Wood pulp-based degradable spunlace wiping material and preparation method thereof

Abstract

The invention relates to the technical field of spunlace wiping materials, in particular to a wood pulp-based degradable spunlace wiping material and a preparation method thereof. Comprising the following steps: step 1: (1) opening and mixing pretreated wood pulp fibers and carboxylated cellulose, carding and lapping, and carrying out primary spunlace reinforcement in sequence to form a degradable base layer; (2) opening and mixing cellulosic fibers and polylactic acid fibers, carding and lapping the cellulosic fibers and polylactic acid fibers on the surface of the degradable base layer, and performing secondary spunlace reinforcement to obtain a degradable spunlace base material; 2, the degradable spunlace base material is placed in the MOF antibacterial color fixing slurry for two times of dipping and two times of rolling, and drying is conducted; further spraying modified dye liquid on the surface, drying, rolling and slitting; therefore, the spunlace wiping material is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-jet wiping materials, in particular to a wood pulp-based degradable water-jet wiping material and a preparation method thereof. BACKGROUND

[0002] As an indispensable product in people's life, water-jet wiping materials can realize convenient and efficient cleaning. However, traditional wiping materials are mainly based on petroleum-based fibers, which have problems such as non-degradability, high resource consumption, and micro-plastic pollution. With the continuous improvement of global environmental protection standards, consumers pay more and more attention to green products, and degradable wiping materials have become a popular research direction in the industry at this stage.

[0003] At present, the research and development of degradable wiping materials in the international market are mainly led by European and American enterprises. For example, Aishenya and Kimberly-Clark have launched wood pulp-based water-jet materials, but most of the products are mainly based on original pulp color, lack of color design, and are difficult to meet the aesthetic needs. And even if a few products try simple coloring, obvious discoloration occurs after rubbing and water, and there are generally problems such as insufficient color stability and poor color fastness. At the same time, in the fields of medical care, maternity and infant care, the antibacterial performance requirements are relatively high, and the antibacterial performance of ordinary degradable wiping materials cannot meet the use standards. And even if a few of them meet the antibacterial standards, the antibacterial agent is not combined firmly with the substrate, and is easy to lose with the friction and humid environment in the use process, resulting in a decrease in antibacterial performance. This limits the application field of degradable wiping materials.

[0004] Therefore, how to realize the dual improvement of color fastness and antibacterial property on the basis of ensuring degradability has become the key to breaking through the application limitations of existing degradable wiping materials.

[0005] In summary, it is of great significance to solve the above problems and prepare a wood pulp-based degradable water-jet wiping material. SUMMARY

[0006] The purpose of the present application is to provide a wood pulp-based degradable water-jet wiping material and a preparation method thereof to solve the problems raised in the background.

[0007] In order to solve the above technical problems, the present application provides the following technical scheme: A preparation method of a wood pulp-based degradable water-jet wiping material, comprising the following steps: Step 1: (1) mixing, carding and laying the pretreated wood pulp fibers and carboxylated cellulose in sequence, and performing primary water-jet reinforcement to form a degradable base layer; (2) mixing the cellulose fibers and polylactic acid fibers, carding and laying them on the surface of the degradable base layer, and performing secondary water-jet reinforcement to obtain a degradable water-jet base material; Step 2: The degradable water-jet base material is placed in the MOF antibacterial fixing paste for two-dip two-nip, dried, and further sprayed with modified dye solution, dried, wound and cut to obtain the water-jet wiping material.

[0008] In a further aspect, the pretreated wood pulp fibers are obtained by plasma treatment; the plasma treatment process parameters are: vacuum degree of 750-850 Pa; atmosphere of pure oxygen; pure oxygen flow rate of 1.2-1.5 L / min; treatment time of 120-130 s; power of 70-80 W. The surface hydroxyl content of the wood pulp fibers treated by plasma is improved, and the wood pulp fibers are tightly combined with the carboxylated cellulose by enhancing the polar effect of hydrogen bond and van der Waals force, so as to optimize the water-jet entanglement effect.

[0009] More preferably, in the raw material of the degradable water-jet base material, the following components are included: 60-80 parts by mass of pretreated wood pulp fibers, 15-20 parts by mass of carboxylated cellulose, 12-15 parts by mass of cellulose fibers, and 10-15 parts by mass of polylactic acid fibers.

[0010] More preferably, the preparation process of the MOF antibacterial fixing paste is as follows: S1-1: At 0-5℃, nitrogen is introduced, N-hydroxymethyl acrylamide, methyl acrylate and methanol are added to divinyltriamine, and the mixture is reacted at room temperature for 3-5 h. After removing methanol, the mixture is reacted at 90-120℃ for 8-12 h. Then, cinnamyl aldehyde and tetrahydrofuran are added, 0.5wt%-0.6wt% acetic acid is used to adjust the pH to 5.5-6.0, and the mixture is reacted at 80-90℃ for 4-6 h to obtain a Schiff base-based hyperbranched polymer; S1-2: Zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are mixed, washed and dried, then added to DMF (N,N-dimethylformamide), acetic acid and deionized water are added, and the mixture is stirred at 110-130℃ for 20-40 min, then washed and dried to obtain UiO-66-I4; S1-3: UiO-66-I4, Schiff base-based hyperbranched polymer and deionized water are dispersed, and citric acid is added to adjust the pH to 5.0-5.5 to obtain the MOF antibacterial fixing paste.

[0011] More preferably, in the raw material of the MOF antibacterial fixing paste, the following components are included: 3-5 parts by mass of UiO-66-I4, 8-12 parts by mass of Schiff base-based hyperbranched polymer, and 120-150 parts by mass of deionized water; and the concentration of citric acid is 0.5wt%-1.5wt%.

[0012] More preferably, the molar ratio of zinc chloride to 2,3,5,6-tetraiodoterephthalic acid in the UiO-66-I4 is 1:0.5~1; the raw material of the Schiff base-based hyperbranched polymer comprises the following components: 1~2 parts of N-hydroxymethyl acrylamide, 2~3.5 parts of methyl acrylate, 2~3 parts of divinyltriamine, 2~2.5 parts of cinnamaldehyde by mass fraction.

[0013] More preferably, the spraying amount of the modified dye solution is 5~10g / cm 2 ; the preparation process of the modified dye solution is as follows: S2-1: Take berberine and 2,4-dimethoxybenzylamine and add them to DMSO (dimethyl sulfoxide), stir at 110~130℃ for 6~8h, cool and wash, freeze-dry, add to methanol, add 10wt%~15wt% hydrochloric acid, stir at room temperature for 5~7h, wash the precipitate and dry to obtain amino berberine; S2-2: Take dehydrated lactic acid and ethylene glycol and add them to toluene, polycondense at 120~160℃ for 2~4h, cool and dry, add to epichlorohydrin, TBAB (tetrabutylammonium bromide), sodium hydroxide and tetrahydrofuran under nitrogen atmosphere, react at 60~65℃ for 5~8h, neutralize, remove tetrahydrofuran and dry to obtain epoxy-terminated lactic acid oligomer; add amino berberine, epoxy-terminated lactic acid oligomer and triethylamine to DMF, react at 45~55℃ for 7~9h and dry to obtain modified berberine; S2-3: Add modified berberine, penetrant and buffer to deionized water and mix to obtain a modified dye solution.

[0014] More preferably, the components of the modified dye solution are as follows in terms of mass percentage: 5~8% modified berberine, 0.4~0.6% penetrant, 0.2~0.8% buffer, and the rest is deionized water; the raw material of the amino berberine comprises the following components: 2~3 parts of berberine, 4~7 parts of 2,4-dimethoxybenzylamine and 0.5~1 part of 10wt%~15wt% hydrochloric acid by mass fraction; the raw material of the modified berberine comprises the following components: 8~12 parts of lactic acid, 1~2 parts of ethylene glycol, 3~6 parts of epichlorohydrin, 0.2~0.5 parts of TBAB, 0.2~0.5 parts of sodium hydroxide, 8~12 parts of amino berberine and 0.5~0.8 parts of triethylamine by mass fraction.

[0015] More preferably, the process parameters of the first water jet reinforcement are as follows: water jet pressure is 3.5~4.5MPa, water jet number is 1~2, water jet height is 35~40mm, and web curtain speed is 10~15m / min. The process parameters of the secondary water jet reinforcement are that the water jet pressure is 5.5-6.5 MPa, the water jet path number is 2-3, the water jet height is 40-45 mm, and the net curtain speed is 15-20 m / min.

[0016] More preferably, the two-dip-two-rolling process is that the degradable water jet base material is placed in the MOF antibacterial fixing slurry, dipped for 12-18 hours, taken out and extruded, which is the first dip-rolling; after the first dip-rolling, the material is placed in the MOF antibacterial fixing slurry again, ultrasonic treated for 30-60 minutes, taken out and extruded again, which is the second dip-rolling.

[0017] Compared with the prior art, the beneficial effects of the present application are: The present scheme uses wood pulp fibers, carboxylated cellulose and other degradable fibers as the base to realize material degradability; by using MOF antibacterial fixing slurry dipping, spraying and modifying dye liquid, the antibacterial and fixing properties of the material are synergistically improved.

[0018] The MOF antibacterial fixing slurry is composed of UiO-66-I4, Schiff base based hyperbranched polymer, citric acid and solvent. Under the action of citric acid, the surface hydroxyl group of MOF dissociates and carries a negative charge; the Schiff base based hyperbranched polymer is deprotonated to form -NH 3+ with a positive charge under the action of citric acid; the two are closely connected through electrostatic interaction.

[0019] The Schiff base based hyperbranched polymer in the MOF antibacterial fixing slurry acts as an adhesive, which is prepared by synthesizing amino hyperbranched polymer through melt polycondensation, and then condensing the terminal amino group with aldehyde group to form Schiff base groups. The hyperbranched structure and terminal Schiff base groups of the adhesive can effectively inhibit the agglomeration of MOF caused by the hydrophilic swelling of traditional chitosan adhesive through coordination bonding with UiO-66-I4 by steric hindrance; at the same time, the hydrophobicity provided by the iodine phenyl groups in tetraiodoterephthalic acid further inhibits the penetration of water molecules, ensuring the structural stability of the MOF antibacterial fixing slurry in the wet state, and realizing the synergistic improvement of antibacterial property and durability.

[0020] UiO-66-I4 in the MOF antibacterial fixing slurry acts as the core component for antibacterial and fixing enhancement, Zn²⁺ as the metal node forms a coordination bond with the tetraiodoterephthalic acid ligand to constitute the MOF framework and provide antibacterial performance; its porous structure and high specific surface area can physically adsorb modified berberine in the modified dye liquid, and the zinc ion can coordinate with the epoxy group in the modified dye liquid, further improving the fixing performance.

[0021] Among them, the modified berberine in the modified dye solution is the core component of the dye solution, and the benzisoquinoline quaternary ammonium salt structure in the molecule provides antibacterial performance. The modified berberine is formed by demethylation of the methoxy group at C9 of berberine to form amino berberine, and then grafted with an epoxy-terminated lactic acid oligomer: on the one hand, the introduction of epoxy group and ether bond enhances the binding force with the fiber, and the lactic acid oligomer is similar to the polylactic acid fiber, which further improves the structural stability and fixing performance; on the other hand, the modified berberine is hydrolyzed by esterase, which further guides the material degradation. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] It should be noted that the following parts are mass parts, and there is no special restriction on the purchase manufacturers of all raw materials involved in the present application. Exemplarily, in the following embodiments, the wood pulp fiber has a product number of L30R, which is purchased from Chengdu Kanghuijing Technology Co., Ltd.; the carboxylated cellulose fiber has a CAS number of 9004-34-6, which is purchased from Maier Technology Co., Ltd.; the cellulose fiber is purchased from Saide Li (China) Fiber Co., Ltd.; the polylactic acid fiber is purchased from Yisheng New Material (Suzhou) Co., Ltd.; N-hydroxymethyl acrylamide has a CAS number of 924-42-5; methyl acrylate has a CAS number of 96-33-3; divinyltriamine has a CAS number of 111-40-0; cinnamyl aldehyde has a CAS number of 104-55-2; zinc chloride has a CAS number of 7646-85-7; 2,3,5,6-tetraiodo-p-xylylene terephthalic acid has a CAS number of 7606-84-0; citric acid has a CAS number of 77-92-9; berberine has a CAS number of 2086-83-1; 2,4-dimethoxybenzylamine has a CAS number of 20781-20-8; lactic acid has a CAS number of 50-21-5; ethylene glycol has a CAS number of 107-21-1; epichlorohydrin has a CAS number of 106-89-8; TBAB has a CAS number of 1643-19-2; triethylamine has a CAS number of 121-44-8; fatty alcohol polyoxyethylene ether has a CAS number of 68131-39-5; DMSO has a CAS number of 67-68-5; chitosan has a relative molecular mass of 50000 and a CAS number of 9012-76-4.

[0024] In the following embodiments, the following is particularly stated: (1) The raw materials of the modified dye liquid are as follows in terms of mass percentage: 6.5% modified berberine, 0.5% penetrant, 0.5% buffer, and the rest is deionized water; wherein the spraying amount of the modified dye liquid is 8 g / cm 2 . The penetrant is a fatty alcohol polyoxyethylene ether; the buffer is a phosphate-citric acid system, and the pH is 5.5; (2) The plasma treatment process parameters are as follows: vacuum degree is 800 Pa; atmosphere is pure oxygen; pure oxygen flow rate is 1.3 L / min; treatment time is 125 s; power is 75 W; the process parameters of the first water jet reinforcement are as follows: water jet pressure is 4 MPa, water jet number is 1, water jet height is 38 mm, and web curtain speed is 13 m / min; the process parameters of the second water jet reinforcement are as follows: water jet pressure is 6 MPa, water jet number is 2, water jet height is 43 mm, and web curtain speed is 18 m / min.

[0025] Example 1: A preparation method of a wood pulp-based degradable water jet wiping material, comprising the following steps: Step 1: S1-1: At 1℃, nitrogen is introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol are added to 2.5 parts of divinyltriamine, reacted at room temperature for 4h, after removing the methanol, reacted at 105℃ for 10h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, and 0.55wt% acetic acid are added to adjust the pH to 5.8, and reacted at 85℃ for 5h to obtain a Schiff base-based hyperbranched polymer; S1-2: zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are mixed, washed, and dried by ball milling according to a molar ratio of 1:0.8, then added to DMF, acetic acid and deionized water are added, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base-based hyperbranched polymer, and 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2 to obtain a MOF antibacterial fixing slurry; Step 2: S2-1: Take 2.5 parts of berberine, 5.5 parts of 2,4-dimethoxybenzylamine into DMSO, stir at 120℃ for 7h, cool and wash, freeze-dried, then add to methanol, add 0.8 parts of 12wt% hydrochloric acid, stir at room temperature for 6h, wash the precipitate and dry to obtain amino berberine; S2-2: Take 10 parts of dehydrated lactic acid, 1.5 parts of ethylene glycol into toluene, polycondense at 140℃ for 3h, cool and dry, then add to 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, tetrahydrofuran, react at 62℃ for 6.5h, neutralize, remove tetrahydrofuran and dry to obtain epoxy-terminated lactic acid oligomer; add 10 parts of amino berberine, epoxy-terminated lactic acid oligomer, 0.6 parts of triethylamine into DMF, react at 50℃ for 8h, dry to obtain modified berberine; S2-3: add modified berberine, penetrant, buffer to deionized water, mix to obtain modified dye solution; Step 3: S3-1: take wood pulp fibers for plasma treatment to obtain pretreated wood pulp fibers; S3-2: take 60 parts of pretreated wood pulp fibers, 15 parts of carboxylated cellulose, sequentially open and mix, card and lay on the surface of the degradable base layer, once water jet reinforcement to form a degradable water jet base material; S3-3: take 12 parts of cellulose fibers, 10 parts of polylactic acid fibers, open and mix, card and lay on the surface of the degradable base layer, twice water jet reinforcement to obtain a degradable water jet base material; Step 4: place the degradable water jet base material in the MOF antibacterial fixing slurry, immerse for 16h, take out and extrude for the first dip; after the first dip, place it again in the MOF antibacterial fixing slurry, ultrasonic treatment for 45min, take out and extrude for the second time, dry; further spray the modified dye solution on the surface, dry, roll, cut to obtain a water jet wiping material.

[0026] Example 2: a preparation method of a wood pulp-based degradable water jet wiping material, comprising the following steps: Step 1: S1-1: at 1℃, nitrogen was introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, methanol were added into 2.5 parts of divinyltriamine, reacted at room temperature for 4h, after removing methanol, reacted at 105℃ for 10h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, 0.55wt% acetic acid were added to adjust the pH to 5.8, reacted at 85℃ for 5h to obtain a Schiff base based hyperbranched polymer; S1-2: zinc chloride, 2,3,5,6-tetraiodoterephthalic acid were mixed by ball milling, washed and dried, then added into DMF, acetic acid and deionized water were added, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base based hyperbranched polymer, 135 parts of deionized water were dispersed, 1wt% citric acid was added to adjust the pH to 5.2 to obtain a MOF antibacterial fixing paste; Step 2: S2-1: 2.5 parts of berberine, 5.5 parts of 2,4-dimethoxybenzylamine were added into DMSO, stirred at 120℃ for 7h, washed and cooled, then freeze-dried and added into methanol, 0.8 parts of 12wt% hydrochloric acid was added, stirred at room temperature for 6h, the precipitate was washed and dried to obtain amino berberine; S2-2: 10 parts of dehydrated lactic acid, 1.5 parts of ethylene glycol were added into toluene, polycondensed at 140℃ for 3h, after cooling and drying, added into 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, tetrahydrofuran, reacted at 62℃ for 6.5h, neutralized, removed tetrahydrofuran and dried to obtain an epoxy-terminated lactic acid oligomer; 10 parts of amino berberine, epoxy-terminated lactic acid oligomer, 0.6 parts of triethylamine were added into DMF, reacted at 50℃ for 8h, dried to obtain a modified berberine; S2-3: the modified berberine, penetrant, buffer were added into deionized water, mixed to obtain a modified dye solution; Step 3: S3-1: wood pulp fibers were subjected to plasma treatment to obtain pretreated wood pulp fibers; S3-2: 70 parts of pretreated wood pulp fibers, 18 parts of carboxylated cellulose were sequentially subjected to opening and mixing, carding and laying, once water jet reinforcement to form a degradable base layer; S3-3: 13 parts of cellulose fibers, 12 parts of polylactic acid fibers were opened and mixed, and laid on the surface of the degradable base layer by carding, and then subjected to secondary water jet reinforcement to obtain a degradable water jet base material; Step 4: the degradable water jet base material was placed in the MOF antibacterial fixing paste, soaked for 16h, taken out and extruded for once dipping; after once dipping, it was placed in the MOF antibacterial fixing paste again, and ultrasonic treated for 45min, taken out and extruded for twice dipping, and dried; the surface was further sprayed with the modified dye solution, dried, wound, cut and obtained a water jet wiping material.

[0027] Embodiment 3: A method for preparing a wood pulp-based degradable hydroentangled wiping material, comprising the following steps: Step 1: S1-1: Under the condition of 1℃, nitrogen was introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol were added into 2.5 parts of divinyltriamine, and reacted at room temperature for 4h, after removing the methanol, reacted at 105℃ for 10h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, and 0.55wt% acetic acid were added to adjust the pH to 5.8, and reacted at 85℃ for 5h to obtain a Schiff base-based hyperbranched polymer; S1-2: zinc chloride and 2,3,5,6-tetraiodoterephthalic acid were mixed according to a molar ratio of 1:0.8, ball-milled, washed, and dried, then added into DMF, acetic acid and deionized water were added, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base-based hyperbranched polymer, and 135 parts of deionized water were dispersed, 1wt% citric acid was added to adjust the pH to 5.2 to obtain a MOF antibacterial fixing slurry; Step 2: S2-1: 2.5 parts of berberine and 5.5 parts of 2,4-dimethoxybenzylamine were added into DMSO, stirred at 120℃ for 7h, cooled and washed, then freeze-dried and added into methanol, 0.8 parts of 12wt% hydrochloric acid was added, stirred at room temperature for 6h, the precipitate was washed and dried to obtain amino berberine; S2-2: 10 parts of dehydrated lactic acid and 1.5 parts of ethylene glycol were added into toluene, and polycondensed at 140℃ for 3h, then cooled and dried, and added into 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, and tetrahydrofuran under nitrogen atmosphere, reacted at 62℃ for 6.5h, neutralized, removed tetrahydrofuran, and dried to obtain an epoxy-terminated lactic acid oligomer; 10 parts of amino berberine, the epoxy-terminated lactic acid oligomer, and 0.6 parts of triethylamine were added into DMF, reacted at 50℃ for 8h, and dried to obtain a modified berberine; S2-3: the modified berberine, a penetrating agent, and a buffer were added into deionized water, mixed, and a modified dye solution was obtained; Step 3: S3-1: wood pulp fibers were subjected to plasma treatment to obtain pretreated wood pulp fibers; S3-2: 80 parts of the pretreated wood pulp fibers and 20 parts of carboxylated cellulose were sequentially subjected to opening and mixing, carding and laying, and once hydroentanglement to form a degradable base layer; S3-3: 15 parts of cellulose fibers and 15 parts of polylactic acid fibers were opened and mixed, and laid on the surface of the degradable base layer by carding, and then subjected to secondary hydroentanglement to obtain a degradable hydroentangled base material; Step 4: the degradable hydroentangled base material was placed in the MOF antibacterial fixing slurry, soaked for 16h, taken out and extruded for once impregnation; after the once impregnation, the material was placed in the MOF antibacterial fixing slurry again, subjected to ultrasonic treatment for 45min, taken out and extruded for twice impregnation, and dried; the surface of the material was further sprayed with the modified dye solution, dried, wound, and cut to obtain a hydroentangled wiping material.

[0028] Comparative Example 1: Based on Example 2, 2, 3, 5, 6-tetraiodoterephthalic acid is adjusted to terephthalic acid, and the rest of the process is unchanged, and is adjusted to: Step 1: S1-1: At 1℃, nitrogen is introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol are added to 2.5 parts of divinyltriamine, reacted at room temperature for 4h, after removing methanol, reacted at 105℃ for 10h; Then add 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, 0.55wt% acetic acid to adjust the pH to 5.8, and react at 85℃ for 5h to obtain a Schiff base based hyperbranched polymer; S1-2: zinc chloride and terephthalic acid are mixed in a molar ratio of 1:0.8, ball milled, washed and dried, added to DMF, added acetic acid and deionized water, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base based hyperbranched polymer, 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2 to obtain MOF antibacterial fixing paste.

[0029] Comparative Example 2: Based on Example 2, the Schiff base based hyperbranched polymer is adjusted to chitosan, and the rest of the process is unchanged, and is adjusted to: Step 1: S1-1: Zinc chloride and 2, 3, 5, 6-tetraiodoterephthalic acid are mixed in a molar ratio of 1:0.8, ball milled, washed and dried, added to DMF, added acetic acid and deionized water, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-2: 4 parts of UiO-66-I4, 10 parts of chitosan, 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2 to obtain MOF antibacterial fixing paste.

[0030] Comparative Example 3: Based on Example 2, N-hydroxymethyl acrylamide, cinnamyl aldehyde are not added, and the rest of the process is unchanged, and is adjusted to: Step 1: S1-1: At 1℃, nitrogen is introduced, 3.5 parts of methyl acrylate, and methanol are added to 2.5 parts of divinyltriamine, reacted at room temperature for 4h, after removing methanol, reacted at 105℃ for 10h; To obtain a hyperbranched polymer; S1-2: zinc chloride and 2, 3, 5, 6-tetraiodoterephthalic acid are mixed in a molar ratio of 1:0.8, ball milled, washed and dried, added to DMF, added acetic acid and deionized water, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 9 parts of hyperbranched polymer, 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2 to obtain MOF antibacterial fixing paste.

[0031] Comparative Example 4: Based on Example 2, the modified berberine is adjusted to be berberine, and the rest of the process is unchanged, and is adjusted to be: Step 2: Berberine, penetrant, buffer are added to deionized water, mixed to obtain a modified dye solution.

[0032] Test Experiment 1: Antibacterial performance test: the spunlace wiping materials prepared by Examples 1-3 and Comparative Examples 1-4 are tested for antibacterial performance by oscillation method according to GB / T20944.3-2008, and the antibacterial performance is detected again after washing for 5 times; the results are shown in Table 1.

[0033] Test Experiment 2: Color fastness test: the spunlace wiping materials prepared by Examples 1-3 and Comparative Examples 1-4 are respectively tested for dry (wet) rubbing fastness, water fastness; the results are shown in Table 2.

[0034] Result analysis: According to the data analysis of Tables 1-2, it can be seen that the present scheme can realize the improvement of antibacterial and fixation dual performance; from the data of Comparative Example 1, it can be seen that 2,3,5,6-tetraiodo terephthalic acid is adjusted to terephthalic acid, which loses the antibacterial ability of iodine group, greatly reduces the antibacterial property, and lacks the synergistic effect between iodine and dye, and the fixation decreases; from the data of Comparative Example 2, it can be seen that the Schiff base based hyperbranched polymer is adjusted to chitosan, which is easy to produce swelling and aggregation, and the structural stability greatly decreases, and the fixation and antibacterial property decrease; from the data of Comparative Example 3, it can be seen that N-hydroxymethyl acrylamide and cinnamaldehyde are not added, the hydrophilicity of the hyperbranched polymer decreases, the Schiff base group cannot be formed, the antibacterial property decreases, and at the same time, the dye molecules cannot form covalent crosslinking, the interfacial bonding force is weak, and the fixation and antibacterial durability greatly decrease; from the data of Comparative Example 4, it can be seen that the modified berberine is adjusted to be berberine, which has poor dispersibility, and the fixation decreases; and the interfacial bonding force with the fiber decreases, the structural stability decreases, and the antibacterial property and durability decrease.

[0035] It is apparent for those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present application should be defined by the appended claims rather than the above description, and all changes falling within the meaning and range of equivalents of the claims are intended to be embraced therein.

Claims

1. A method of making a wood pulp based degradable hydroentangled wiping material, characterized by: Comprise the following steps: Step 1: (1) the pretreated wood pulp fibers, carboxylated cellulose are sequentially opened and mixed, carded and laid, and once water jet reinforced to form a degradable base layer; (2) take cellulose fiber, polylactic acid fiber and open and mix, carded and laid on the surface of the degradable base layer, twice water jet reinforced, to obtain a degradable water jet base material; Step 2: the degradable water jet base material is placed in the MOF antibacterial fixing dyeing slurry for two dip two roll, drying; its surface is further sprayed with modified dye liquid, drying, winding cutting, to obtain a water jet wiping material.

2. A process for the preparation of a wood pulp based degradable hydroentangled wiping material according to claim 1, characterized in that: The raw materials of the degradable water jet base material include the following components: 60-80 parts of pretreated wood pulp fiber, 15-20 parts of carboxylated cellulose, 12-15 parts of cellulose fiber, and 10-15 parts of polylactic acid fiber by mass fraction.

3. A process for the preparation of a wood pulp based degradable hydroentangled wiping material as claimed in claim 1, wherein: The preparation process of the MOF antibacterial fixing dyeing slurry is as follows: S1-1: at 0-5℃, nitrogen is introduced, N-hydroxymethyl acrylamide, methyl acrylate and methanol are added to divinyltriamine, and the reaction is carried out at room temperature for 3-5h, after removing methanol, the reaction is carried out at 90-120℃ for 8-12h; then cinnamyl aldehyde and tetrahydrofuran are added, 0.5wt%-0.6wt% acetic acid is used to adjust the pH to 5.5-6.0, and the reaction is carried out at 80-90℃ for 4-6h to obtain a Schiff base based hyperbranched polymer; S1-2: after mixing, washing and drying, the zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are added to DMF, acetic acid and deionized water are added, and stirring is carried out at 110-130℃ for 20-40min, and then washing and drying are carried out to obtain UiO-66-I4; S1-3: the UiO-66-I4, the Schiff base based hyperbranched polymer and deionized water are dispersed, citric acid is added to adjust the pH to 5.0-5.5 to obtain the MOF antibacterial fixing dyeing slurry.

4. A process for the production of a wood pulp based degradable hydroentangled wiping material according to claim 3, characterized in that: The raw materials of the MOF antibacterial fixing dyeing slurry include the following components, 3-5 parts of UiO-66-I4, 8-12 parts of Schiff base based hyperbranched polymer and 120-150 parts of deionized water by mass fraction; wherein the concentration of citric acid is 0.5wt%-1.5wt%.

5. A process for the production of a wood pulp based degradable hydroentangled wiping material according to claim 4, characterized in that: The UiO-66-I4 includes zinc chloride and 2,3,5,6-tetraiodoterephthalic acid with a molar ratio of 1:0.5-1; the raw materials of the Schiff base based hyperbranched polymer include the following components: 1-2 parts of N-hydroxymethyl acrylamide, 2-3.5 parts of methyl acrylate, 2-3 parts of divinyltriamine and 2-2.5 parts of cinnamyl aldehyde by mass fraction.

6. The method of claim 1, wherein: The spraying amount of the modified dye liquid is 5-10 g / cm 2 The preparation process of the modified dye liquid is: S2-1: take berberine and 2,4-dimethoxybenzylamine and add them to DMSO, stir at 110-130℃ for 6-8h, cool and wash, freeze-dry, then add to methanol, add 10wt%-15wt% hydrochloric acid, stir at room temperature for 5-7h, wash the precipitate and dry to obtain amino berberine; S2-2: After dehydration, lactic acid and ethylene glycol are added to toluene, and polycondensation is carried out at 120-160℃ for 2-4h. After cooling and drying, they are added to epichlorohydrin, TBAB, sodium hydroxide, and tetrahydrofuran under a nitrogen atmosphere, and reaction is carried out at 60-65℃ for 5-8h. After neutralization, tetrahydrofuran is removed, and drying is carried out to obtain an epoxy-terminated lactic acid oligomer. Amino berberine, epoxy-terminated lactic acid oligomer, and triethylamine are added to DMF, and reaction is carried out at 45-55℃ for 7-9h. After drying, a modified berberine is obtained. S2-3: The modified berberine, penetrant, and buffer are added to deionized water, mixed, and a modified dye solution is obtained.

7. A process for the production of a wood pulp based degradable hydroentangled wiping material according to claim 6, characterized in that: The components of the modified dye solution are as follows in terms of mass percentage: 5-8% modified berberine, 0.4-0.6% penetrant, 0.2-0.8% buffer, and the rest is deionized water. The raw material of the amino berberine includes the following components: 2-3 parts berberine, 4-7 parts 2,4-dimethoxybenzylamine, and 0.5-1 part 10wt%-15wt% hydrochloric acid, in terms of mass fraction. The raw material of the modified berberine includes the following components: 8-12 parts lactic acid, 1-2 parts ethylene glycol, 3-6 parts epichlorohydrin, 0.2-0.5 parts TBAB, 0.2-0.5 parts sodium hydroxide, 8-12 parts amino berberine, and 0.5-0.8 parts triethylamine, in terms of mass fraction.

8. The method of claim 1, wherein: The process parameters of the first water jet reinforcement are as follows: water jet pressure is 3.5-4.5MPa, water jet path number is 1-2, water jet height is 35-40mm, and web curtain speed is 10-15m / min. The process parameters of the second water jet reinforcement are as follows: water jet pressure is 5.5-6.5MPa, water jet path number is 2-3, water jet height is 40-45mm, and web curtain speed is 15-20m / min.

9. The method of claim 1, wherein: The process of the two-dip-two-pad is as follows: the degradable water jet base material is placed in the MOF antibacterial fixing paste, dipped for 12-18h, taken out and extruded, and the first dip-pad is obtained. After the first dip-pad, it is placed in the MOF antibacterial fixing paste again, ultrasonic treated for 30-60min, taken out and extruded for the second time, and the second dip-pad is obtained.

10. A water jet wiping material prepared by the preparation method of a wood pulp-based degradable water jet wiping material according to any one of claims 1-9.

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