Antibacterial toilet paper and processing method thereof

Abstract

The invention discloses antibacterial toilet paper and a processing method thereof, and particularly relates to the technical field of papermaking. The antibacterial toilet paper is composed of a natural antibacterial agent, a modified inorganic antibacterial agent, microcapsules and optimized paper pulp, the natural antibacterial agent comprises a wormwood extract and a honeysuckle extract, the modified inorganic antibacterial agent is nano zinc oxide with hydroxyl grafted on the surface, and the microcapsules are chitosan microcapsules. The processing method of the antibacterial toilet paper comprises the steps of pulp pretreatment and enzymolysis pulping, ultrasonic dispersion and coupling of a composite antibacterial agent, mixed pulp reaction, fourdrinier papermaking forming, low-temperature drying and micro-calendering, surface chitosan solution spraying treatment and silicone oil dipping treatment. Through the synergistic effect of a natural-inorganic composite antibacterial system, microcapsule coating slow release and fiber surface modification treatment, firm adhesion and uniform distribution of an antibacterial agent are achieved, the antibacterial durability, broad spectrum and use safety of the antibacterial toilet paper are remarkably improved, and meanwhile the good physical performance and soft touch feeling of the paper are kept.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of papermaking, and relates to an antibacterial toilet paper and a processing method thereof. BACKGROUND

[0002] At present, in the research and application of antibacterial toilet paper, the problems of easy migration and shedding of antibacterial agents, short antibacterial duration are common. Traditional processes mostly use chemical antibacterial agents such as quaternary ammonium salts, which are introduced into the paper base through simple physical mixing or surface coating. The binding force between such antibacterial agents and fibers mainly depends on weak physical adsorption. In the use process, especially when wet, the antibacterial components are easily and quickly dissolved and migrated, resulting in high initial antibacterial rate but poor durability, short antibacterial time, and inability to meet the demand for long-term protection.

[0003] Secondly, the poor compatibility of antibacterial agents with pulp fibers further restricts the performance of antibacterial toilet paper. In particular, nano-inorganic antibacterial agents such as nano-zinc oxide and nano-silver, due to their large specific surface area and high surface energy, are prone to agglomeration in the pulp water system, and are difficult to disperse uniformly. This not only reduces the effective utilization rate of the antibacterial agent, but also may cause the strength of the paper to decrease and the hand feeling to be rough. In addition, the antibacterial agent without surface modification lacks chemical bonding sites with cellulose fibers, and has weak compatibility, which is easy to distribute unevenly in the process of papermaking and drying, affecting the stability of product performance.

[0004] In addition, the antibacterial spectrum of the existing antibacterial toilet paper is relatively narrow, and there may be safety and environmental hazards. A single type of antibacterial agent is often only effective against specific microorganisms, making it difficult to achieve broad-spectrum antibacterial. While some chemical synthetic antibacterial agents have high antibacterial efficiency, they can stimulate the skin, cause allergies, and have poor biodegradability, and the residues are not environmentally friendly. Therefore, developing a composite antibacterial system that has broad-spectrum, long-acting, safety and good compatibility with fibers has become a technical difficulty that needs to be broken through in the field of antibacterial toilet paper. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present application provide an antibacterial toilet paper and a processing method thereof, which solve the problems of easy migration and shedding of antibacterial agents used in antibacterial toilet paper, short antibacterial duration, poor compatibility of antibacterial agents with pulp fibers, and narrow antibacterial spectrum.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] An antibacterial toilet paper, specifically comprising the following components:

[0008] Natural antibacterial agent, modified inorganic antibacterial agent, microcapsule, and optimized pulp.

[0009] Preferably, the natural antibacterial agent is composed of 5-10 parts by weight of wormwood extract and 3-8 parts by weight of honeysuckle extract, the modified inorganic antibacterial agent is 1-3 parts by weight of nano zinc oxide with a particle size of ≤50 nm and a surface grafted with hydroxyl groups, and the microcapsule is 2-5 parts by weight of chitosan.

[0010] Preferably, the optimized pulp is composed of 80 parts by weight of broadleaf wood pulp, 20 parts by weight of coniferous wood pulp, 0.5-1 part by weight of cationic starch, 0.2-0.5 part by weight of sodium alginate, 0.05-0.1 part by weight of cellulase, and 0.05-0.1 part by weight of KH550 coupling agent.

[0011] Preferably, the microcapsule is used as a wall material, and the natural antibacterial agent and the modified inorganic antibacterial agent are a core-shell structure microcapsule with the natural antibacterial agent and the modified inorganic antibacterial agent as a composite core material attached to the wall material.

[0012] A processing method of antibacterial toilet paper, comprising the following steps:

[0013] S1: soaking broadleaf wood pulp and coniferous wood pulp in a constant-temperature water bath, then placing them in a PFI beater for beating, and then adding cellulase, sodium alginate, and cationic starch in sequence to obtain mixed pulp;

[0014] S2: ultrasonic dispersion of wormwood extract, honeysuckle extract, nano zinc oxide with a surface grafted with hydroxyl groups, chitosan microcapsule, and KH550 coupling agent to obtain a composite antibacterial agent;

[0015] S3: mixing and stirring the mixed pulp prepared in S1 and the composite antibacterial agent prepared in S2 to obtain modified pulp, and then placing the modified pulp in a sealed reaction kettle for standing;

[0016] S4: preparing paper from the pulp prepared in S3 by a long net papermaking process;

[0017] S5: drying the paper prepared in S4, and then immediately performing micro-calendering treatment on the dried paper to obtain pretreated paper;

[0018] S6: spraying chitosan solution on the surface of the pretreated paper prepared in S5 by using a spraying device, and then immediately drying the paper in a vacuum drying oven;

[0019] S7: immersing the paper prepared in S6 in a silicone oil immersion roller for 2 seconds, and finally drying the paper in an air blast dryer for 5 minutes to obtain antibacterial toilet paper.

[0020] Preferably, in step S1, the hardwood pulp and softwood pulp are soaked in a constant temperature water bath at 25-30°C for 30 minutes. In step S1, the PFI pulper speed is 1000-3000 rpm and the pulp concentration is controlled at 4-5%. In step S1, cellulase, sodium alginate and cationic starch are added in sequence and then mixed at 35-40°C and 500-600 rpm for 20 minutes to obtain a mixed pulp.

[0021] Preferably, in step S2, an ultrasonic disperser is used to ultrasonically disperse the particles in a water bath at 300W, 40kHz, and 30℃ for 15-20 minutes.

[0022] Preferably, in step S3, the mixed slurry and the composite antibacterial agent are placed in a mixer with a speed of 50~100 rpm and stirred continuously for 5 minutes, and in step S3, the modified slurry is placed in a sealed reaction vessel at 50~60℃ and allowed to stand for 30~40 minutes.

[0023] Preferably, in step S4, the papermaking speed is set to 80-100 m / min, the wire section dewatering pressure to 0.15-0.17 MPa, and the press line pressure to 80-90 kN / m. The basis weight of the finished paper in step S4 is controlled at 18-20 g / m. S5 sets the drying oven temperature to 60~70℃ and continues drying for 2 hours. S5 also sets the pressure of the microcalendered paper to 0.3~0.5MPa and the roller temperature to 80℃.

[0024] Preferably, the spraying dosage of chitosan solution in S6 is 3~5g / The solution mass fraction is 0.3~0.5%, the temperature of the S6 vacuum drying oven is set to 50~60℃ and dried for 10 minutes, the silicone oil concentration of the paper passing through in S7 is 1~2%, and the drying temperature of the blower dryer in S7 is 40~45℃.

[0025] The technical effects and advantages of the antibacterial toilet paper and its processing method of the present invention are as follows:

[0026] 1. This invention utilizes a system composed of natural antibacterial components, modified inorganic antibacterial agents, and microcapsule encapsulation to achieve a broad-spectrum, highly efficient, and long-lasting antibacterial effect. Artemisia argyi and honeysuckle extracts, along with nano-zinc oxide with surface-grafted hydroxyl groups, are encapsulated in chitosan microcapsules to form a synergistic composite antibacterial system. This system's antibacterial spectrum covers Gram-positive bacteria, Gram-negative bacteria, and fungi. Furthermore, through the sustained-release effect of the microcapsules and the synergistic effect of each component, the antibacterial product possesses excellent initial antibacterial rate and long-lasting antibacterial ability, fundamentally overcoming the shortcomings of single antibacterial agents, such as narrow antibacterial spectrum and short duration of action.

[0027] 2、The application solves the problem of agglomeration by using modified inorganic antibacterial agent to improve the binding force, thereby ensuring the stable existence and efficient use of the antibacterial component in the paper, and the dispersibility and compatibility of the nano zinc oxide on the surface of the water phase and the pulp fiber are significantly improved by surface hydroxyl grafting modification of the nano zinc oxide, thereby effectively preventing the agglomeration failure of the nano particles, the surface active groups of the modified nano zinc oxide are increased, and through the bridging effect of the KH550 coupling agent, the pulp fiber and the natural antibacterial component form a more firm chemical bonding and physical adsorption, thereby greatly reducing the migration and shedding rate of the antibacterial agent during use, and realizing the persistent stability of the antibacterial efficiency.

[0028] 3、The natural antibacterial component used in the application is wormwood extract / jasmine extract, which has the characteristics of no irritation and biodegradability, and the wormwood and jasmine extracts derived from plants are mild and non-irritating to human skin, have good biocompatibility, and avoid the risk of allergy or irritation caused by chemical residues, the natural ingredients and their carrier chitosan are biodegradable materials, which are easily decomposed by the environment after the product is discarded, and meet the green and sustainable development concept.

[0029] 4、The application adopts chitosan-coated composite antibacterial agent to realize slow-release antibacterial effect, prolong the service life, and build multi-level antibacterial protection, chitosan is a natural cationic polysaccharide, which has good antibacterial property and film-forming property, the composite antibacterial agent is coated in chitosan through microencapsulation technology, on the one hand, an antibacterial agent reservoir is formed in the paper, the active ingredients are released by slow dissolution of the chitosan matrix, and the persistence of the antibacterial effect is realized, on the other hand, the chitosan solution sprayed on the surface of the paper can quickly form a dense antibacterial protective film, providing instant and strong surface contact antibacterial effect, and the double mechanisms jointly guarantee the antibacterial efficiency of the product during the entire service cycle.

[0030] 5、The application uses broadleaf wood pulp and coniferous wood pulp, which has good softness and fiber binding force, and the added cationic starch can enhance the adsorbability of the antibacterial agent and the fiber, thereby balancing the excellent use experience and functional durability, 80% of the broadleaf wood pulp provides good softness and delicate touch of the paper, and 20% of the coniferous wood pulp enhances the dry and wet strength and toughness of the paper, the added cationic starch in the optimized base material can strongly adsorb the negatively charged pulp fiber and antibacterial agent through its positive charge, thereby playing a bridge and anchoring role, significantly improving the retention rate and distribution uniformity of the antibacterial agent in the fiber network, and ensuring the functionality without sacrificing the inherent physical properties of the paper.

[0031] 6、The application adopts enzymatic pulping to degrade the surface structure of the fiber, expose more hydroxyl groups, thereby increasing the binding sites of the paper fiber and the antibacterial agent, and realizing the in-situ firm adhesion of the antibacterial agent. Adding trace cellulase in the pulping process can selectively and mildly hydrolyze part of the non-crystalline cellulose on the surface of the fiber, expose more active groups such as hydroxyl groups and carboxyl groups, and these newly added active sites enhance the chemical reactivity of the fiber surface and the surface functional groups of the modified nano zinc oxide and KH550 coupling agent, and promote the formation of covalent bonds or strong hydrogen bonds.

[0032] 7、The application adopts ultrasonic dispersion of the composite antibacterial agent to prevent subsequent coating from falling off, ensures the high uniform distribution and stable combination of the functional components in the paper base, and through the ultrasonic dispersion treatment of high power and specific frequency, the soft agglomeration of the nano zinc oxide is effectively destroyed under the cooperation of the KH550 coupling agent, and the wormwood / honeysuckle extract, chitosan microcapsule and other components are fully dispersed and mixed to form a uniform and stable composite antibacterial agent dispersion liquid.

[0033] 8、The application adopts synergistic forming under low temperature conditions to improve the flatness of the paper, so as to not destroy the structure and activity of the antibacterial agent, and maintain the activity of each functional component. The entire processing flow, drying and micro-calendaring links are carried out at a relatively low temperature. Low-temperature drying avoids the destruction of heat-sensitive active ingredients in the natural extract and the degradation of the organic polymer structure of chitosan and starch caused by high temperature, maximally retains the antibacterial efficiency, and the micro-calendaring process effectively improves the smoothness and tightness of the paper surface under appropriate pressure and temperature, improves the hand feeling and appearance, and the mild physical treatment will not crush the fiber structure loaded with the antibacterial agent or damage the integrity of the microcapsule, realizing the dual purposes of improving the physical properties of the paper and protecting the function. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 It is a flowchart of an antibacterial sanitary paper and a processing method thereof according to the application. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0036] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. Example 1

[0037] This embodiment provides an antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0038] Experimental materials:

[0039] Natural antibacterial agents: 10 parts by weight of Artemisia argyi extract, 8 parts by weight of Lonicera japonica extract;

[0040] Modified inorganic antibacterial agent: 3 parts by weight of nano zinc oxide with surface-grafted hydroxyl groups and a particle size ≤50nm;

[0041] Microcapsules: 5 parts by weight of chitosan;

[0042] Pulp: 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 1 part by weight of cationic starch, and 0.5 parts by weight of sodium alginate;

[0043] Additives: 0.1 parts by weight of cellulase, 0.1 parts by weight of KH550 coupling agent.

[0044] Experimental objective:

[0045] Prepare an antibacterial toilet paper.

[0046] Experimental steps:

[0047] S1: Soak the hardwood pulp and softwood pulp in a constant temperature water bath at 30°C for 30 minutes, then place them in a PFI pulper at 3000 rpm and control the pulp concentration at 5% and the pulping time at 15 minutes. Then add cellulase, sodium alginate and cationic starch dropwise and mix at 40°C and 600 rpm for 20 minutes to obtain a mixed pulp.

[0048] S2: Artemisia argyi extract, honeysuckle extract, nano zinc oxide with hydroxyl groups grafted on the surface, chitosan microcapsules, and KH550 coupling agent were placed in a water bath with a power of 300W, a frequency of 40kHz, and a temperature of 30℃ and dispersed in an ultrasonic disperser for 15 minutes to obtain a composite antibacterial agent.

[0049] S3: The mixed slurry prepared in S1 and the composite antibacterial agent prepared in S2 are placed in a mixer with a speed of 50 rpm and stirred for 5 minutes to obtain a modified slurry. Then the modified slurry is placed in a sealed reaction vessel at 60°C and allowed to stand for 30 minutes.

[0050] S4: Place the pulp prepared in S3 into a long-wire papermaking process with a machine speed of 100m / min, a wire dewatering pressure of 0.17MPa, and a press line pressure of 90kN / m, and control the basis weight of the finished paper at 20g / m. ;

[0051] S5: Place the prepared paper in a drying oven at 70°C and dry for 2 hours. Then immediately calender the dried paper with a pressure of 0.5MPa and a roller temperature of 80°C for 1 minute to obtain pretreated paper.

[0052] S6: The spraying dosage on the surface of the pretreated paper prepared in S5 using a spraying device is 5g / 0.5% chitosan solution, then immediately place the paper in a vacuum drying oven at 50°C for 10 minutes to dry;

[0053] S7: The paper prepared in S6 is impregnated in a silicone oil impregnation roller with a silicone oil concentration of 2% for 2 seconds, and finally the paper is dried in a 40℃ blower dryer for 5 minutes to prepare antibacterial toilet paper.

[0054] Experimental results: See Table 1 for details.

[0055] Table 1: Test Results of Example 1 Antibacterial rate Bacteriostatic time DCM extract Canadian freeness Tensile index Tear index Burst index Bulk Example 1 ≥ 99.5% ≥ 72h ≤ 0.20 308±14 71.7±4.0 6.7±0.3 5.1±0.3 13.6±0.04

[0056] Example 1 employs a "natural-inorganic" composite antibacterial system and optimized process. Its superior antibacterial performance stems from a triple synergistic mechanism. Artemisia argyi and honeysuckle extracts, along with nano-zinc oxide grafted with hydroxyl groups, form a broad-spectrum antibacterial synergistic effect, acting on the microbial cell membrane and internal metabolism respectively, producing a synergistic enhancement effect. Chitosan microcapsules encapsulate the aforementioned antibacterial agents, achieving in-situ sustained release within the paper fiber network, significantly extending the antibacterial duration. Furthermore, KH550 coupling agent and enzymatic pulping pretreatment significantly increase the chemical bonding and physical adsorption sites between the antibacterial agent and the pulp fiber surface, resulting in an extremely low antibacterial agent shedding rate. In terms of physical properties, 3000 rpm PFI pulping fully fibrillates the fibers, and subsequent microcalendering and chitosan / silicone oil surface treatment ensure excellent strength while achieving suitable bulk and surface smoothness, achieving an optimal balance between antibacterial durability, paper physical strength, and usability. Example 2

[0057] This embodiment provides an antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0058] Experimental materials:

[0059] Natural antibacterial agents: 10 parts by weight of Artemisia argyi extract, 8 parts by weight of Lonicera japonica extract;

[0060] Microcapsules: 5 parts by weight of chitosan;

[0061] Pulp: 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 1 part by weight of cationic starch, and 0.5 parts by weight of sodium alginate;

[0062] Additives: 0.1 parts by weight of cellulase, 0.1 parts by weight of KH550 coupling agent.

[0063] Experimental objective:

[0064] No modified inorganic antibacterial agent is added in this embodiment.

[0065] Experimental steps:

[0066] S1: Soak the hardwood pulp and softwood pulp in a constant temperature water bath at 30°C for 30 minutes, then place them in a PFI pulper at 3000 rpm and control the pulp concentration at 5% and the pulping time at 15 minutes. Then add cellulase, sodium alginate and cationic starch dropwise and mix at 40°C and 600 rpm for 20 minutes to obtain a mixed pulp.

[0067] S2: Artemisia argyi extract, honeysuckle extract, chitosan microcapsules, and KH550 coupling agent were placed in a water bath at 300W, 40kHz, and 30℃ and dispersed in an ultrasonic disperser for 15 minutes to obtain a composite antibacterial agent.

[0068] S3: The mixed slurry prepared in S1 and the composite antibacterial agent prepared in S2 are placed in a mixer with a speed of 50 rpm and stirred for 5 minutes to obtain a modified slurry. Then the modified slurry is placed in a sealed reaction vessel at 60°C and allowed to stand for 30 minutes.

[0069] S4: Place the pulp prepared in S3 into a long-wire papermaking process with a machine speed of 100m / min, a wire dewatering pressure of 0.17MPa, and a press line pressure of 90kN / m, and control the basis weight of the finished paper at 20g / m. ;

[0070] S5: Place the prepared paper in a drying oven at 70°C and dry for 2 hours. Then immediately calender the dried paper with a pressure of 0.5MPa and a roller temperature of 80°C for 1 minute to obtain pretreated paper.

[0071] S6: The spraying dosage on the surface of the pretreated paper prepared in S5 using a spraying device is 5g / 0.5% chitosan solution, then immediately place the paper in a vacuum drying oven at 50°C for 10 minutes to dry;

[0072] S7: The paper prepared in S6 is impregnated in a silicone oil impregnation roller with a silicone oil concentration of 2% for 2 seconds, and finally the paper is dried in a 40℃ blower dryer for 5 minutes to prepare antibacterial toilet paper.

[0073] Experimental results: See Table 2 for details.

[0074] Table 2: Test Results of Example 2 Antibacterial rate Bacteriostatic time DCM extract Canadian freeness Tensile index Tear index Burst index Bulk Example 2 ≥98.0% ≥48h ≤0.22% 308±14 71.0±4.0 6.6±0.3 5.0±0.3 1.37±0.04

[0075] The difference between Example 2 and Example 1 is that no modified inorganic antibacterial agent is added. Instead, the antibacterial performance is slightly reduced because the nano zinc oxide has broad-spectrum antibacterial and photocatalytic activity and can produce a synergistic effect with the natural extract, enhancing the inhibitory ability against Gram-negative bacteria and fungi. The antibacterial spectrum is narrowed and the inhibition time is shortened. However, the natural extract still has a certain antibacterial basis, indicating that the nano zinc oxide has no significant reinforcing effect on the fiber structure in the system. Its main function is to enhance the antibacterial effect. Example 3

[0076] This embodiment provides an antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0077] Experimental materials:

[0078] Natural antibacterial agents: 10 parts by weight of Artemisia argyi extract, 8 parts by weight of Lonicera japonica extract;

[0079] Modified inorganic antibacterial agent: 3 parts by weight of nano zinc oxide with surface-grafted hydroxyl groups and a particle size ≤50nm;

[0080] Microcapsules: 5 parts by weight of chitosan;

[0081] Pulp: 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 1 part by weight of cationic starch, and 0.5 parts by weight of sodium alginate;

[0082] Additives: 0.1 parts by weight of cellulase, 0.1 parts by weight of KH550 coupling agent.

[0083] Experimental objective:

[0084] Reduce the PFI pulping speed.

[0085] Experimental steps:

[0086] S1: Soak the hardwood pulp and softwood pulp in a constant temperature water bath at 30°C for 30 minutes, then place them in a PFI pulper at 1000 rpm and control the pulp concentration at 5% and the pulping time at 15 minutes. Then add cellulase, sodium alginate and cationic starch dropwise and mix at 40°C and 600 rpm for 20 minutes to obtain a mixed pulp.

[0087] S2: Artemisia argyi extract, honeysuckle extract, nano zinc oxide with hydroxyl groups grafted on the surface, chitosan microcapsules, and KH550 coupling agent were placed in a water bath with a power of 300W, a frequency of 40kHz, and a temperature of 30℃ and dispersed in an ultrasonic disperser for 15 minutes to obtain a composite antibacterial agent.

[0088] S3: The mixed slurry prepared in S1 and the composite antibacterial agent prepared in S2 are placed in a mixer with a speed of 50 rpm and stirred for 5 minutes to obtain a modified slurry. Then the modified slurry is placed in a sealed reaction vessel at 60°C and allowed to stand for 30 minutes.

[0089] S4: Place the pulp prepared in S3 into a long-wire papermaking process with a machine speed of 100m / min, a wire dewatering pressure of 0.17MPa, and a press line pressure of 90kN / m, and control the basis weight of the finished paper at 20g / m. ;

[0090] S5: Place the prepared paper in a drying oven at 70°C and dry for 2 hours. Then immediately calender the dried paper with a pressure of 0.5MPa and a roller temperature of 80°C for 1 minute to obtain pretreated paper.

[0091] S6: The spraying dosage on the surface of the pretreated paper prepared in S5 using a spraying device is 5g / 0.5% chitosan solution, then immediately place the paper in a vacuum drying oven at 50°C for 10 minutes to dry;

[0092] S7: The paper prepared in S6 is impregnated in a silicone oil impregnation roller with a silicone oil concentration of 2% for 2 seconds, and finally the paper is dried in a 40℃ blower dryer for 5 minutes to prepare antibacterial toilet paper.

[0093] Experimental results: See Table 3 for details.

[0094] Table 3: Test Results of Example 3 Antibacterial rate Bacteriostatic time DCM extract Canadian freeness Tensile index Tear index Burst index Bulk Example 3 ≥99.5% ≥72h ≤0.20 352±16 56.1±3.2 6.2±0.5 3.6±0.2 1.47±0.04

[0095] Example 3 reduced the PFI beating speed from 3000 to 1000, resulting in a decrease in fiber fibrillation and a reduction in the interfiber bonding area. The decrease in beating speed directly led to an increase in Canadian fiber freeness, a significant decrease in tensile index and burst index, and an increase in bulk. The antibacterial properties were not affected, indicating that the binding of the antibacterial agent to the fiber mainly depends on chemical coupling and microencapsulation, rather than the physical beating degree. This example shows that the beating speed mainly affects the physical strength of the paper and has no significant effect on the loading and release of the composite antibacterial system. Example 4

[0096] This embodiment provides an antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0097] Experimental materials:

[0098] Natural antibacterial agents: 10 parts by weight of Artemisia argyi extract, 8 parts by weight of Lonicera japonica extract;

[0099] Modified inorganic antibacterial agent: 3 parts by weight of nano zinc oxide with surface-grafted hydroxyl groups and a particle size ≤50nm;

[0100] Microcapsules: 5 parts by weight of chitosan;

[0101] Pulp: 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 1 part by weight of cationic starch, and 0.5 parts by weight of sodium alginate;

[0102] Additives: 0.1 parts by weight of cellulase, 0.1 parts by weight of KH550 coupling agent.

[0103] Experimental objective:

[0104] The application of chitosan solution and silicone oil impregnation is omitted.

[0105] Experimental steps:

[0106] S1: Soak the hardwood pulp and softwood pulp in a constant temperature water bath at 30°C for 30 minutes, then place them in a PFI pulper at 3000 rpm and control the pulp concentration at 5% and the pulping time at 15 minutes. Then add cellulase, sodium alginate and cationic starch dropwise and mix at 40°C and 600 rpm for 20 minutes to obtain a mixed pulp.

[0107] S2: Artemisia argyi extract, honeysuckle extract, nano zinc oxide with hydroxyl groups grafted on the surface, chitosan microcapsules, and KH550 coupling agent were placed in a water bath with a power of 300W, a frequency of 40kHz, and a temperature of 30℃ and dispersed in an ultrasonic disperser for 15 minutes to obtain a composite antibacterial agent.

[0108] S3: The mixed slurry prepared in S1 and the composite antibacterial agent prepared in S2 are placed in a mixer with a speed of 50 rpm and stirred for 5 minutes to obtain a modified slurry. Then the modified slurry is placed in a sealed reaction vessel at 60°C and allowed to stand for 30 minutes.

[0109] S4: Place the pulp prepared in S3 into a long-wire papermaking process with a machine speed of 100m / min, a wire dewatering pressure of 0.17MPa, and a press line pressure of 90kN / m, and control the basis weight of the finished paper at 20g / m. ;

[0110] S5: Place the prepared paper in a drying oven at 70°C and dry for 2 hours. Then immediately calender the dried paper with a pressure of 0.5MPa and a roller temperature of 80°C for 1 minute to obtain pretreated paper.

[0111] Experimental results: See Table 4 for details.

[0112] Table 4: Test Results of Example 4

[0113] Example 4 eliminated the surface spraying of chitosan solution and silicone oil impregnation process, resulting in the lack of a chitosan slow-release layer and a silicone oil hydrophobic protective layer on the paper surface. The chitosan solution forms an antibacterial film on the surface, which can delay the release of internal antibacterial agents and enhance surface antibacterial activity; the silicone oil provides hydrophobicity, reducing the leaching and migration of antibacterial agents by moisture during use. After elimination, the antibacterial durability decreased, and the DCM extract content increased, indicating that the surface antibacterial agent was more prone to migration. Example 5

[0114] This embodiment provides an antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0115] Experimental materials:

[0116] Natural antibacterial agents: 10 parts by weight of Artemisia argyi extract, 8 parts by weight of Lonicera japonica extract;

[0117] Modified inorganic antibacterial agent: 3 parts by weight of nano zinc oxide with surface-grafted hydroxyl groups and a particle size ≤50nm;

[0118] Microcapsules: 5 parts by weight of chitosan;

[0119] Pulp: 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 1 part by weight of cationic starch, and 0.5 parts by weight of sodium alginate;

[0120] Additives: 0.1 parts by weight of cellulase, 0.1 parts by weight of KH550 coupling agent.

[0121] Experimental objective:

[0122] Reduce the machine speed, wire section dewatering pressure, and press line pressure in the long-wire papermaking process.

[0123] Experimental steps:

[0124] S1: Soak the hardwood pulp and softwood pulp in a constant temperature water bath at 30°C for 30 minutes, then place them in a PFI pulper at 3000 rpm and control the pulp concentration at 5% and the pulping time at 15 minutes. Then add cellulase, sodium alginate and cationic starch dropwise and mix at 40°C and 600 rpm for 20 minutes to obtain a mixed pulp.

[0125] S2: Artemisia argyi extract, honeysuckle extract, nano zinc oxide with hydroxyl groups grafted on the surface, chitosan microcapsules, and KH550 coupling agent were placed in a water bath with a power of 300W, a frequency of 40kHz, and a temperature of 30℃ and dispersed in an ultrasonic disperser for 15 minutes to obtain a composite antibacterial agent.

[0126] S3: The mixed slurry prepared in S1 and the composite antibacterial agent prepared in S2 are placed in a mixer with a speed of 50 rpm and stirred for 5 minutes to obtain a modified slurry. Then the modified slurry is placed in a sealed reaction vessel at 60°C and allowed to stand for 30 minutes.

[0127] S4: Place the pulp prepared in S3 into a long-wire papermaking process with a machine speed of 80m / min, a wire dewatering pressure of 0.15MPa, and a press line pressure of 80kN / m, and control the basis weight of the finished paper at 18g / m. ;

[0128] S5: Place the prepared paper in a drying oven at 70°C and dry for 2 hours. Then immediately calender the dried paper with a pressure of 0.5MPa and a roller temperature of 80°C for 1 minute to obtain pretreated paper.

[0129] S6: The spraying dosage on the surface of the pretreated paper prepared in S5 using a spraying device is 5g / 0.5% chitosan solution, then immediately place the paper in a vacuum drying oven at 50°C for 10 minutes to dry;

[0130] S7: The paper prepared in S6 is impregnated in a silicone oil impregnation roller with a silicone oil concentration of 2% for 2 seconds, and finally the paper is dried in a 40℃ blower dryer for 5 minutes to prepare antibacterial toilet paper.

[0131] Experimental results: See Table 5 for details.

[0132] Table 5: Test Results of Example 5

[0133] Example 5 reduced the machine speed, dewatering pressure, and press line pressure in the four-wire papermaking process, resulting in insufficient dewatering of the wet paper during the forming and pressing stages. This weakened the interfiber bonding, leading to a decrease in the physical strength of the paper, an increase in bulk, and a more porous structure. The fact that the antibacterial properties were not affected indicates that the antibacterial agent had achieved uniform loading in the pulp through ultrasonic dispersion and coupling agent modification. The papermaking process parameters mainly affect the physical structure of the paper and have no significant impact on the distribution and activity of the antibacterial agent. This example highlights the controllability of process parameters on the mechanical properties of paper and is suitable for applications requiring higher softness. Comparative Example 1

[0134] This embodiment provides a traditional antibacterial toilet paper and its processing method, the specific implementation steps of which include:

[0135] Experimental materials:

[0136] Pulp: 100 parts by weight of bleached hardwood commercial pulp board;

[0137] Chemical antibacterial agent: 0.5 parts by weight of benzalkonium chloride;

[0138] Wet strength agent: 0.3 parts by weight of polyamide epichlorohydrin resin (PAE);

[0139] Dispersant: 0.1 parts by weight of polyacrylamide (PAM).

[0140] Experimental objective:

[0141] Antibacterial toilet paper was prepared using conventional chemical antibacterial agents and a simple mixing process to highlight the technical advantages of the composite antibacterial system and optimized process of this invention.

[0142] Experimental steps:

[0143] S1: Bleached hardwood pulpboard is subjected to conventional hydraulic disintegration to control the pulp consistency to 4.5% to obtain the base pulp.

[0144] S2: Then, benzalkonium chloride, PAE wet strength agent and PAM dispersant are directly added to the base slurry and mechanically stirred at 300 rpm for 10 minutes at room temperature to obtain the mixed slurry;

[0145] S3: The mixed pulp is processed into paper using a conventional cylinder paper machine at a speed of 60 m / min, with the basis weight of the finished paper controlled at 20 g / L. ;

[0146] S4: The paper obtained from papermaking is dried in a drying cylinder at 105°C, and then rolled to obtain the finished traditional antibacterial toilet paper.

[0147] Experimental results: See Table 6 for details.

[0148] Table 6: Test Results of Comparative Example 1 Antibacterial rate Bacteriostatic time DCM extract Canadian freeness Tensile index Tear index Burst index Bulk Comparative Example 1 ≥99.0% ≥12h ≤0.80% 510±10 58.0±3.5 5.8±0.4 3.8±0.3 1.50±0.05

[0149] Comparative Example 1 employed a conventional process combining a single chemical antibacterial agent with a simple physical mixture. While its initial antibacterial rate was acceptable, the inhibition time was extremely short. This is because the chemical antibacterial agent only adheres to the fiber surface through physical adsorption, and it readily dissolves and migrates upon contact with water during use. Furthermore, the simple processing method did not modify the fibers or introduce reinforcing agents, resulting in weak bonding between the antibacterial agent and the fiber, leading to mediocre physical strength of the paper. Without any surface softening treatment, the paper felt rather stiff.

[0150] Example 1 employs a complete natural-inorganic composite antibacterial system, combined with a complete set of optimized processing techniques from enzymatic hydrolysis and pulping to ultrasonic dispersion and coupling to stepwise surface treatment. It is a representative preferred solution of the present invention, aiming to verify the synergistic effect and comprehensive performance of each component and process.

[0151] Example 2 uses a simplified antibacterial system without modified inorganic antibacterial agent nano zinc oxide, retaining only natural extracts and chitosan microcapsules. Its design aims to verify the key synergistic effect of modified inorganic antibacterial agents in broadening the antibacterial spectrum and enhancing antibacterial durability, and to evaluate its impact on the physical structure of paper.

[0152] Example 3 employs a mild beating process with reduced PFI beating revolutions, while other components and process steps remain consistent with Example 1. The study investigates the independent effects of beating strength, a key physical treatment parameter, on pulp fiber splitting treatment and the final physical strength of paper, such as tensile strength, bursting index, and bulk. It also examines the mechanism of action of the compound antibacterial agent on its binding and antibacterial properties.

[0153] Example 4 employs a simplified post-treatment process that eliminates the surface spraying of chitosan solution and silicone oil impregnation, focusing on verifying the intrinsic properties of the internal composite antimicrobial system. This design isolates and evaluates the specific contributions of surface functionalization treatment to providing an initial antimicrobial barrier, enhancing hydrophobicity, delaying the migration of internal antimicrobial agents, and improving the feel of the paper surface.

[0154] Example 5 employs a loose papermaking process that reduces the speed of the wire paper machine, the dewatering pressure, and the pressure of the press line. The study investigates the controllability of the process intensity during the forming and pressing stages on the compactness of the paper's microstructure, physical and mechanical strength, and softness. At the same time, it examines whether such process adjustments will affect the uniformity of the distribution of antibacterial agents within the paper and their antibacterial efficacy.

[0155] Comparative Example 1 employs a traditional process based on a single chemical antibacterial agent and involving simple physical mixing and conventional cylinder papermaking. As a representative of the prior art in stark contrast to the present invention, it serves to highlight the significant progress and ingenuity of the present invention in addressing the long-lasting effect and strong adhesion of antibacterial agents, as well as the improvement of the overall performance of paper.

[0156] refer to Figure 1 The flowchart describes a process based on an optimized mixture of hardwood and softwood pulp. The process involves enzymatic pulping to activate the fiber surface, followed by ultrasonic dispersion of Artemisia argyi and honeysuckle extracts, surface-hydroxyl-modified nano-zinc oxide, chitosan microcapsules, and KH550 coupling agent to create a composite antibacterial agent. This agent is then uniformly mixed with the pulp and reacted. The paper is then formed using a long-wire papermaking process, followed by low-temperature drying and microcalendering to stabilize the paper structure. Finally, an antibacterial protective film is constructed by spraying a chitosan solution onto the surface, and the paper is impregnated with silicone oil to impart hydrophobicity, ultimately yielding the antibacterial toilet paper product. The entire process is interconnected, achieving a robust loading of antibacterial components, sustained-release synergistic effects, and a balance between paper physical properties and usability. This demonstrates the technological innovation of this invention across the entire process, from substrate modification and functional compounding to post-processing.

[0157] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims.

[0158] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An antibacterial toilet paper, characterized in that, Specifically, it includes the following components: Natural antibacterial agents, modified inorganic antibacterial agents, microcapsules, and optimized pulp.

2. The antibacterial toilet paper as described in claim 1, characterized in that, The natural antibacterial agent is composed of 5-10 parts by weight of Artemisia argyi extract and 3-8 parts by weight of Lonicera japonica extract. The modified inorganic antibacterial agent is 1-3 parts by weight of nano zinc oxide with surface grafted hydroxyl groups and a particle size ≤50nm. The microcapsules are 2-5 parts by weight of chitosan.

3. The antibacterial toilet paper as described in claim 1, characterized in that, The optimized pulp consists of 80 parts by weight of hardwood pulp, 20 parts by weight of softwood pulp, 0.5-1 parts by weight of cationic starch, 0.2-0.5 parts by weight of sodium alginate, 0.05-0.1 parts by weight of cellulase, and 0.05-0.1 parts by weight of KH550 coupling agent.

4. The antibacterial toilet paper as described in claim 1, characterized in that, The microcapsules serve as the wall material, with natural antibacterial agents and modified inorganic antibacterial agents forming the composite core material, which are attached to the core-shell structure of the microcapsules.

5. A processing method for antibacterial toilet paper, characterized in that, Includes the following steps: S1: Soak hardwood pulp and softwood pulp in a constant temperature water bath, then place them in a PFI pulper for pulping, and then add cellulase, sodium alginate and cationic starch dropwise to obtain a mixed pulp. S2: A composite antibacterial agent is obtained by ultrasonically dispersing Artemisia argyi extract, Lonicera japonica extract, nano zinc oxide with hydroxyl groups grafted on the surface, chitosan microcapsules, and KH550 coupling agent. S3: Mix the mixed slurry prepared in S1 with the composite antibacterial agent prepared in S2 to obtain a modified slurry, and then place the modified slurry in a sealed reaction vessel to stand. S4: The pulp prepared in S3 is processed into paper using a four-wire papermaking process; S5: Dry the paper prepared in S4, and then immediately calender the dried paper to obtain pretreated paper. S6: Spray chitosan solution onto the surface of the pretreated paper prepared in S5 using a spraying device, and then immediately place the paper in a vacuum drying oven to dry. S7: The paper prepared in S6 is impregnated in a silicone oil impregnation roller for 2 seconds, and finally the paper is placed in a blower dryer to dry for 5 minutes to prepare antibacterial toilet paper.

6. The processing method of antibacterial toilet paper as described in claim 5, characterized in that, In S1, hardwood pulp and softwood pulp are soaked in a constant temperature water bath at 25~30℃ for 30 minutes. In S1, the PFI pulper speed is 1000~3000 rpm and the pulp concentration is controlled at 4~5%. Cellulase, sodium alginate and cationic starch are added in sequence in S1 and then mixed at 35~40℃ and 500~600 rpm for 20 minutes to obtain mixed pulp.

7. The processing method of antibacterial toilet paper as described in claim 5, characterized in that, In S2, an ultrasonic disperser is set up to ultrasonically disperse the particles for 15-20 minutes in a water bath at 300W, 40kHz, and 30℃.

8. The processing method of antibacterial toilet paper as described in claim 5, characterized in that, In step S3, the mixed slurry and composite antibacterial agent are placed in a mixer with a speed of 50~100 rpm and stirred continuously for 5 minutes. In step S3, the modified slurry is placed in a sealed reaction vessel at 50~60℃ and allowed to stand for 30~40 minutes.

9. The processing method of antibacterial toilet paper as described in claim 5, characterized in that, In S4, the machine speed for the long-wire papermaking process is set at 80~100m / min, the dewatering pressure at the wire section is 0.15~0.17MPa, and the press line pressure is 80~90kN / m. The basis weight of the finished paper in S4 is controlled at 18~20g / L. S5 sets the drying oven temperature to 60~70℃ and continues drying for 2 hours. S5 also sets the pressure of the microcalendered paper to 0.3~0.5MPa and the roller temperature to 80℃.

10. The processing method of antibacterial toilet paper as described in claim 5, characterized in that, The spraying dosage of chitosan solution in S6 is 3~5g / The solution mass fraction is 0.3~0.5%, the temperature of the S6 vacuum drying oven is set to 50~60℃ and dried for 10 minutes, the silicone oil concentration of the paper passing through in S7 is 1~2%, and the drying temperature of the blower dryer in S7 is 40~45℃.

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