Antibacterial sanitary towel surface layer material and sanitary towel

Abstract

The invention discloses an antibacterial sanitary towel surface layer material and a sanitary towel, and relates to the technical field of daily necessities. When the antibacterial sanitary towel surface layer material is prepared, bamboo pulp fibers and a salicylaldehyde Schiff base calcium complex react to prepare modified bamboo pulp fibers; the preparation method comprises the following steps: enabling 3-imidazole-1-propionic acid and 1-chlorohexane to react to prepare propionyl imidazolium salt; the preparation method comprises the following steps: carrying out reaction on China hemp fibers and propionyl imidazolium salt to prepare modified China hemp fibers; the preparation method comprises the following steps: polymerizing vinyl perfluoro caprylate and 5-allylimidazolidine-2, 4-diketone, and chloridizing with sodium hypochlorite to obtain an antibacterial water-repellent finishing agent; the modified bamboo pulp fibers and the modified China hemp fibers are subjected to opening, carding, lapping and overlapping respectively and then subjected to spunlace reinforcement, a composite surface layer is prepared, the composite surface layer is coated with an antibacterial water-repellent finishing agent and dried, and the antibacterial sanitary towel surface layer material is prepared. The antibacterial sanitary towel surface layer material prepared by the invention has excellent antibacterial property and anti-back-permeation property.

Description

Technical Field

[0001] The invention relates to the technical field of daily necessities, in particular to an antibacterial sanitary napkin surface material and a sanitary napkin. Background Art

[0002] With economic development and the improvement of women's health awareness, the market consumption of women's sanitary products has been increasing. Among women's sanitary products, sanitary napkins occupy the first place in the market with an absolute advantage. Under the general environment of consumption upgrading, sanitary napkin products are also developing towards differentiation, high-end and green. The natural, healthy and environmentally friendly characteristics of spunlace non-woven materials make them have great development potential in the application of sanitary napkin surface layers. The main problems of spunlace non-woven materials used for sanitary napkin surface layers in current research are difficult degradation and high re-seepage. Based on the above problems, the present invention replaces traditional chemical fibers with hemp fibers and bamboo pulp fibers, and improves the degradation and re-seepage properties of spunlace non-woven materials by modifying the raw materials and post-processing processes, and further improves the antibacterial properties, thereby greatly improving the health, comfort and environmental protection performance of sanitary napkin products. Summary of the invention

[0003] The purpose of the present invention is to provide an antibacterial sanitary napkin surface material and a sanitary napkin to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] An antibacterial sanitary napkin surface material, characterized in that the antibacterial sanitary napkin surface material is prepared by reacting bamboo pulp fiber and salicylaldehyde Schiff base calcium complex to obtain modified bamboo pulp fiber; reacting hemp fiber and propionic acid imidazole salt to obtain modified hemp fiber; respectively opening, combing and laying the modified bamboo pulp fiber and the modified hemp fiber, superimposing and reinforcing by hydroentanglement to obtain a composite surface layer, coating the composite surface layer with an antibacterial water-repellent finishing agent, and drying to obtain the antibacterial sanitary napkin surface material;

[0006] The salicylaldehyde Schiff base calcium complex is prepared by reacting a salicylaldehyde Schiff base ligand and calcium chloride;

[0007] The salicylaldehyde Schiff base ligand is prepared by reacting 3-(3,4-diaminopropyl) propionic acid and salicylaldehyde;

[0008] The propionic imidazole salt is prepared by reacting 3-imidazole-1-propionic acid and 1-chlorohexane;

[0009] The antibacterial water-repellent finishing agent is prepared by polymerizing vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione and then chlorinating with sodium hypochlorite.

[0010] As an optimization, the method for preparing the antibacterial sanitary napkin surface material comprises the following preparation steps:

[0011] (1) 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde are added in a molar ratio of 1:2 to methanol (10 to 12 times the mass of 3-(3,4-diaminopropyl)propionic acid), stirred at 50 to 60°C and 300 to 500 r / min for 3 to 4 hours, and dried at 50 to 60°C for 10 to 12 hours under vacuum conditions to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand, calcium chloride aqueous solution, and ethyl acetate are mixed uniformly in a mass ratio of 1:(1.3 to 1.5):(10 to 12), stirred at 60 to 70°C and 300 to 500 r / min for 4 to 5 hours, and dried under vacuum conditions at 50 to 60°C for 10 to 12 hours. The mixture was dried at 60-70°C for 8-10 hours under vacuum conditions to obtain a salicylaldehyde Schiff base calcium complex; bamboo pulp fiber, salicylaldehyde Schiff base calcium complex and dichloromethane were uniformly mixed in a mass ratio of 1:(0.2-0.3):(10-12), 0.02-0.03 times the mass of bamboo pulp fiber of N,N-dicycloethylcarbodiimide and 0.03-0.05 times the mass of bamboo pulp fiber of 4-dimethylaminopyridine were added, the mixture was stirred at 70-80°C and 300-500r / min for 2-3 hours, filtered, and dried at 50-60°C for 10-12 hours under vacuum conditions to obtain modified bamboo pulp fiber;

[0012] (2) adding 3-imidazole-1-propionic acid and 1-chlorohexane in a molar ratio of 1:1 to chloroform (10 to 12 times the mass of 3-imidazole-1-propionic acid), stirring at 50 to 60°C and 300 to 500 r / min for 6 to 7 hours, and drying at 50 to 60°C for 8 to 10 hours under vacuum conditions to obtain propionic acid imidazole salt; adding hemp fiber, propionic acid imidazole salt, and dichloromethane in a mass ratio of 1:(0.2 to 0.3):(10-12) mix evenly, add 0.02-0.03 times the mass of hemp fiber N,N-dicycloethylcarbodiimide, add 0.03-0.05 times the mass of hemp fiber 4-dimethylaminopyridine, stir at 70-80 ° C, 300-500 r / min for 2-3 hours, filter, and dry at 50-60 ° C for 10-12 hours under vacuum conditions to obtain modified hemp fiber;

[0013] (3) Vinyl perfluorooctanoate, 5-allylimidazolidine-2,4-dione, emulsifier, and deionized water are mixed uniformly in a mass ratio of 1: (0.6-0.8): (0.1-0.12): (20-22), stirred at 10-30°C and 300-500r / min for 20-30min, heated to 70-80°C, and added dropwise at a rate of 0.03-0.04 times the total mass of vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione within 10min. The mixture is stirred for 3-4h, cooled to room temperature, and an aqueous sodium hypochlorite solution of 7-8 times the mass of 5-allylimidazolidine-2,4-dione is added. The pH is adjusted to 6.8-7.0 with an aqueous sulfuric acid solution, ultrasonically treated for 1-2h, and dried at 50-60°C under vacuum for 8-10h to prepare an antibacterial water-repellent finishing agent.

[0014] (4) mixing an antibacterial water-repellent finishing agent and deionized water in a mass ratio of 1:(3-4) to prepare a water-repellent finishing liquid; loosening, combing, and web-laying the modified bamboo pulp fiber and the modified hemp fiber, respectively, and stacking the modified bamboo pulp fiber and the modified hemp fiber in a mass ratio of 4:6, so that the modified bamboo pulp fiber is on the lower layer and the modified hemp fiber is on the upper layer, and the density after stacking is 50-60 g / m 2 , placed in a flat screen spunlaced machine for spunlaced reinforcement to obtain a composite surface layer; the water-repellent finishing liquid is evenly coated on the modified hemp fiber layer of the composite surface layer, with a coating amount of 10-12 g / m 2 , under vacuum conditions, dried at 50-60°C for 8-10 hours to obtain the antibacterial sanitary napkin surface material.

[0015] As an optimization, the mass fraction of the calcium chloride aqueous solution in step (1) is 20% to 30%.

[0016] As an optimization, the preparation method of the initiator solution in step (3) is: ammonium persulfate and deionized water are mixed uniformly in a mass ratio of 1:(6-8) to prepare an initiator solution.

[0017] As an optimization, the mass fraction of the sodium hypochlorite aqueous solution in step (3) is 10% to 12%.

[0018] As an optimization, the mass fraction of the aqueous sulfuric acid solution in step (3) is 20% to 24%.

[0019] As an optimization, the preparation method of the emulsifier in step (3) is: cetyltrimethylammonium chloride, emulsifier AEO-4 and emulsifier AEO-9 are mixed in a mass ratio of 3:2:4.

[0020] As an optimization, the process parameters of the hydroentanglement reinforcement in step (4) are: setting the hydroentanglement pressure of the flat mesh hydroentanglement machine to 40-50 MPa, the mesh curtain speed to 4 m / min, the water needle distance to 14 mm, and the water spray hole diameter to 0.2 mm.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] When preparing the antibacterial sanitary napkin surface layer material, the present invention comprises the following steps: 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde are reacted to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand and calcium chloride are reacted to obtain salicylaldehyde Schiff base calcium complex; bamboo pulp fiber and salicylaldehyde Schiff base calcium complex are reacted to obtain modified bamboo pulp fiber; 3-imidazole-1-propionic acid and 1-chlorohexane are reacted to obtain propionic imidazole salt; hemp fiber and propionic imidazole salt are reacted to obtain modified hemp fiber; vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione are polymerized, and then chlorinated with sodium hypochlorite to obtain an antibacterial water-repellent finishing agent; the modified bamboo pulp fiber and the modified hemp fiber are respectively loosened, combed, and laid, and then superimposed and hydroentangled to obtain a composite surface layer, which is coated with the antibacterial water-repellent finishing agent and dried to obtain the antibacterial sanitary napkin surface layer material.

[0023] First, 3-(3,4-diaminopropyl) propionic acid and salicylaldehyde are reacted to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand and calcium chloride are reacted to obtain salicylaldehyde Schiff base calcium complex; the carboxyl group on the salicylaldehyde Schiff base calcium complex is esterified with part of the hydroxyl groups on the bamboo pulp fiber to obtain modified bamboo pulp fiber, and the calcium complex is grafted on the modified bamboo pulp fiber; the surfaces of bamboo pulp fiber and hemp fiber have grooves, which have good moisture absorption and moisture discharge properties and also make it easy for menstrual blood to re-seep, and the modified bamboo pulp fiber is grafted with the calcium complex. The calcium complex will release calcium ions after encountering menstrual blood. Calcium ions are a coagulation factor and are activated by a series of enzymatic reactions in menstrual blood, which will coagulate the menstrual blood and reduce the amount of menstrual blood back-seepage. Bamboo pulp fiber is a new type of environmentally friendly fiber, which belongs to cellulose fiber. There are many grooves distributed in the longitudinal section of bamboo pulp fiber. The groove structure can increase the internal pores of the material and cause a capillary effect, thereby improving the moisture absorption and release properties of the fiber. Bamboo pulp fiber also has the advantages of good hand feel, easy dyeing, excellent liquid absorption and permeability, environmental protection, and antibacterial.

[0024] Secondly, 3-imidazole-1-propionic acid and 1-chlorohexane are reacted to obtain propionic imidazole salt; the carboxyl group on the propionic imidazole salt is esterified with some hydroxyl groups on the hemp fiber to obtain modified hemp fiber, and the imidazole salt structure is introduced into the modified hemp fiber; the hemp fiber has cracks and holes in the longitudinal direction and is connected to the middle cavity through capillaries, which allows water vapor molecules to be quickly transferred, so the material has excellent moisture absorption and breathability, hemp has a stable molecular structure, a high degree of orientation, good moisture absorption performance, and is not prone to static electricity. In addition, hemp contains more than 60 kinds of hemp phenols, which have special functions such as broad-spectrum antibacterial, insect-proof, and moth-proof. It is a natural fiber with development potential in multiple fields. Grafting imidazole salts on hemp fibers can further enhance the antibacterial properties of the antibacterial sanitary napkin surface material.

[0025] Finally, vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione were polymerized and then chlorinated with sodium hypochlorite to obtain an antibacterial water-repellent finishing agent; a large number of fluorine atoms and imidazolidinone cyclic halamine structures were introduced into the antibacterial water-repellent finishing agent; the modified bamboo pulp fiber and the modified hemp fiber were opened, combed, and laid, and then superimposed and hydroentangled to obtain a composite surface layer, which was coated with an antibacterial water-repellent finishing agent and dried to obtain an antibacterial sanitary napkin surface material; in the presence of water molecules, the N-Cl bond in the imidazolidinone cyclic halamine structure was slowly decomposed. It releases hypohalous acid or hypohalite radicals with strong oxidizing properties, directly attacking some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby achieving a bactericidal effect and further improving the antibacterial properties of the antibacterial sanitary napkin surface material; the surface of bamboo pulp fiber and hemp fiber have grooves, which have good moisture absorption and moisture discharge properties while also making it easy for menstrual blood to seep back; the hemp fiber side of the composite surface layer is treated with water repellent to close some hydrophilic groups, and under the action of differential capillary effect, the antibacterial sanitary napkin surface material is given unidirectional liquid guiding properties, thereby reducing the amount of menstrual blood seepage. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0027] Embodiment 1:

[0028] An antibacterial sanitary napkin surface material, the preparation method of the antibacterial sanitary napkin surface material comprises the following preparation steps:

[0029] (1) 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde were added in a molar ratio of 1:2 to methanol (10 times the mass of 3-(3,4-diaminopropyl)propionic acid), stirred at 50°C and 300 r / min for 4 h, and dried at 50°C for 12 h under vacuum conditions to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand, 20% calcium chloride aqueous solution, and ethyl acetate were mixed uniformly in a mass ratio of 1:1.3:10, stirred at 60°C and 300 r / min for 12 h, and then dried at 50°C for 12 h. The mixture was stirred for 5 hours, dried at 60°C for 10 hours under vacuum conditions to obtain salicylaldehyde Schiff base calcium complex; bamboo pulp fiber, salicylaldehyde Schiff base calcium complex and dichloromethane were uniformly mixed at a mass ratio of 1:0.2:10, 0.02 times the mass of bamboo pulp fiber of N, N-dicycloethylcarbodiimide and 0.03 times the mass of bamboo pulp fiber of 4-dimethylaminopyridine were added, stirred at 70°C and 300r / min for 3 hours, filtered, and dried at 50°C for 12 hours under vacuum conditions to obtain modified bamboo pulp fiber;

[0030] (2) 3-imidazole-1-propionic acid and 1-chlorohexane were added to chloroform (10 times the mass of 3-imidazole-1-propionic acid) in a molar ratio of 1:1, stirred at 50°C and 300 r / min for 7 hours, and dried at 50°C for 10 hours under vacuum conditions to obtain propionic acid imidazole salt; hemp fiber, propionic acid imidazole salt, and dichloromethane were mixed uniformly in a mass ratio of 1:0.2:10, 0.02 times the mass of hemp fiber N,N-dicycloethylcarbodiimide and 0.03 times the mass of hemp fiber 4-dimethylaminopyridine were added, stirred at 70°C and 300 r / min for 3 hours, filtered, and dried at 50°C for 12 hours under vacuum conditions to obtain modified hemp fiber;

[0031] (3) Ammonium persulfate and deionized water are mixed at a mass ratio of 1:6 to prepare an initiator solution; vinyl perfluorooctanoate, 5-allylimidazolidine-2,4-dione, an emulsifier, and deionized water are mixed at a mass ratio of 1:0.6:0.1:20, stirred at 10°C and 300r / min for 30min, heated to 70°C, and the initiator solution of 0.03 times the total mass of vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione is added dropwise at a uniform rate within 10min, and the stirring reaction is continued for 4h, cooled to room temperature, and a 10% sodium hypochlorite aqueous solution with a mass fraction of 7 times the mass of 5-allylimidazolidine-2,4-dione is added, and the pH is adjusted to 6.8 with a mass fraction of 20 sulfuric acid aqueous solution, ultrasonically treated for 1h, and dried at 50°C for 10h under vacuum conditions to prepare an antibacterial water-repellent finishing agent;

[0032] (4) The antibacterial water-repellent finishing agent and deionized water are mixed evenly in a mass ratio of 1:3 to prepare a water-repellent finishing liquid; the modified bamboo pulp fiber and the modified hemp fiber are respectively loosened, combed, and laid, and the modified bamboo pulp fiber and the modified hemp fiber are stacked in a mass ratio of 4:6, so that the modified bamboo pulp fiber is on the lower layer and the modified hemp fiber is on the upper layer, and the density after stacking is 50g / m 2 , placed in a flat-net spunlaced machine for spunlaced reinforcement, the spunlaced pressure of the flat-net spunlaced machine was set to 40MPa, the screen speed was 4m / min, the water needle distance was 14mm, the water spray hole diameter was 0.2mm, and a composite surface layer was obtained; the water-repellent finishing liquid was evenly coated on the modified hemp fiber layer of the composite surface layer, and the coating amount was 10g / m 2 , dried at 50°C for 10 h under vacuum conditions to obtain the antibacterial sanitary napkin surface material.

[0033] Embodiment 2:

[0034] An antibacterial sanitary napkin surface material, the preparation method of the antibacterial sanitary napkin surface material comprises the following preparation steps:

[0035] (1) 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde were added in a molar ratio of 1:2 to methanol (11 times the mass of 3-(3,4-diaminopropyl)propionic acid), stirred at 55°C and 400 r / min for 3.5 h, and dried at 55°C for 11 h under vacuum conditions to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand, 25% calcium chloride aqueous solution, and ethyl acetate were mixed uniformly in a mass ratio of 1:1.4:11, stirred at 65°C and 400 r / min for 4 .5h, dried at 65℃ for 9h under vacuum conditions to obtain salicylaldehyde Schiff base calcium complex; bamboo pulp fiber, salicylaldehyde Schiff base calcium complex and dichloromethane were mixed evenly at a mass ratio of 1:0.25:11, 0.025 times the mass of bamboo pulp fiber N,N-dicycloethylcarbodiimide and 0.04 times the mass of bamboo pulp fiber 4-dimethylaminopyridine were added, stirred at 75℃ and 400r / min for 2.5h, filtered, and dried at 55℃ for 11h under vacuum conditions to obtain modified bamboo pulp fiber;

[0036] (2) 3-imidazole-1-propionic acid and 1-chlorohexane were added to chloroform (11 times the mass of 3-imidazole-1-propionic acid) in a molar ratio of 1:1, stirred at 55°C and 400 r / min for 6.5 hours, and dried at 55°C for 9 hours under vacuum conditions to obtain propionic acid imidazole salt; hemp fiber, propionic acid imidazole salt, and dichloromethane were mixed evenly in a mass ratio of 1:0.25:11, N,N-dicycloethylcarbodiimide (0.025 times the mass of hemp fiber) and 4-dimethylaminopyridine (0.04 times the mass of hemp fiber) were added, stirred at 75°C and 400 r / min for 2.5 hours, filtered, and dried at 55°C for 11 hours under vacuum conditions to obtain modified hemp fiber;

[0037] (3) ammonium persulfate and deionized water are mixed at a mass ratio of 1:7 to prepare an initiator solution; vinyl perfluorooctanoate, 5-allylimidazolidine-2,4-dione, an emulsifier, and deionized water are mixed at a mass ratio of 1:0.7:0.11:21, stirred at 20°C and 400r / min for 25min, heated to 75°C, and the initiator solution of 0.035 times the total mass of vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione is added dropwise at a uniform rate within 10min, and the stirring reaction is continued for 3.5h, cooled to room temperature, and 7.5 times the mass of 5-allylimidazolidine-2,4-dione is added. The mass fraction of 11% sodium hypochlorite aqueous solution is adjusted to pH 6.9 with a mass fraction of 22% sulfuric acid aqueous solution, ultrasonically treated for 1.5h, and dried at 55°C under vacuum conditions for 9h to prepare an antibacterial water-repellent finishing agent;

[0038] (4) The antibacterial water-repellent finishing agent and deionized water are mixed evenly at a mass ratio of 1:3.5 to prepare a water-repellent finishing liquid; the modified bamboo pulp fiber and the modified hemp fiber are opened, combed, and laid respectively, and the modified bamboo pulp fiber and the modified hemp fiber are stacked at a mass ratio of 4:6, so that the modified bamboo pulp fiber is on the lower layer and the modified hemp fiber is on the upper layer, and the density after stacking is 55g / m 2 , placed in a flat-net spunlaced machine for spunlaced reinforcement, the spunlaced pressure of the flat-net spunlaced machine was set to 45MPa, the screen speed was 4m / min, the water needle distance was 14mm, the water spray hole diameter was 0.2mm, and a composite surface layer was obtained; the water-repellent finishing liquid was evenly coated on the modified hemp fiber layer of the composite surface layer, and the coating amount was 11g / m 2 , dried at 55°C under vacuum conditions for 9 hours to obtain the antibacterial sanitary napkin surface material.

[0039] Embodiment 3:

[0040] An antibacterial sanitary napkin surface material, the preparation method of the antibacterial sanitary napkin surface material comprises the following preparation steps:

[0041] (1) 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde were added in a molar ratio of 1:2 to methanol (12 times the mass of 3-(3,4-diaminopropyl)propionic acid), stirred at 60°C and 500 r / min for 3 h, and dried at 60°C for 10 h under vacuum conditions to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand, 30% calcium chloride aqueous solution, and ethyl acetate were mixed uniformly in a mass ratio of 1:1.5:12, stirred at 70°C and 500 r / min for 3 h, and dried at 60°C for 10 h under vacuum conditions to obtain salicylaldehyde Schiff base ligand; The mixture was stirred for 4 hours, dried at 70°C for 8 hours under vacuum conditions to obtain salicylaldehyde Schiff base calcium complex; bamboo pulp fiber, salicylaldehyde Schiff base calcium complex and dichloromethane were uniformly mixed at a mass ratio of 1:0.3:12, 0.03 times the mass of bamboo pulp fiber N, N-dicycloethylcarbodiimide and 0.05 times the mass of bamboo pulp fiber 4-dimethylaminopyridine were added, stirred at 80°C and 500r / min for 2 hours, filtered, and dried at 60°C for 10 hours under vacuum conditions to obtain modified bamboo pulp fiber;

[0042] (2) 3-imidazole-1-propionic acid and 1-chlorohexane were added to chloroform (12 times the mass of 3-imidazole-1-propionic acid) in a molar ratio of 1:1, stirred at 60°C and 500 r / min for 6 hours, and dried at 60°C for 8 hours under vacuum conditions to obtain propionic acid imidazole salt; hemp fiber, propionic acid imidazole salt, and dichloromethane were mixed evenly in a mass ratio of 1:0.3:12, 0.03 times the mass of hemp fiber N,N-dicycloethylcarbodiimide and 0.05 times the mass of hemp fiber 4-dimethylaminopyridine were added, stirred at 80°C and 500 r / min for 2 hours, filtered, and dried at 60°C for 10 hours under vacuum conditions to obtain modified hemp fiber;

[0043] (3) ammonium persulfate and deionized water are mixed at a mass ratio of 1:8 to prepare an initiator solution; vinyl perfluorooctanoate, 5-allylimidazolidine-2,4-dione, an emulsifier, and deionized water are mixed at a mass ratio of 1:0.8:0.12:22, stirred at 30°C and 500r / min for 20min, heated to 80°C, and the initiator solution of 0.04 times the total mass of vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione is added dropwise at a uniform rate within 10min, and the stirring reaction is continued for 3h, cooled to room temperature, and a 12% sodium hypochlorite aqueous solution of 8 times the mass of 5-allylimidazolidine-2,4-dione is added, and the pH is adjusted to 7.0 with a 24% sulfuric acid aqueous solution, ultrasonically treated for 2h, and dried at 60°C under vacuum for 8h to prepare an antibacterial water-repellent finishing agent;

[0044] (4) The antibacterial water-repellent finishing agent and deionized water are mixed evenly in a mass ratio of 1:4 to prepare a water-repellent finishing liquid; the modified bamboo pulp fiber and the modified hemp fiber are respectively loosened, combed, and laid, and the modified bamboo pulp fiber and the modified hemp fiber are stacked in a mass ratio of 4:6, so that the modified bamboo pulp fiber is on the lower layer and the modified hemp fiber is on the upper layer, and the density after stacking is 60g / m 2 , placed in a flat-net spunlaced machine for spunlaced reinforcement, the spunlaced pressure of the flat-net spunlaced machine was set to 50MPa, the screen speed was 4m / min, the water needle distance was 14mm, the water spray hole diameter was 0.2mm, and a composite surface layer was obtained; the water-repellent finishing liquid was evenly coated on the modified hemp fiber layer of the composite surface layer, and the coating amount was 12g / m 2 , dried at 60°C for 8h under vacuum conditions to obtain the antibacterial sanitary napkin surface material.

[0045] Comparative Example 1:

[0046] The difference between the preparation method of the antibacterial sanitary napkin surface material of Comparative Example 1 and Example 2 is that step (1) is not performed, and step (4) is modified as follows: the antibacterial water-repellent finishing agent and deionized water are mixed evenly in a mass ratio of 1:3.5 to prepare a water-repellent finishing liquid; the bamboo pulp fiber and the modified hemp fiber are opened, combed, and laid, and the bamboo pulp fiber and the modified hemp fiber are overlapped in a mass ratio of 4:6, so that the bamboo pulp fiber is in the lower layer and the modified hemp fiber is in the upper layer, and the density after overlapping is 55g / m 2 , placed in a flat-net spunlaced machine for spunlaced reinforcement, the spunlaced pressure of the flat-net spunlaced machine was set to 45MPa, the screen speed was 4m / min, the water needle distance was 14mm, the water spray hole diameter was 0.2mm, and a composite surface layer was obtained; the water-repellent finishing liquid was evenly coated on the modified hemp fiber layer of the composite surface layer, and the coating amount was 11g / m 2 , and dried at 55° C. for 9 hours under vacuum conditions to obtain an antibacterial sanitary napkin surface material. The remaining steps are the same as in Example 2.

[0047] Comparative Example 2:

[0048] The difference between the preparation method of the antibacterial sanitary napkin surface material of Comparative Example 2 and Example 2 is that step (2) is not performed, and step (4) is modified as follows: the antibacterial water-repellent finishing agent and deionized water are mixed evenly at a mass ratio of 1:3.5 to prepare a water-repellent finishing liquid; the modified bamboo pulp fiber and the hemp fiber are opened, combed, and laid, and the modified bamboo pulp fiber and the hemp fiber are overlapped at a mass ratio of 4:6, so that the modified bamboo pulp fiber is in the lower layer and the hemp fiber is in the upper layer, and the density after overlapping is 55g / m 2, placed in a flat-net spunlaced machine for spunlaced reinforcement, the spunlaced pressure of the flat-net spunlaced machine was set to 45MPa, the screen speed was 4m / min, the water needle distance was 14mm, the water spray hole diameter was 0.2mm, and a composite surface layer was obtained; the water-repellent finishing liquid was evenly coated on the hemp fiber layer of the composite surface layer, and the coating amount was 11g / m 2 , and dried at 55° C. for 9 hours under vacuum conditions to obtain an antibacterial sanitary napkin surface material. The remaining steps are the same as in Example 2.

[0049] Comparative Example 3:

[0050] The difference between the preparation method of the antibacterial sanitary napkin surface material of Comparative Example 3 and Example 2 is that step (3) is not performed, and step (4) is modified as follows: the modified bamboo pulp fiber and the modified hemp fiber are respectively loosened, combed, and laid, and the modified bamboo pulp fiber and the modified hemp fiber are stacked at a mass ratio of 4:6, so that the modified bamboo pulp fiber is in the lower layer and the modified hemp fiber is in the upper layer, and the density after stacking is 55g / m 2 , placed in a flat-net spunlacing machine for spunlacing reinforcement, the spunlacing pressure of the flat-net spunlacing machine was set to 45 MPa, the screen delivery speed was 4 m / min, the water needle distance was 14 mm, and the water spray hole diameter was 0.2 mm, to obtain an antibacterial sanitary napkin surface material. The remaining steps are the same as in Example 2.

[0051] Test Example 1

[0052] Anti-rewetting performance test

[0053] Test method: Refer to Appendix B of GB / T3013 to test the back permeation of the examples and comparative examples, replace the test solution used in the experiment with anticoagulated pig blood, cut the examples and comparative examples into samples with a size of 100 mm × 100 mm, test each sample 5 times, and take the average value. The results are shown in Table 1.

[0054] Table 1

[0055] Re-seepage amount (g) Re-seepage amount (g) Example 1 0.6237 Comparative Example 1 1.2874 Example 2 0.5893 Comparative Example 2 0.6438 Example 3 0.6174 Comparative Example 3 1.3383

[0056] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the antibacterial sanitary napkin surface layer material prepared by the present invention has good anti-reseepage performance.

[0057] By comparison, the re-infiltration amount of Examples 1 to 3 is less than that of Comparative Example 1, indicating that 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde are reacted to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand and calcium chloride are reacted to obtain salicylaldehyde Schiff base calcium complex; the carboxyl group on the salicylaldehyde Schiff base calcium complex is esterified with part of the hydroxyl groups on the bamboo pulp fiber to obtain modified bamboo pulp fiber, and the calcium complex is grafted on the modified bamboo pulp fiber; the surfaces of the bamboo pulp fiber and the hemp fiber have grooves, which have good moisture absorption and moisture discharge properties, and also make it easy for menstrual blood to re-infiltrate. The calcium complex grafted on the modified bamboo pulp fiber will release calcium ions after encountering menstrual blood. Calcium ions are a coagulation factor, which is activated under a series of enzymatic reactions in the menstrual blood, coagulates the menstrual blood, and reduces the re-infiltration amount of menstrual blood.

[0058] By comparison, the re-seepage amount of Examples 1 to 3 is less than that of Comparative Example 3, indicating that vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione are polymerized and then chlorinated with sodium hypochlorite to obtain an antibacterial water-repellent finishing agent; the modified bamboo pulp fiber and the modified hemp fiber are respectively loosened, combed, and laid, and then superimposed and hydroentangled to obtain a composite surface layer, which is coated with an antibacterial water-repellent finishing agent and dried to obtain an antibacterial sanitary napkin surface material; the surfaces of the bamboo pulp fiber and the hemp fiber have grooves, which have good moisture absorption and discharge properties while also making it easy for menstrual blood to re-seep; the hemp fiber side of the composite surface layer is treated with water-repellent treatment to close some hydrophilic groups, and the antibacterial sanitary napkin surface material is given a unidirectional liquid-conducting property under the action of the differential capillary effect, thereby reducing the re-seepage amount of menstrual blood.

[0059] Test Example 2

[0060] Antimicrobial performance testing

[0061] Test method: The antibacterial properties of the examples and comparative examples were tested with reference to standard GB / T20944.2. Escherichia coli (ATCC11229) was selected as the test bacteria, and the antibacterial rate was calculated by comparing the number of colonies of Escherichia coli cultured in agar medium for 16 hours, thereby analyzing the antibacterial properties of the examples and comparative examples. The results are shown in Table 2.

[0062] Table 2

[0063] Antibacterial rate (%) Antibacterial rate (%) Example 1 99.87 Comparative Example 1 99.85 Example 2 99.91 Comparative Example 2 92.37 Example 3 99.89 Comparative Example 3 90.48

[0064] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the antibacterial sanitary napkin surface material prepared by the present invention has good antibacterial properties.

[0065] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that 3-imidazole-1-propionic acid and 1-chlorohexane are reacted to obtain propionic imidazole salts; the carboxyl group on the propionic imidazole salts is esterified with part of the hydroxyl groups on the hemp fiber to obtain modified hemp fiber, and the imidazole salt structure is introduced into the modified hemp fiber; the hemp fiber has cracks and holes in the longitudinal direction and is connected to the middle cavity through capillaries, which allows water vapor molecules to be quickly transferred, so the material has excellent moisture absorption and air permeability, the hemp molecular structure is stable, the orientation degree is high, the moisture absorption performance is good, and it is not easy to generate static electricity. In addition, hemp contains more than 60 kinds of hemp phenol substances, which have special functions such as broad-spectrum antibacterial, insect-proof, and moth-proof. It is a natural fiber with development potential in multiple fields. Grafting imidazole salts on hemp fibers can further enhance the antibacterial properties of the antibacterial sanitary napkin surface material.

[0066] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 3, indicating that vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione are polymerized and then chlorinated with sodium hypochlorite to obtain an antibacterial water-repellent finishing agent; an imidazolidinone cyclic halamine structure is introduced into the antibacterial water-repellent finishing agent; the modified bamboo pulp fiber and the modified hemp fiber are respectively opened, combed, and laid, and then hydroentangled to obtain a composite surface layer after superposition, which is coated with an antibacterial water-repellent finishing agent and dried to obtain an antibacterial sanitary napkin surface material; under the action of water molecules, the N-Cl bond in the imidazolidinone cyclic halamine structure slowly decomposes to release hypohalous acid or hypohalite radicals with strong oxidizing properties, which directly attack some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby achieving a bactericidal effect and further improving the antibacterial properties of the antibacterial sanitary napkin surface material.

[0067] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An antibacterial sanitary napkin surface material, characterized in that: The antibacterial sanitary napkin surface material is prepared by reacting bamboo pulp fiber and salicylaldehyde Schiff base calcium complex to obtain modified bamboo pulp fiber; reacting hemp fiber and propionic acid imidazole salt to obtain modified hemp fiber; respectively opening, combing and laying the modified bamboo pulp fiber and the modified hemp fiber, superimposing and reinforcing by water spunlace to obtain a composite surface layer, coating the composite surface layer with an antibacterial water-repellent finishing agent, and drying to obtain the antibacterial sanitary napkin surface material; The salicylaldehyde Schiff base calcium complex is prepared by reacting a salicylaldehyde Schiff base ligand and calcium chloride; The salicylaldehyde Schiff base ligand is prepared by reacting 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde; The propionic imidazole salt is prepared by reacting 3-imidazole-1-propionic acid and 1-chlorohexane; The antibacterial water-repellent finishing agent is prepared by polymerizing vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione and then chlorinating with sodium hypochlorite.

2. The antibacterial sanitary napkin surface material according to claim 1, characterized in that: The preparation method of the antibacterial sanitary napkin surface layer material comprises the following preparation steps: (1) 3-(3,4-diaminopropyl)propionic acid and salicylaldehyde are added in a molar ratio of 1:2 to methanol (10 to 12 times the mass of 3-(3,4-diaminopropyl)propionic acid), stirred at 50 to 60°C and 300 to 500 r / min for 3 to 4 hours, and dried at 50 to 60°C for 10 to 12 hours under vacuum conditions to obtain salicylaldehyde Schiff base ligand; salicylaldehyde Schiff base ligand, calcium chloride aqueous solution, and ethyl acetate are mixed uniformly in a mass ratio of 1:(1.3 to 1.5):(10 to 12), stirred at 60 to 70°C and 300 to 500 r / min for 4 to 5 hours, and dried under vacuum conditions at 50 to 60°C for 10 to 12 hours. The mixture was dried at 60-70°C for 8-10 hours under vacuum conditions to obtain a salicylaldehyde Schiff base calcium complex; bamboo pulp fiber, salicylaldehyde Schiff base calcium complex and dichloromethane were uniformly mixed in a mass ratio of 1:(0.2-0.3):(10-12), 0.02-0.03 times the mass of bamboo pulp fiber of N,N-dicycloethylcarbodiimide and 0.03-0.05 times the mass of bamboo pulp fiber of 4-dimethylaminopyridine were added, the mixture was stirred at 70-80°C and 300-500r / min for 2-3 hours, filtered, and dried at 50-60°C for 10-12 hours under vacuum conditions to obtain modified bamboo pulp fiber; (2) adding 3-imidazole-1-propionic acid and 1-chlorohexane in a molar ratio of 1:1 to chloroform (10 to 12 times the mass of 3-imidazole-1-propionic acid), stirring at 50 to 60°C and 300 to 500 r / min for 6 to 7 hours, and drying at 50 to 60°C for 8 to 10 hours under vacuum conditions to obtain propionic acid imidazole salt; adding hemp fiber, propionic acid imidazole salt, and dichloromethane in a mass ratio of 1:(0.2 to 0.3):(10-12) mix evenly, add 0.02-0.03 times the mass of hemp fiber N,N-dicycloethylcarbodiimide, add 0.03-0.05 times the mass of hemp fiber 4-dimethylaminopyridine, stir at 70-80 ° C, 300-500 r / min for 2-3 hours, filter, and dry at 50-60 ° C for 10-12 hours under vacuum conditions to obtain modified hemp fiber; (3) Vinyl perfluorooctanoate, 5-allylimidazolidine-2,4-dione, emulsifier, and deionized water are mixed uniformly in a mass ratio of 1: (0.6-0.8): (0.1-0.12): (20-22), stirred at 10-30°C and 300-500r / min for 20-30min, heated to 70-80°C, and added dropwise at a rate of 0.03-0.04 times the total mass of vinyl perfluorooctanoate and 5-allylimidazolidine-2,4-dione within 10min. The mixture is stirred for 3-4h, cooled to room temperature, and an aqueous sodium hypochlorite solution of 7-8 times the mass of 5-allylimidazolidine-2,4-dione is added. The pH is adjusted to 6.8-7.0 with an aqueous sulfuric acid solution, ultrasonically treated for 1-2h, and dried at 50-60°C under vacuum for 8-10h to prepare an antibacterial water-repellent finishing agent. (4) mixing an antibacterial water-repellent finishing agent and deionized water in a mass ratio of 1:(3-4) to prepare a water-repellent finishing liquid; loosening, combing, and laying the modified bamboo pulp fiber and the modified hemp fiber, respectively, and stacking the modified bamboo pulp fiber and the modified hemp fiber in a mass ratio of 4:6, so that the modified bamboo pulp fiber is on the lower layer and the modified hemp fiber is on the upper layer, and the density after stacking is 50-60 g / m 2 , placed in a flat screen spunlaced machine for spunlaced reinforcement to obtain a composite surface layer; the water-repellent finishing liquid is evenly coated on the modified hemp fiber layer of the composite surface layer, with a coating amount of 10-12 g / m 2 , under vacuum conditions, dried at 50-60°C for 8-10 hours to obtain the antibacterial sanitary napkin surface material.

3. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The mass fraction of the calcium chloride aqueous solution in step (1) is 20% to 30%.

4. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The preparation method of the initiator solution in step (3) is as follows: ammonium persulfate and deionized water are uniformly mixed in a mass ratio of 1:(6-8) to prepare an initiator solution.

5. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The mass fraction of the sodium hypochlorite aqueous solution in step (3) is 10% to 12%.

6. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The mass fraction of the sulfuric acid aqueous solution in step (3) is 20% to 24%.

7. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The preparation method of the emulsifier in step (3) is as follows: hexadecyltrimethylammonium chloride, emulsifier AEO-4 and emulsifier AEO-9 are mixed in a mass ratio of 3:2:

4.

8. The antibacterial sanitary napkin surface material according to claim 2, characterized in that: The process parameters of the hydroentanglement reinforcement in step (4) are as follows: the hydroentanglement pressure of the flat mesh hydroentanglement machine is set to 40-50 MPa, the mesh curtain speed is set to 4 m / min, the water needle distance is set to 14 mm, and the water spray hole diameter is set to 0.2 mm.

9. A sanitary napkin, characterized in that: The surface layer of the sanitary napkin is the antibacterial sanitary napkin surface layer material according to any one of claims 1 to 8.