A creping adhesive and method of making the same

Abstract

The application discloses a creping adhesive and a preparation method thereof, and belongs to the field of papermaking additives. The creping adhesive comprises the following components: 1-20 parts of a vinyl pyrrolidone organic silicon copolymer, 60-98.8 parts of a polyamide polyamine epichlorohydrin resin, 0.1-10 parts of a functional additive, and 0.1-10 parts of a modifier. The vinyl pyrrolidone organic silicon copolymer is synthesized through aqueous solution free radical polymerization, and the copolymer is blended with a traditional polyamide polyamine epichlorohydrin resin to be used as the creping adhesive. The amount of the vinyl pyrrolidone organic silicon copolymer can be adjusted to adjust the film-forming property, the hardness and the rewettability of a coating, so that the creping adhesive can meet the needs of paper machines for different speeds and types of household paper, and the produced household paper has better hand feeling and softness.

Description

Technical Field

[0001] This invention belongs to the field of papermaking additives, and in particular to a creping and sticking agent and its preparation method. Background Technology

[0002] The production of tissue paper typically involves a crucial creping process, and creping adhesive is an essential additive in this process. It primarily increases the adhesion between the paper web and the Yankee dryer cylinder surface. A specific concentration of adhesive is evenly sprayed onto the surface of the dryer cylinder, and after drying, it forms an adhesive film. This film tightly adheres to the paper web transferred from the press section, preventing it from falling off and improving creping efficiency. The creped paper web exhibits good softness, bulk, and an excellent hand feel. Creping adhesive not only plays a vital role in the creping process but also protects the dryer cylinder and doctor blades, thus extending their service life. A good adhesive requires not only moderate adhesion, good film-forming properties, and a coating with appropriate hardness, but also a certain degree of rewetting ability (i.e., the ability of the adhesive to be activated on the dryer cylinder surface due to the moisture content of the paper web when in contact with the cylinder surface) and good tearing properties. The quality of the adhesive has a significant impact on the feel, softness, and bulk of the paper.

[0003] Polyamide polyamine polymer is indeed a relatively common type of adhesive for tank clogging. However, it has certain defects as an adhesive, such as poor film-forming properties, hard film, and insufficient rewetting. Many patents have provided various methods to improve these defects, such as our company's prior applications CN112694619A and CN114292406A. Summary of the Invention

[0004] To overcome the above-mentioned technical defects, the present invention provides a wrinkling and sticking agent and its preparation method to solve the problems involved in the background art.

[0005] This invention provides a wrinkling and sealing agent, comprising:

[0006]

[0007] Preferably or optionally, the vinylpyrrolidone organosilicon copolymer has the following structure:

[0008]

[0009] Where x is an integer from 5 to 20, m is an integer from 3 to 10, n is an integer from 1 to 10, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or methyl, and R3 is hydrogen or methyl.

[0010] Preferably or optionally, the method for preparing the vinylpyrrolidone organosilicon copolymer includes:

[0011] N-vinylpyrrolidone and hydrophilic organosilicon monomers are subjected to free radical copolymerization in aqueous solution to obtain vinylpyrrolidone organosilicon copolymers;

[0012] The hydrophilic organosilicon monomer is a hydrophilic organosilicon monomer containing ethylene oxide segments.

[0013] Preferably or optionally, the functional additive is one or more of diammonium hydrogen phosphate, diammonium dihydrogen phosphate, and sodium pyrophosphate.

[0014] Preferably or optionally, the modifier is one or more of glycerol, diglycerol, triglyceride, diethylene glycol, 1,2,6-hexanetriol, pentaerythritol, polyethylene glycol, sorbitol, and inositol.

[0015] This invention also provides a method for preparing a wrinkle-inducing and adhesive agent, comprising the following steps:

[0016] Step 1: N-vinylpyrrolidone and hydrophilic organosilicon monomers are subjected to free radical copolymerization in aqueous solution to obtain vinylpyrrolidone organosilicon copolymer;

[0017] Step 2: Polyamide polyamine polymer is obtained by reacting polyamines with dicarboxylic acids; then the polyamide polyamine polymer is crosslinked with epichlorohydrin to obtain polyamide polyamine epichlorohydrin resin.

[0018] Step 3: Mix vinylpyrrolidone silicone copolymer and polyamide polyamine epichlorohydrin resin in a predetermined ratio, and then add a predetermined amount of functional additives and modifiers to the mixture to obtain wrinkling and sticking agent.

[0019] Preferably or optionally, step 1 includes:

[0020] Step 1-1: Remove the polymerization inhibitor from the N-vinylpyrrolidone monomer by vacuum distillation;

[0021] Step 1-2: Add some of the N-vinylpyrrolidone monomer, hydrophilic organosilicon monomer, and deionized water treated in step 1-1 to the reaction vessel, and stir until homogeneous;

[0022] Steps 1-3: Add an appropriate amount of activator, purge with nitrogen to displace the oxygen in the flask, then heat to 55-65℃, add an appropriate amount of initiator, and at the same time start to drop another part of the N-vinylpyrrolidone monomer solution treated in step 1-1, drop it over 1-2 hours, and then keep the reaction at 65-75℃ for 4-8 hours.

[0023] Steps 1-4: After heat preservation, add an appropriate amount of terminator, heat to 75-85℃, continue the reaction for 1-4 hours, cool to room temperature, and discharge to obtain a transparent colorless to light yellow viscous aqueous solution.

[0024] Preferably or optionally, the activator is one or more of monoethylamine, triethylamine, and tetramethylammonium hydroxide;

[0025] The initiator is one or more of the following: hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, tert-butyl hydroperoxide, tert-butyl benzoic acid peroxide, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobisisobutylammonium valerate, and azobisisopropylimidazoline.

[0026] The terminator is sodium bisulfite.

[0027] Preferably or optionally, in step 1, the mass fractions of each material are as follows: 29-40 parts of N-vinylpyrrolidone monomer, 1-11 parts of hydrophilic organosilicon monomer, 0.05-0.60 parts of co-activator, 0.05-0.50 parts of initiator, and 0.10-1.00 parts of terminator.

[0028] Preferably or optionally, the polyaminoamine is selected from one or a mixture of several of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hydroxyethylethylenediamine, hydroxypropylethylenediamine, and aminoethylaminopropylamine;

[0029] Preferably or optionally, the dicarboxylic acid is selected from one or a mixture of several of succinic acid, glutaric acid, adipic acid, and azelaic acid.

[0030] This invention relates to a creping adhesive and its preparation method. Compared with the prior art, it has the following advantages: This invention synthesizes a vinylpyrrolidone organosilicon copolymer through free radical polymerization of aqueous solution. This copolymer is then blended with traditional polyamide polyamine epichlorohydrin resin and used as a creping adhesive. The film-forming properties, hardness, and rewetting properties of the coating can be adjusted by the amount of vinylpyrrolidone organosilicon copolymer added, thereby adapting to the needs of different machine speeds and types of tissue paper making machines. In addition, it can make the produced tissue paper have a better hand feel and softness. Detailed Implementation

[0031] In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention. However, it will be apparent to those skilled in the art that the invention can be practiced without one or more of these details. In other instances, certain technical features well-known in the art have not been described in order to avoid obscuring the invention. Invention Overview

[0033] Polyamide polyamine epichlorohydrin resin is used as a creping adhesive in the paper industry. This polymer is primarily used in the drying section of tissue paper production. The drying temperature of the drying cylinders typically reaches 90-120℃. At this high temperature and low relative humidity, the polyamide epoxy resin film on the cylinder surface becomes hard and brittle, exhibiting defects such as poor film-forming properties, a hard film layer, and insufficient rewetting ability. Furthermore, the required adhesion force for creping varies depending on the characteristics of the tissue paper product and the equipment parameters, necessitating adjustments to the performance of the adhesive accordingly.

[0034] Therefore, this invention improves the brittleness of polyvinylpyrrolidone (PVP) films by copolymerizing vinylpyrrolidone with hydrophilic organosilicon monomers containing ethylene oxide segments, thereby enabling the copolymer to be used better as a tackifier. At the same time, the polydimethylsiloxane structure in the organosilicon polymer has good smoothness, low surface tension, and no skin irritation, which can impart excellent smoothness and softness to paper.

[0035] Based on this, the present invention addresses the shortcomings of using polyamide polyamine epichlorohydrin resin alone by introducing a blend of vinylpyrrolidone silicone copolymer and polyamide polyamine epichlorohydrin resin. At the same time, the film-forming properties, hardness, and rewetting properties of the coating can be adjusted by changing the amount of vinylpyrrolidone silicone copolymer added, thereby adapting to the needs of different machine speeds and types of tissue paper making machines. In addition, it can make the produced tissue paper have a better feel and softness.

[0036] Specifically, this invention provides a creping adhesive and its preparation method. The creping adhesive, by weight, comprises the following components: 1-20 parts of vinylpyrrolidone silicone copolymer; 60-98.8 parts of polyamide polyamine epichlorohydrin resin; 0.1-10 parts of functional additives; and 0.1-10 parts of modifier. Preferably, the composition is 8-12 parts of vinylpyrrolidone silicone copolymer; 70-80 parts of polyamide polyamine epichlorohydrin resin; 0.1-10 parts of functional additives; and 0.1-10 parts of modifier. Excessive use of vinylpyrrolidone silicone copolymer will result in a film that is too soft and easily scraped off by the doctor blade, thus affecting paper creping. It will also increase the amount of adhesive used, raising production costs. Furthermore, vinylpyrrolidone silicone copolymer is relatively expensive, and from a cost-benefit perspective, it is not advisable to use too much. If too little vinylpyrrolidone silicone copolymer is used, the resulting film will be too hard, the doctor blade will wear out severely, and the surface of the drying cylinder will be damaged, requiring frequent replacement of the doctor blade and grinding of the drying cylinder surface. In addition, too little vinylpyrrolidone silicone copolymer will also result in poor rewetting properties of the sticking agent, while a large amount will cause the coating to gradually thicken, resulting in coarse paper texture, uneven tearing and wrinkling, and affecting the quality of the finished paper.

[0037] The wrinkling and sticking agent preparation method includes the following steps: Step 1, N-vinylpyrrolidone and hydrophilic organosilicon monomers are subjected to free radical copolymerization in aqueous solution to obtain vinylpyrrolidone organosilicon copolymer; Step 2, polyamide polyamine polymer is obtained by reacting polyamines and dicarboxylic acids; then the polyamide polyamine polymer is subjected to crosslinking reaction with epichlorohydrin to obtain polyamide polyamine epichlorohydrin resin; Step 3, vinylpyrrolidone organosilicon copolymer and polyamide polyamine epichlorohydrin resin are mixed in a predetermined ratio, and then a predetermined amount of functional additives and modifiers are added to the mixture to obtain wrinkling and sticking agent.

[0038] The vinylpyrrolidone organosilicon copolymer has the following structural formula:

[0039]

[0040] Where x is an integer from 5 to 20, m is an integer from 3 to 10, n is an integer from 1 to 10, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or methyl, and R3 is hydrogen or methyl.

[0041] In a further embodiment, step 1 specifically includes: step 1-1, removing the polymerization inhibitor by vacuum distillation of the N-vinylpyrrolidone monomer; step 1-2, adding a portion of the N-vinylpyrrolidone monomer treated in step 1-1, a hydrophilic organosilicon monomer, and deionized water to a reaction vessel, and stirring until homogeneous; step 1-3, adding an appropriate amount of activator, purging nitrogen gas to displace the oxygen in the flask, then heating to 55-65°C, adding an appropriate amount of initiator, and simultaneously starting to drop another portion of the N-vinylpyrrolidone monomer solution treated in step 1-1, completing the dropwise addition within 1-2 hours, and then maintaining the temperature at 65-75°C for 4-8 hours; step 1-4, after the temperature maintenance is completed, adding an appropriate amount of terminator, heating to 75-85°C, continuing the reaction for 1-4 hours, cooling to room temperature, and discharging to obtain a transparent, colorless to light yellow viscous aqueous solution.

[0042] It should be noted that the polymerization rates of the two monomers differ significantly. The NVP monomer is relatively easy to polymerize, while the hydrophilic organosilicon monomer is more difficult to polymerize. Moreover, the amounts of the two monomers differ considerably. Therefore, the NVP monomer is added in stages to improve the degree of polymerization of the vinylpyrrolidone organosilicon copolymer and the uniformity of the distribution of hydrophilic organosilicon monomer segments.

[0043] The hydrophilic organosilicon monomer is a hydrophilic organosilicon monomer containing ethylene oxide segments, and has the following structure:

[0044]

[0045] Where m is an integer from 3 to 10, n is an integer from 1 to 10, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or methyl, and R3 is hydrogen or methyl.

[0046] The hydrophilic organosilicon monomer contains ethylene oxide segments (-O-CH2-CH2-), which greatly enhances the hydrophilicity of the vinylpyrrolidone organosilicon copolymer. Moreover, the vinylpyrrolidone organosilicon copolymer is obtained through vinyl copolymerization, which has relatively high stability and can exist stably in the high temperature and strong acid and alkali environment of the drying cylinder.

[0047] The co-activator is one or more of monoethylamine, triethylamine, and tetramethylammonium hydroxide; the initiator is one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, tert-butyl hydroperoxide, tert-butyl benzoic acid peroxide, azobisisobutylamidine hydrochloride (AIBA, V-50 initiator), azobisisobutylimidazoline hydrochloride (AIBI, VA-044 initiator), azobiscyanopentanoic acid (ACVA, V-501 initiator), and azobisisopropylimidazoline (AIP, VA-061 initiator); the terminator is sodium bisulfite. The mass fractions of each material are as follows: N-vinylpyrrolidone monomer 29-40 parts, hydrophilic organosilicon monomer 1-11 parts, co-activator 0.05-0.60 parts, initiator 0.05-0.50 parts, and terminator 0.10-1.00 parts.

[0048] In a further embodiment, in step 2, the polymeric organic amine is selected from one or a mixture of several of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hydroxyethylethylenediamine, hydroxypropylethylenediamine, and aminoethylaminopropylamine; the dicarboxylic acid is selected from one or a mixture of several of succinic acid, glutaric acid, adipic acid, and azelaic acid; the molar ratio of the polymeric organic amine to the dicarboxylic acid is 0.8-1.2:0.8-1.2, the reaction temperature is controlled at 140-180℃, and the reaction time is 1-8h; the mass of epichlorohydrin is 2-20% of the mass of the polyamide polyamine polymer aqueous solution, the crosslinking reaction temperature is 40-80℃, and the reaction time is 1-5h.

[0049] In a further embodiment, the functional additive described herein is one or more of diammonium hydrogen phosphate, sodium dihydrogen phosphate, and sodium pyrophosphate, and the modifier is one or more of glycerol, diglycerol, triglyceride, diethylene glycol, 1,2,6-hexanetriol, pentaerythritol, polyethylene glycol, sorbitol, and inositol.

[0050] The present invention will be further described below with reference to the embodiments. The examples described are intended to explain the present invention and should not be construed as limiting the present invention.

[0051] Example 1

[0052] Before use, N-vinylpyrrolidone (NVP) monomer was subjected to vacuum distillation to remove the polymerization inhibitor. In a four-necked flask equipped with a condenser, thermometer, dropping funnel, and stirrer, 25g of NVP monomer, 5g of polydimethylsiloxane containing ethylene oxide segments, and 50g of deionized water were added and stirred until homogeneous. 0.4g of monoethylamine, a co-activator, was added, and nitrogen gas was introduced to displace the oxygen in the flask. The temperature was raised to 60°C, and 0.5g of initiator (35wt% hydrogen peroxide) was added. Simultaneously, the NVP monomer solution (18g NVP monomer + 30g deionized water) was added dropwise over one hour. The reaction was then maintained at 65-75°C for 6 hours. Then, 0.2g of terminator (sodium bisulfite) was added, the temperature was raised to 80-85°C, and the reaction continued for 2 hours. After cooling to room temperature, a transparent, colorless to light yellow viscous aqueous solution with a solid content of approximately 40% (reactant A) was discharged.

[0053] Add 6.8 parts of diethylenetriamine and 8.5 parts of adipic acid to a reaction flask, stir well, and heat to 150°C, continuously evaporating the generated water. After reacting for 1 hour, continue heating to 165-175°C and react for another 4 hours. Then add 6 parts of deionized water to terminate the reaction, and finally add 7 parts of dilution water to obtain a polyamide polyamine polymer with a solid content of 50%. Add 27 parts of polyamide polyamine polymer and 18 parts of deionized water to a reaction flask, stir well, and then add 1.3 parts of epichlorohydrin dropwise. Then heat to 60°C and react for 2-2.5 hours. After reacting at 60°C for 1.5 hours, take a sample every 15 minutes to measure the viscosity. When the solution viscosity reaches 250-400 mPa·s, quickly add water to terminate the reaction to obtain the crosslinked product. Cool the above materials to below 35°C, add 0.02 parts of 10% liquid alkali to adjust the pH, then add 0.1 parts of bactericide BIT-20, and finally add water to adjust the solid content to 15%, thus obtaining reactant B.

[0054] After mixing 10g of reactant A and 75g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglycerides and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0055] Example 2

[0056] The preparation of reactant A is the same as in Example 1.

[0057] Add 10 parts triethylenetetramine and 10 parts adipic acid to a reaction flask, stir well, and heat to 150°C. Continuously evaporate the water generated during the reaction. After reacting for 1 hour, continue heating to 165-175°C and react for another 2 hours. Then add 5 parts water to terminate the reaction. Finally, add 10 parts dilution water to obtain a polyamide polyamine polymer with a solid content of 50%. Add 28 parts polyamide polyamine polymer and 19 parts water to a reaction flask, stir well, and then add 1.4 parts epichlorohydrin dropwise. Heat to 65°C and react for 2-2.5 hours. After reacting at 65°C for 1.5 hours, take a sample every 15 minutes to measure the viscosity. When the solution viscosity reaches 300-450 mPa·s, add water to terminate the reaction, obtaining a crosslinked product. Cool the above materials to below 35°C, add 0.05 parts 10% liquid alkali to adjust the pH, then add 0.1 parts of bactericide BIT-20, and finally add water to adjust the solid content to 15%, obtaining reactant B.

[0058] After mixing 10g of reactant A and 75g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglycerides and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0059] Example 3

[0060] Before use, N-vinylpyrrolidone (NVP) monomer was subjected to vacuum distillation to remove the polymerization inhibitor. In a four-necked flask equipped with a condenser, thermometer, dropping funnel, and stirrer, 23g of NVP monomer, 10g of polydimethylsiloxane containing ethylene oxide segments, and 50g of deionized water were added and stirred until homogeneous. 0.4g of monoethylamine, a co-activator, was added, and nitrogen gas was introduced to displace the oxygen in the flask. The temperature was raised to 60°C, and 0.5g of initiator (35wt% hydrogen peroxide) was added. Simultaneously, the NVP monomer solution (15g NVP monomer + 30g deionized water) was added dropwise over one hour. The reaction was then maintained at 65-75°C for 6 hours. Then, 0.2g of terminator (sodium bisulfite) was added, the temperature was raised to 80-85°C, and the reaction continued for 2 hours. After cooling to room temperature, a transparent, colorless to light yellow viscous aqueous solution (reactant A) with a solid content of approximately 40% was discharged.

[0061] The preparation of reactant B is the same as in Example 1.

[0062] After mixing 10g of reactant A and 75g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglycerides and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0063] Example 4

[0064] The preparation of reactant A is the same as in Example 3.

[0065] The preparation of reactant B is the same as in Example 2.

[0066] After mixing 10g of reactant A and 75g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglycerides and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0067] Example 5

[0068] The preparation of reactants A and B is the same as in Example 1.

[0069] After mixing 15g of reactant A with 70g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglyceride and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0070] Example 6

[0071] The preparation of reactants A and B is the same as in Example 2.

[0072] After mixing 15g of reactant A with 70g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglyceride and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0073] Example 7

[0074] The preparation of reactants A and B is the same as in Example 3.

[0075] After mixing 15g of reactant A with 70g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglyceride and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0076] Example 8

[0077] The preparation of reactants A and B is the same as in Example 4.

[0078] After mixing 15g of reactant A with 70g of reactant B evenly, add 5g of diammonium hydrogen phosphate, 5g of diglyceride and 5g of deionized water, and stir evenly to obtain the tank clogging agent product.

[0079] Comparative Example 1

[0080] The preparation of reactant B is the same as in Example 1.

[0081] Take 85g of reactant B, then add 5g of diammonium hydrogen phosphate, 5g of diglycerol and 5g of deionized water, and stir until homogeneous to obtain the tank clogging agent product.

[0082] Comparative Example 2

[0083] The preparation of reactant B is the same as in Example 2.

[0084] Take 85g of reactant B, then add 5g of diammonium hydrogen phosphate, 5g of diglycerol and 5g of deionized water, and stir until homogeneous to obtain the tank clogging agent product.

[0085] Detection example

[0086] The adhesive samples prepared in Examples 1-4 and Comparative Examples 1-2 of this invention (all adhesives were diluted to a solid content of 20%) were tested for adhesion, film hardness, and rewetting ratio. The adhesion test method was based on the method disclosed in patent CN101235610A, "Preparation of a Polyamide-Epoxychloropropane Resin Adhesive," (unit: kg). Film hardness was tested as follows: the adhesive was sprayed onto a stainless steel platform heated to 110°C. After the adhesive cured into a film, a coating scratch test was conducted using pencils of different hardnesses. The rewetting ratio test method was based on the method disclosed in CN103415550B, "Polyamine Polyamide-Based Amine Epihaloalcohol Composition and its Preparation and Use Method." Specific test results are shown in the table below.

[0087]

[0088]

[0089] discuss

[0090] Comparing the various embodiments and comparative examples in the table above, the adhesion, film hardness, and rewetting ratio of the adhesive samples prepared in Examples 1 to 4 are all superior to those in Comparative Examples 1 and 2. Comparing Examples 1 and 3, and Examples 2 and 4, the difference lies in the ratio of NVP monomer to hydrophilic organosilicon monomer. As the proportion of hydrophilic organosilicon monomer increases, the adhesion of the prepared adhesive samples deteriorates, the film hardness softens, and the rewetting ratio improves. Comparing Examples 1 to 8, it can be seen that as the content of vinylpyrrolidone organosilicon copolymer increases, the adhesion and rewetting ratio improve, and the film hardness softens. It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

Claims

1. A wrinkling and sealing agent, characterized in that, Based on parts by mass, it includes the following components: 1-20 parts of vinylpyrrolidone silicone copolymer; Polyamide polyamine epichlorohydrin resin 60-98.8 parts; Functional additives: 0.1-10 parts; Modifier 0.1-10 parts; The vinylpyrrolidone organosilicon copolymer has the following structural formula: ； Where x is an integer from 5 to 20, m is an integer from 3 to 10, n is an integer from 1 to 10, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or methyl, and R3 is hydrogen or methyl. The functional additive is one or more of diammonium hydrogen phosphate, diammonium dihydrogen phosphate, and sodium pyrophosphate; The modifier is one or more of glycerol, diglycerol, triglyceride, diethylene glycol, 1,2,6-hexanetriol, pentaerythritol, polyethylene glycol, sorbitol, and inositol.

2. The wrinkling and sticking agent according to claim 1, characterized in that, The preparation method of the vinylpyrrolidone organosilicon copolymer includes: N-vinylpyrrolidone and hydrophilic organosilicon monomers are subjected to free radical copolymerization in aqueous solution to obtain vinylpyrrolidone organosilicon copolymers; The hydrophilic organosilicon monomer is a hydrophilic organosilicon monomer containing ethylene oxide segments.

3. A method for preparing the wrinkling and sticking agent according to claim 1 or 2, characterized in that, Includes the following steps: Step 1: N-vinylpyrrolidone and hydrophilic organosilicon monomers are subjected to free radical copolymerization in aqueous solution to obtain vinylpyrrolidone organosilicon copolymer; Step 2: Polyamide polyamine polymer is obtained by reacting polyamines with dicarboxylic acids; then the polyamide polyamine polymer is crosslinked with epichlorohydrin to obtain polyamide polyamine epichlorohydrin resin. Step 3: Mix vinylpyrrolidone silicone copolymer and polyamide polyamine epichlorohydrin resin in a predetermined ratio, and then add a predetermined amount of functional additives and modifiers to the mixture to obtain wrinkling and sticking agent.

4. The method for preparing the wrinkling and sticking agent according to claim 3, characterized in that, Step 1 includes: Step 1-1: Remove the polymerization inhibitor from the N-vinylpyrrolidone monomer by vacuum distillation; Step 1-2: Add some of the N-vinylpyrrolidone monomer, hydrophilic organosilicon monomer, and deionized water treated in step 1-1 to the reaction vessel, and stir until homogeneous; Steps 1-3: Add an appropriate amount of activator, purge with nitrogen to displace the oxygen in the flask, then heat to 55-65℃, add an appropriate amount of initiator, and at the same time start to drop another part of the N-vinylpyrrolidone monomer solution treated in step 1-1, drop it over 1-2 hours, and then keep the reaction at 65-75℃ for 4-8 hours. Steps 1-4: After heat preservation, add an appropriate amount of terminator, heat to 75-85℃, continue the reaction for 1-4 hours, cool to room temperature, and discharge to obtain a transparent colorless to light yellow viscous aqueous solution.

5. The method for preparing the wrinkling and sticking agent according to claim 4, characterized in that, The activator is one or more of monoethylamine, triethylamine, and tetramethylammonium hydroxide.

6. The method for preparing the wrinkling and sticking agent according to claim 4, characterized in that, The initiator is one or more of the following: hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, tert-butyl hydroperoxide, tert-butyl benzoic acid peroxide, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanopentanoic acid, and azobisisopropylimidazoline.

7. The method for preparing the wrinkling and sticking agent according to claim 4, characterized in that, The terminator is sodium bisulfite.

8. The method for preparing the wrinkling and sticking agent according to claim 4, characterized in that, In step 1, the mass fractions of each material are as follows: 29-40 parts of N-vinylpyrrolidone monomer, 1-11 parts of hydrophilic organosilicon monomer, 0.05-0.60 parts of co-activator, 0.05-0.50 parts of initiator, and 0.10-1.00 parts of terminator.

9. The method for preparing the wrinkling and sticking agent according to claim 3, characterized in that, The polyamino amine is selected from one or a mixture of several of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hydroxyethylethylenediamine, hydroxypropylethylenediamine, and aminoethylaminopropylamine.

10. The method for preparing the wrinkling and sticking agent according to claim 3, characterized in that, The aforementioned dicarboxylic acid is selected from one or a mixture of several of succinic acid, glutaric acid, adipic acid, and azelaic acid.

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