阅读说明：本技术 一种抑菌耐磨球类皮革及其制作方法 (Antibacterial wear-resistant ball leather and manufacturing method thereof ) 是由 陈公湖 陈侯灿 于 2020-06-05 设计创作，主要内容包括：本发明涉及一种抑菌耐磨球类皮革及其制作方法,所述球类皮革包括基布、粘结层、发泡层以及表面层；所述表面层包括以下重量份数的组分：水性聚氨酯树脂80-90份、二甲基甲酰胺100-120份、聚丙烯酸钠10-15份、水2-5份、硅烷偶联剂KH550 3-5份、炭黑10-15份、介孔二氧化硅-二氧化钛复合粉体15-20份、改性SiC粉体8-12份、N,N–二正丁基二硫氨基甲酸镍2-5份、聚乙二醇10-15份、双氧水1-1.5份、亚硫酸氢钠0.5-0.8份、发泡剂2-4份、色粉12-15份；本发明的球类皮革具有极佳的耐磨、耐候性能且其对大肠杆菌、金黄色葡萄球菌等几乎所有的微生物都具有很强的杀菌能力。(The invention relates to antibacterial wear-resistant ball leather and a manufacturing method thereof, wherein the ball leather comprises base cloth, a bonding layer, a foaming layer and a surface layer; the surface layer comprises the following components in parts by weight: 80-90 parts of waterborne polyurethane resin, 120 parts of dimethylformamide, 10-15 parts of sodium polyacrylate, 2-5 parts of water, 3-5 parts of silane coupling agent KH550, 10-15 parts of carbon black, 15-20 parts of mesoporous silica-titanium dioxide composite powder, 8-12 parts of modified SiC powder, 2-5 parts of N, N-di-N-butyl nickel dithiocarbamate, 10-15 parts of polyethylene glycol, 1-1.5 parts of hydrogen peroxide, 0.5-0.8 part of sodium bisulfite, 2-4 parts of foaming agent and 12-15 parts of toner; the ball leather has excellent wear resistance and weather resistance, and has strong bactericidal capacity on almost all microorganisms such as escherichia coli, staphylococcus aureus and the like.)

1. The antibacterial wear-resistant ball leather is characterized in that: it comprises a base cloth, a bonding layer, a foaming layer and a surface layer;

wherein the surface layer comprises the following components in parts by weight: 80-90 parts of waterborne polyurethane resin, 120 parts of dimethylformamide, 10-15 parts of sodium polyacrylate, 2-5 parts of water, 3-5 parts of silane coupling agent KH550, 10-15 parts of carbon black, 15-20 parts of mesoporous silica-titanium dioxide composite powder, 8-12 parts of modified SiC powder, 2-5 parts of N, N-di-N-butyl nickel dithiocarbamate, 10-15 parts of polyethylene glycol, 1-1.5 parts of hydrogen peroxide, 0.5-0.8 part of sodium bisulfite, 2-4 parts of foaming agent and 12-15 parts of toner;

the foaming layer comprises the following components in parts by weight: 80-100 parts of waterborne polyurethane resin, 80-90 parts of dimethylformamide, 10-15 parts of carbon black, 30-40 parts of ground calcium carbonate, 5-8 parts of foaming agent and 5-5 parts of emulsifier S-803.

2. The bacteriostatic wear-resistant ball leather according to claim 1, which is characterized in that: the foaming agent is one or a mixture of an AC foaming agent and p-toluenesulfonyl hydrazide.

3. The bacteriostatic wear-resistant ball leather according to claim 1, which is characterized in that: the base cloth is knitted cloth or non-woven cloth.

4. The bacteriostatic wear-resistant ball leather according to claim 1, which is characterized in that: the adhesive layer is formed by an adhesive, and the adhesive is a water-soluble phenolic resin adhesive.

5. The method for manufacturing the bacteriostatic wear-resistant ball leather as claimed in claim 1, which is characterized by comprising the following steps of: it comprises the following steps:

preparing surface layer slurry in step (1):

step a: preparing mesoporous silicon dioxide-titanium dioxide composite powder;

step b: preparing modified SiC powder;

step c: mixing waterborne polyurethane resin, dimethylformamide, sodium polyacrylate, water, a silane coupling agent KH550, N-di-N-butyl nickel dithiocarbamate, polyethylene glycol, hydrogen peroxide, sodium bisulfite, a foaming agent and toner, heating to a molten state, wherein the heating temperature is 220-;

preparing foaming layer slurry in step (2): heating waterborne polyurethane resin, dimethylformamide and an emulsifier S-80 at the temperature of 210-220 ℃ for 30-40min, then adding a foaming agent, carbon black and heavy calcium carbonate, and stirring at the speed of 40-50r/min for 30-40min to obtain foaming layer slurry;

and (3) slurry blade coating: coating the surface layer slurry obtained in the step (1) on release paper, and drying at 100-120 ℃ for 60-80s to form a surface layer; then, coating the foaming layer slurry obtained in the step (2) on the dried surface layer in a scraping way, and drying the coating at the temperature of 100 ℃ and 120 ℃ for 60-80s to form a foaming layer; and then, coating a water-soluble phenolic resin adhesive on the foaming layer in a scraping way to be used as a bonding layer, then covering a base cloth, drying at the temperature of 80-100 ℃, and then stripping off release paper to obtain the antibacterial wear-resistant ball leather.

6. The manufacturing method of the bacteriostatic wear-resistant ball leather according to claim 5, which is characterized in that: the specific operation method of the step a in the step (1) comprises the following steps:

i, preparing mesoporous SiO₂：

Dissolving hexadecyl trimethyl ammonium chloride in deionized water, and stirring at a constant temperature of 60 ℃ until the solution is clear to obtain a hexadecyl trimethyl ammonium chloride aqueous solution;

heating and mixing tetraethyl orthosilicate and triethylamine at 90-95 ℃ for 25-30min, and cooling to room temperature to obtain a primary mixed solution;

thirdly, adding the primary mixed liquid obtained in the second step into the aqueous solution of the hexadecyl trimethyl ammonium chloride obtained in the first step to obtain final mixed liquid; stirring the final mixed solution at room temperature for reaction for 3-5h to obtain turbid solution, then carrying out centrifugal separation on the turbid solution, and collecting a centrifugal product, namely a crude product;

④ washing the crude product obtained in step ③ with ethanol and water, drying in an oven at 60-65 deg.C for 1-2h, placing the dried semi-finished product in a muffle furnace, slowly heating to 550 deg.C and 560 deg.C at a rate of 1-3 deg.C/min, and calcining for 5-6h to obtain mesoporous SiO₂(ii) a Wherein, mesoporous SiO is prepared₂The mole ratio of tetraethyl orthosilicate, hexadecyl trimethyl ammonium chloride, triethylamine and deionized water is 1: 0.18: 8.0: 130, 130;

II, preparing mesoporous silicon dioxide-titanium dioxide composite powder:

firstly, preparing a titanium tetrachloride-ethanol solution: mixing titanium tetrachloride and ethanol in a volume ratio of 1:2 to obtain a titanium tetrachloride-ethanol solution;

then the mesoporous SiO is put into₂Ultrasonically dispersing into absolute ethyl alcohol to obtain mesoporous SiO with the weight percentage concentration of 15 percent₂-ethanol solution, followed by the mesoporous SiO₂Heating the ethanol solution to 60 ℃ and keeping the temperature constant, and then adding the mesoporous SiO₂Dropwise adding titanium tetrachloride-ethanol solution into the ethanol solution while stirring to obtain mesoporous SiO₂The mol ratio of the titanium tetrachloride to the titanium tetrachloride is 1:1.2, the dripping time is controlled to be 20min, the stirring is continued for 3 to 4 hours after the dripping is finished, the heating is stopped, and the mixture is aged for 24 hours at normal temperature;

then, at normal temperature, adding water into the reaction system, wherein the molar ratio of the water to the titanium tetrachloride is 2:1, stirring for 1-2h to obtain white turbid liquid, performing centrifugal separation, putting the obtained centrifugal product into a drying oven, and drying for 1-2h at the temperature of 60-65 ℃; and placing the dried semi-finished product in a muffle furnace, and roasting for 5-6h at the temperature of 500-550 ℃ to obtain the mesoporous silicon dioxide-titanium dioxide composite powder.

7. The manufacturing method of the bacteriostatic wear-resistant ball leather according to claim 5, which is characterized in that: the specific operation method of the step b in the step (1) comprises the following steps: adding 50 parts of SiC powder with the diameter of 10 mu m D50, 150 parts of toluene and KH 5601.5 parts of silane coupling agent into a reaction bottle in parts by weight, and introducing N₂In N at₂Stirring and reacting for 6h at 85 ℃ under protection, after the reaction is finished, carrying out vacuum filtration while the reaction is hot, and then ultrasonically dispersing the filtration product in an ultrasonic medium, wherein the ultrasonic time is controlled to be 30 min; and centrifuging for 25min, placing the centrifugal product in an oven, and drying at 110 ℃ for 12h to obtain the modified SiC powder.

8. The manufacturing method of the bacteriostatic wear-resistant ball leather according to claim 7, which is characterized in that: the ultrasonic medium is a mixed solution obtained by mixing acetone and water according to the volume ratio of 2: 1.

Technical Field

The invention relates to antibacterial wear-resistant ball leather and a manufacturing method thereof.

Background

Ball games (e.g., basketball) are a popular form of play. At present, the existing ball leather comprises genuine leather and imitated genuine leather, and the ball leather which takes polyvinyl chloride (PVC) and Polyurethane (PU) as raw materials is widely applied in the market. The traditional ball leather has poor weather resistance and wear resistance, does not have the functions of bacteriostasis and disinfection, so that the ball is easy to breed bacteria and mildew, and simultaneously easily infects viruses and bacteria to athletes to cause cross infection. Therefore, it is necessary to design a ball leather with good wear resistance, bacteriostasis, antibiosis and disinfection effects.

Disclosure of Invention

The invention aims to provide bacteriostatic wear-resistant ball leather with wear resistance and excellent bacteriostatic effect and a manufacturing method thereof.

The purpose of the invention is realized by the following technical scheme: an antibacterial wear-resistant ball leather comprises a base cloth, a bonding layer, a foaming layer and a surface layer;

wherein the surface layer comprises the following components in parts by weight: 80-90 parts of waterborne polyurethane resin, 120 parts of dimethylformamide, 10-15 parts of sodium polyacrylate, 2-5 parts of water, 3-5 parts of silane coupling agent KH550, 10-15 parts of carbon black, 15-20 parts of mesoporous silica-titanium dioxide composite powder, 8-12 parts of modified SiC powder, 2-5 parts of N, N-di-N-butyl nickel dithiocarbamate, 10-15 parts of polyethylene glycol, 1-1.5 parts of hydrogen peroxide, 0.5-0.8 part of sodium bisulfite, 2-4 parts of foaming agent and 12-15 parts of toner;

the foaming layer comprises the following components in parts by weight: 80-100 parts of waterborne polyurethane resin, 80-90 parts of dimethylformamide, 10-15 parts of carbon black, 30-40 parts of ground calcium carbonate, 5-8 parts of foaming agent and 5-5 parts of emulsifier S-803.

The manufacturing method of the antibacterial wear-resistant ball leather comprises the following steps:

preparing surface layer slurry in step (1):

step a: preparing mesoporous silicon dioxide-titanium dioxide composite powder;

step b: preparing modified SiC powder;

step c: mixing waterborne polyurethane resin, dimethylformamide, sodium polyacrylate, water, a silane coupling agent KH550, N-di-N-butyl nickel dithiocarbamate, polyethylene glycol, hydrogen peroxide, sodium bisulfite, a foaming agent and toner, heating to a molten state, wherein the heating temperature is 220-;

preparing foaming layer slurry in step (2): heating waterborne polyurethane resin, dimethylformamide and an emulsifier S-80 at the temperature of 210-220 ℃ for 30-40min, then adding a foaming agent, carbon black and heavy calcium carbonate, and stirring at the speed of 40-50r/min for 30-40min to obtain foaming layer slurry;

and (3) slurry blade coating: coating the surface layer slurry obtained in the step (1) on release paper, and drying at 100-120 ℃ for 60-80s to form a surface layer; then, coating the foaming layer slurry obtained in the step (2) on the dried surface layer in a scraping way, and drying the coating at the temperature of 100 ℃ and 120 ℃ for 60-80s to form a foaming layer; and then, coating a water-soluble phenolic resin adhesive on the foaming layer in a scraping way to be used as a bonding layer, then covering a base cloth, drying at the temperature of 80-100 ℃, and then stripping off release paper to obtain the antibacterial wear-resistant ball leather.

Compared with the prior art, the invention has the advantages that: 1. the ball leather has excellent wear resistance and weather resistance. 2. The ball leather has strong bactericidal capacity on almost all microorganisms such as escherichia coli, staphylococcus aureus, mould and the like, and has good bacteriostatic and antiviral effects even under weak light. 3. The ball leather of the invention has soft texture, and balls made of the leather have good elasticity. 4. The ball leather can be used for manufacturing basketballs, rugby balls and the like.

Detailed Description

The present invention will be described in detail with reference to the following examples:

an antibacterial wear-resistant ball leather comprises a base cloth, a bonding layer, a foaming layer and a surface layer;

wherein the surface layer comprises the following components in parts by weight: 80-90 parts of waterborne polyurethane resin, 120 parts of dimethylformamide, 10-15 parts of sodium polyacrylate, 2-5 parts of water, 3-5 parts of silane coupling agent KH550, 10-15 parts of carbon black, 15-20 parts of mesoporous silica-titanium dioxide composite powder, 8-12 parts of modified SiC powder, 2-5 parts of N, N-di-N-butyl nickel dithiocarbamate, 10-15 parts of polyethylene glycol, 1-1.5 parts of hydrogen peroxide, 0.5-0.8 part of sodium bisulfite, 2-4 parts of foaming agent and 12-15 parts of toner;

the foaming layer comprises the following components in parts by weight: 80-100 parts of waterborne polyurethane resin, 80-90 parts of dimethylformamide, 10-15 parts of carbon black, 30-40 parts of ground calcium carbonate, 5-8 parts of foaming agent and 5-5 parts of emulsifier S-803.

The foaming agent is one or a mixture of an AC foaming agent and p-toluenesulfonyl hydrazide.

The base cloth is knitted cloth or non-woven cloth.

The adhesive layer is formed by an adhesive, and the adhesive is a water-soluble phenolic resin adhesive.

The manufacturing method of the antibacterial wear-resistant ball leather comprises the following steps:

preparing surface layer slurry in step (1):

step a: preparing mesoporous silicon dioxide-titanium dioxide composite powder:

i, preparing mesoporous SiO₂：

Dissolving hexadecyl trimethyl ammonium chloride in deionized water, and stirring at a constant temperature of 60 ℃ until the solution is clear to obtain a hexadecyl trimethyl ammonium chloride aqueous solution;

heating and mixing tetraethyl orthosilicate and triethylamine at 90-95 ℃ for 25-30min, and cooling to room temperature to obtain a primary mixed solution;

thirdly, adding the primary mixed liquid obtained in the second step into the aqueous solution of the hexadecyl trimethyl ammonium chloride obtained in the first step to obtain final mixed liquid; stirring the final mixed solution at room temperature for reaction for 3-5h to obtain turbid solution, then carrying out centrifugal separation on the turbid solution, and collecting a centrifugal product, namely a crude product;

④ washing the crude product obtained in step ③ with ethanol and water, drying in an oven at 60-65 deg.C for 1-2h, placing the dried semi-finished product in a muffle furnace, slowly heating to 550 deg.C and 560 deg.C at a rate of 1-3 deg.C/min, and calcining for 5-6h to obtain mesoporous SiO₂(ii) a Wherein, mesoporous SiO is prepared₂The mole ratio of tetraethyl orthosilicate, hexadecyl trimethyl ammonium chloride, triethylamine and deionized water is 1: 0.18: 8.0: 130, 130;

II, preparing mesoporous silicon dioxide-titanium dioxide composite powder:

firstly, preparing a titanium tetrachloride-ethanol solution: mixing titanium tetrachloride and ethanol in a volume ratio of 1:2 to obtain a titanium tetrachloride-ethanol solution;

then the mesoporous SiO is put into₂Ultrasonically dispersing into absolute ethyl alcohol to obtain mesoporous SiO with the weight percentage concentration of 15 percent₂Ethanol solution (i.e. mesoporous SiO)₂15% by weight in absolute ethanol), followed by mixing the mesoporous SiO₂Heating the ethanol solution to 60 ℃ and keeping the temperature constant, and then adding the mesoporous SiO₂Dropwise adding titanium tetrachloride-ethanol solution into the ethanol solution while stirring to obtain mesoporous SiO₂The mol ratio of the titanium tetrachloride to the titanium tetrachloride is 1:1.2, the dripping time is controlled to be 20min, the stirring is continued for 3 to 4 hours after the dripping is finished, the heating is stopped, and the mixture is aged for 24 hours at normal temperature;

then, at normal temperature, adding water into the reaction system, wherein the molar ratio of the water to the titanium tetrachloride is 2:1, stirring for 1-2h to obtain white turbid liquid, performing centrifugal separation, putting the obtained centrifugal product into a drying oven, and drying for 1-2h at the temperature of 60-65 ℃; and placing the dried semi-finished product in a muffle furnace, and roasting for 5-6h at the temperature of 500-550 ℃ to obtain the mesoporous silicon dioxide-titanium dioxide composite powder. The mesoporous silica-titanium dioxide composite powder can be used as a filler of a surface layer and also has a bacteriostatic function, and the pore structure of the mesoporous silica can load titanium dioxide, so that the ball leather has good bacteriostatic and antiviral effects even under weak light. The mesoporous silica-titanium dioxide composite powder can be stably dispersed in other raw materials of a surface layer by combining with a quantitative silane coupling agent KH550, so that the mesoporous silica-titanium dioxide composite powder can be well dissolved with other materials, and the prepared leather has the best performance.

Step b: preparing modified SiC powder:

adding 50 parts of SiC powder with the diameter of 10 mu m D50, 150 parts of toluene and KH 5601.5 parts of silane coupling agent into a reaction bottle in parts by weight, and introducing N₂In N at₂Stirring and reacting for 6h at 85 ℃ under protection, after the reaction is finished, carrying out vacuum filtration while the reaction is hot, and then ultrasonically dispersing the filtration product in an ultrasonic medium, wherein the ultrasonic time is controlled to be 30 min; then centrifuging for 25min, placing the centrifugal product in an oven, and drying at 110 ℃ for 12h to obtain the modified SiC powderAnd (3) a body. Wherein the ultrasonic medium is a mixed solution obtained by mixing acetone and water according to the volume ratio of 2: 1. The ultrasonic frequency is set to 20-28kHz during ultrasonic dispersion.

The leather has good wear resistance due to the addition of the modified SiC powder, and the modified SiC powder has good dispersibility, can be well dissolved with other raw materials on the surface layer, and has good performance.

Step c: mixing waterborne polyurethane resin, dimethylformamide, sodium polyacrylate, water, a silane coupling agent KH550, N-di-N-butyl nickel dithiocarbamate, polyethylene glycol, hydrogen peroxide, sodium bisulfite, a foaming agent and toner, heating to a molten state, wherein the heating temperature is 220-;

preparing foaming layer slurry in step (2): heating waterborne polyurethane resin, dimethylformamide and an emulsifier S-80 at the temperature of 210-220 ℃ for 30-40min, then adding a foaming agent, carbon black and heavy calcium carbonate, and stirring at the speed of 40-50r/min for 30-40min to obtain foaming layer slurry;

and (3) slurry blade coating: coating the surface layer slurry obtained in the step (1) on release paper, and drying at 100-120 ℃ for 60-80s to form a surface layer; then, coating the foaming layer slurry obtained in the step (2) on the dried surface layer in a scraping way, and drying the coating at the temperature of 100 ℃ and 120 ℃ for 60-80s to form a foaming layer; and then, coating a water-soluble phenolic resin adhesive on the foaming layer in a scraping way to be used as a bonding layer, then covering a base cloth, drying at the temperature of 80-100 ℃, and then stripping off release paper to obtain the antibacterial wear-resistant ball leather.

The invention is explained in more detail below with reference to specific examples: