is 20,000, and carboxymethylation degree is 0.65) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 35 ℃, 45g of fatty alcohol polyoxyethylene ether (carbon chain length is C12-C16, average repeat unit of polyoxyethylene ether is 9) and 15g of sodium glutamate diacetate are added to 1000g of deionized water, and stirring is carried out.

Comparative example 1 (without sodium carboxymethylcellulose)

Preparing a soaping anti-sticking agent: 50g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) is sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 40 ℃, 60g of fatty alcohol-polyoxyethylene ether (the carbon chain length is C12-C18, the average repeating unit of the polyoxyethylene ether is 9) and 5g of sodium glutamate diacetate are added, and the mixture is complemented to 1000g by deionized water and stirred.

COMPARATIVE EXAMPLE 2 (sodium carboxymethylcellulose outside the scope of the claims)

Preparing a soaping anti-sticking agent: 50g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 20g of sodium carboxymethyl cellulose (molecular weight is 15,000, and carboxymethylation degree is 1.0) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 40 ℃, 60g of fatty alcohol polyoxyethylene ether (carbon chain length is C12-C18, average repeating unit of polyoxyethylene ether is 9) and 5g of sodium glutamate diacetate are added to 1000g of deionized water, and stirring is carried out.

Comparative example 3 (carboxymethyl chitosan having too low a molecular weight)

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of carboxymethyl chitosan is 8,000, the carboxymethylation degree is 0.9, and the deacetylation degree is 55%; preparing a solution of the carboxymethyl chitosan with deionized water, wherein the concentration is 3 wt%; under the protection of nitrogen, sequentially adding cerium ammonium nitrate accounting for 85% of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone accounting for 600% of the mass of the carboxymethyl chitosan; heating to 60 ℃, reacting for 6h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 5,000, dialyzing in deionized water for 3 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

Preparing a soaping anti-sticking agent: 50g of carboxymethyl chitosan-poly (N-vinyl pyrrolidone) and 20g of sodium carboxymethyl cellulose (molecular weight is 15,000, and carboxymethylation degree is 0.6) are sequentially added into 800mL of deionized water at room temperature while stirring, after dissolution, the temperature is raised to 40 ℃, 60g of fatty alcohol polyoxyethylene ether (carbon chain length is C12-C18, average repeating unit of polyoxyethylene ether is 9) and 5g of sodium glutamate diacetate are added to 1000g of deionized water, and stirring is carried out.

Comparative example 4 (too high grafting amount of N-vinylpyrrolidone)

Preparation of carboxymethyl chitosan-poly (N-vinylpyrrolidone): the molecular weight of the carboxymethyl chitosan is 30,000, the carboxymethylation degree is 0.9, and the deacetylation degree is 55%; preparing a solution of the carboxymethyl chitosan with deionized water, wherein the concentration is 3 wt%; under the protection of nitrogen, sequentially adding cerium ammonium nitrate accounting for 85% of the mass of the carboxymethyl chitosan and monomer N-vinyl pyrrolidone accounting for 900% of the mass of the carboxymethyl chitosan; heating to 60 ℃, reacting for 6h, putting the reaction system into a dialysis bag with the molecular weight cut-off of 15,000, dialyzing in deionized water for 3 days, and freeze-drying and collecting to obtain the copolymer carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

The soaping anti-sticking performance test process is as follows:

1. the used cloth is: active black cotton yarn cards;

2. the soaping process comprises the following steps: the dosage of the soaping anti-sticking agent is 1g/L, the bath ratio is 1: 10, the soaping temperature is 85 ℃, and the soaping time is 10 min.

3. And (3) testing color fastness: the rubbing color fastness of the fabric is carried out according to GB/T3820-; the staining of the fabric after soaping was evaluated as follows: and (3) putting the control white cloth and the colored cloth into a soap washing solution, washing under the condition of a soaping process, measuring the La b value of the white cloth stained in the test, and calculating the color difference value delta E value of the white cloth stained in the test, wherein the smaller delta E value is, the better the staining prevention effect is.

Compared with the example 1, the comparative example 1 does not add the sodium carboxymethyl cellulose, and the obvious effect is not better than the example 1 from the color fastness evaluation result after soaping, and the color difference value of the white cloth after washing is far larger than that of the example 1. The sodium carboxymethyl cellulose can generate a synergistic interaction with other components in the system, and the soaping effect of the composition is greatly improved. Compared with example 1, in comparative example 2, although sodium carboxymethyl cellulose is also added, the carboxymethylation degree is higher and is 1.0, the water solubility is increased, the deposition probability of the carboxymethyl cellulose on the surface of the fabric is reduced, stronger interaction between the carboxymethyl cellulose and each component in the system is generated, and the soaping effect is rather poor. As can be seen from comparative examples 1 and 2, the introduction of sodium carboxymethylcellulose of appropriate specification can greatly improve the soaping effect of the composition. The carboxymethyl chitosan used in comparative example 3 has a lower molecular weight than that of example 1, but the soaping effect is rather poor, probably because the chain length of chitosan is within a certain range to have a better dye adsorption ability. N-vinylpyrrolidone mono in comparative example 4.

Claims

1. The environment-friendly soaping anti-sticking agent composition is characterized by comprising the following components in percentage by mass:

2 to 10 percent of carboxymethyl chitosan-poly (N-vinyl pyrrolidone),

1 to 5 percent of sodium carboxymethyl cellulose,

3 to 10 percent of nonionic surfactant,

0.5 to 2 percent of chelating agent,

the balance of water;

the molecular weight of the carboxymethyl chitosan is 10,000-50,000, the carboxymethylation degree is 0.7-1.2, and the deacetylation degree is 50-90%; the mass of the N-vinyl pyrrolidone is 600 percent of 300-;

the molecular weight of the sodium carboxymethyl cellulose is 15,000-50,000, and the carboxymethylation degree is 0.6-0.8.

2. The environmentally friendly soaping stain resist composition of claim 1, wherein said carboxymethyl chitosan-poly (N-vinyl pyrrolidone) is prepared by the following method: preparing a carboxymethyl chitosan solution, and sequentially adding ammonium ceric nitrate and a functional monomer N-vinyl pyrrolidone under the protection of nitrogen; heating to 55-65 ℃, reacting for 5-7h, putting the reaction system into a dialysis bag, dialyzing in deionized water for 2-4 days, and freeze-drying and collecting to obtain the carboxymethyl chitosan-poly (N-vinyl pyrrolidone).

3. The environmentally friendly soaping stain resist composition of claim 2, wherein the concentration of the carboxymethyl chitosan solution is 3-10 wt%.

4. The environmentally friendly soaping stain resist composition according to claim 2 or 3, wherein the amount of the cerium ammonium nitrate is 35-85% by mass of the carboxymethyl chitosan.

5. The environment-friendly soaping anti-stick agent composition as claimed in claim 2 or 3, wherein the dialysis bag has a molecular weight cut-off of 5000-.

6. The environmentally friendly soaping stain resist composition of claim 1, wherein the non-ionic surfactant comprises one or more of alkyl glycoside, fatty alcohol polyoxyethylene ether.

7. The environmentally friendly soaping stain resist composition of claim 1, wherein the chelating agent comprises one or more of glutamic acid diacetate, methylglycine diacetate, and ethylenediamine disuccinate.

8. The environmentally friendly soaping stain resist composition of claim 1, wherein the water is deionized water with conductivity < 5 μ s/cm.

9. A method for preparing the environmentally friendly soaping stain resist composition according to any one of claims 1 to 8, characterized by: sequentially adding sodium carboxymethylcellulose and carboxymethyl chitosan-poly (N-vinyl pyrrolidone) into water at room temperature, stirring while adding, after dissolving, heating to 35-40 deg.C, adding fatty alcohol-polyoxyethylene ether and chelating agent, and stirring.