CN113303555B - Deodorizing casual shoes capable of reducing peculiar smell - Google Patents

Deodorizing casual shoes capable of reducing peculiar smell Download PDF

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CN113303555B
CN113303555B CN202110669445.9A CN202110669445A CN113303555B CN 113303555 B CN113303555 B CN 113303555B CN 202110669445 A CN202110669445 A CN 202110669445A CN 113303555 B CN113303555 B CN 113303555B
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agent
parts
antibacterial
sodium bicarbonate
pore
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CN113303555A (en
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吴承权
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Fujian Joyyou Sports Goods Co ltd
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Fujian Joyyou Sports Goods Co ltd
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    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0245—Uppers; Boot legs characterised by the constructive form
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Plant Pathology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The application relates to the technical field of casual shoes, and particularly discloses a deodorizing casual shoe capable of reducing peculiar smell. The deodorizing leisure shoes with the odor reduction function comprise shoe bodies, wherein each shoe body comprises a vamp, a midsole and an outsole, antibacterial coatings are coated on the inner side surface of each vamp and the top surface of each midsole, each antibacterial coating is formed by heating and curing antibacterial materials, and each antibacterial material is prepared from the following raw materials in parts by weight: 60-80 parts of polyacrylate emulsion, 10-20 parts of antibacterial agent, 5-12 parts of cross-linking agent, 2-5 parts of dispersing agent and 6-15 parts of pore-forming agent; the antibacterial agent consists of titanium dioxide and zinc oxide in the mass ratio of (2-5) (1-3), the cross-linking agent is a silane coupling agent, the dispersing agent is diethylene glycol, and the pore-forming agent is at least one of paraformaldehyde and sodium bicarbonate. The deodorizing casual shoes for reducing the peculiar smell have the advantages of reducing the peculiar smell and being good in air permeability.

Description

Deodorizing casual shoes capable of reducing peculiar smell
Technical Field
The application relates to the technical field of casual shoes, in particular to a deodorizing casual shoe capable of reducing peculiar smell.
Background
With the continuous development of economy and society, the living standard of people is continuously improved, and various leisure activities such as walking, body building, traveling, hiking, climbing and the like are increasingly favored by people. In these leisure activities, the leisure shoes are used as necessary articles for daily use, and not only meet the daily basic requirements, but also have requirements on comfort and functionality.
During the wearing process of the casual shoes, a great deal of bacteria and fungi can be bred in the warm and moist environment in the shoes, so that peculiar smell and odor are diffused, and great trouble is brought to the wearer. Therefore, the functional modification of the casual shoes, such as the antibacterial deodorization function, is greatly sought after by the public, the prior antibacterial deodorization sports shoes are generally compounded by adopting a polymer bonding material and an antibacterial material, and then the antibacterial modification treatment is carried out on the parts of the inner side of the vamp, the inner side of the upper, the insole, the sole and the like of the casual shoes.
However, the antibacterial layer formed by the polymer adhesive and the antibacterial material is generally poor in air permeability, so that sweat feet and wet sticky body feeling are easy to occur to a wearer, and the wearing experience is poor.
Disclosure of Invention
In order to solve the problem of poor air permeability of the antibacterial layer, the application provides deodorizing casual shoes capable of reducing peculiar smell.
The application provides a deodorizing casual shoe capable of reducing peculiar smell, which adopts the following technical scheme:
the utility model provides a deodorizing leisure shoes of reduction peculiar smell, includes the shoes body, the shoes body includes vamp, insole and outsole, vamp medial surface and insole top surface all are coated with antibacterial coating, antibacterial coating is by antibacterial material heat cure formation, antibacterial material is made by the raw materials including following parts by weight: 60-80 parts of polyacrylate emulsion, 10-20 parts of antibacterial agent, 5-12 parts of cross-linking agent, 2-5 parts of dispersing agent and 6-15 parts of pore-forming agent; the antibacterial agent consists of titanium dioxide and zinc oxide in the mass ratio of (2-5) (1-3), the cross-linking agent is a silane coupling agent, the dispersing agent is diethylene glycol, and the pore-forming agent is at least one of paraformaldehyde and sodium bicarbonate.
By adopting the technical scheme, as the antibacterial agent is mixed with the polyacrylate emulsion, titanium dioxide and zinc oxide are uniformly dispersed in the polyacrylate emulsion, and then the binding force between the titanium dioxide and zinc oxide and a polyacrylate macromolecular chain is better under the assistance of the silane coupling agent, so that an antibacterial coating with better uniformity is formed after heating and curing. In addition, the paraformaldehyde and the sodium bicarbonate can be filled into the antibacterial coating, and after being heated, the paraformaldehyde and the sodium bicarbonate are decomposed to release gas, and tiny bubbles are formed, so that a micro-pore structure is formed in the antibacterial coating, and the air permeability of the antibacterial coating is greatly improved while the antibacterial performance is ensured.
Preferably, the antibacterial material is prepared from the following raw materials in parts by weight: 65-70 parts of polyacrylate emulsion, 12-17 parts of antibacterial agent, 7-10 parts of cross-linking agent, 3-4.5 parts of dispersing agent and 8-13 parts of pore-forming agent; the antibacterial agent consists of titanium dioxide and zinc oxide in the mass ratio of (2-5) (1-3), the cross-linking agent is a silane coupling agent, the dispersing agent is diethylene glycol, and the pore-forming agent is at least one of paraformaldehyde and sodium bicarbonate.
By adopting the technical scheme, the mechanical property and the air permeability of the antibacterial coating are better by adjusting the dosages of the cross-linking agent, the polyacrylic emulsion and the pore-forming agent through optimizing the proportion of raw materials.
Preferably, the mass ratio of the pore-forming agent to the polyacrylate emulsion is 1 (5-10), and the solid content of the polyacrylate emulsion is 30-60%.
By adopting the technical scheme, the pore structure of the antibacterial coating prepared according to the proportion is stable and uniform, the condition that the antibacterial performance is reduced due to the fact that the pore diameter of micropores is large due to excessive gas quantity is reduced, and the antibacterial performance and the air permeability of the antibacterial coating reach a relatively balanced composite state.
Preferably, the pore-forming agent consists of paraformaldehyde and sodium bicarbonate in the mass ratio of (0.5-1.2) to (3-7).
By adopting the technical scheme, on one hand, the pore-forming agent compounded according to the proportion can form a finer void structure, and on the other hand, the sodium bicarbonate can provide alkaline conditions for the paraformaldehyde, so that the decomposition temperature of the paraformaldehyde is reduced, and the stability of the performance of other components in the antibacterial coating is ensured.
Preferably, the sodium bicarbonate is modified sodium bicarbonate, and the modified sodium bicarbonate is prepared by coating sodium bicarbonate with alkyl quaternary ammonium salt.
Through adopting above-mentioned technical scheme, after alkyl quaternary ammonium salt cladding sodium bicarbonate, the macromolecular chain segment of alkyl quaternary ammonium salt can form a little aggregate of individual after the sodium bicarbonate is dispersed, reduces the too fine condition of bubble that leads to the gas release to form that the sodium bicarbonate is too dispersed, can not fine void structure, and alkyl quaternary ammonium salt also has fine antibacterial property in addition, cooperates with titanium dioxide and zinc oxide, further improves antibacterial property and the gas permeability of antibacterial coating.
Preferably, the alkyl quaternary ammonium salt is at least one of octadecyl dimethyl trimethyl silicon propyl ammonium chloride and N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride.
By adopting the technical scheme, the octadecyl dimethyl trimethyl silicon propyl ammonium chloride and the N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride have excellent antibacterial performance, have larger steric hindrance and molecular chain binding force, can be firmly combined in the antibacterial coating, and improve the service life and penetration and washing resistance of the antibacterial coating. In addition, the organosilicon group on the octalkyl dimethyl trimethyl silylpropyl ammonium chloride and the N, N-dimethyl dodecyl aminopropyl trimethoxy silane ammonium chloride can improve the hydrophobicity of sodium bicarbonate to a certain extent, and reduce the phenomenon that the sodium bicarbonate is excessively dispersed in the antibacterial coating.
Preferably, the alkyl quaternary ammonium salt is octadecyl dimethyl trimethyl silicon propyl ammonium chloride and N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride, and the mass ratio is (5-8) (2-3).
By adopting the technical scheme, the alkyl silicone quaternary ammonium salt compounded according to the proportion ensures that the size of the sodium bicarbonate aggregate is uniform, the dispersibility is good, the formed micro-pore structure is more uniform, and the antibacterial performance of the prepared antibacterial coating is better.
Preferably, the antibacterial material also comprises (0.5-1) weight part of emulsifier, wherein the emulsifier is polyoxyethylene ether sulfonate.
By adopting the technical scheme, the polyoxyethylene ether sulfonate molecule comprises nucleophilic groups and non-anchoring chain segments, wherein the nucleophilic groups are in anchoring combination with titanium dioxide, zinc oxide, paraformaldehyde and sodium bicarbonate, and the non-anchoring groups are combined with polyacrylate chain segments, so that stable dispersoids are formed, the dispersibility of the antibacterial agent and the pore-forming agent is improved, and the isotropy of the antibacterial coating is further improved.
Preferably, the raw materials of the antibacterial material further comprise (1-2) weight parts of polyvinyl alcohol.
Through adopting above-mentioned technical scheme, polyvinyl alcohol can provide a large amount of hydroxyl, plays auxiliary film-forming's effect, in addition, also can carry out partial decomposition after the polyvinyl alcohol is heated, helps pore-forming agent to form micro-pore structure, further improves antibacterial coating's gas permeability.
In summary, the present application has the following beneficial effects:
1. as the antibacterial agent and the pore-forming agent are dispersed in the polyacrylate emulsion, a uniform antibacterial coating is formed under the action of the crosslinking agent and the dispersing agent, and a micro-pore structure is formed under the action of the pore-forming agent, the antibacterial performance is ensured, and the air permeability of the antibacterial coating is greatly improved.
2. The quaternary ammonium salt is preferably adopted for modification, so that on one hand, the antibacterial performance of the antibacterial coating is further improved, and on the other hand, the micro-pore structure of the antibacterial coating is improved.
3. The quaternary ammonium salt adopts the organic silicon quaternary ammonium salt, so that the antibacterial performance is improved, the probability of excessive dispersion of sodium bicarbonate is reduced, and the distribution uniformity and the dimensional stability of the micro-pore structure of the antibacterial coating are improved.
Detailed Description
The present application is described in further detail below with reference to examples.
In the raw material of the antibacterial coating, the titanium dioxide is nano titanium dioxide, and the average particle size of the nano titanium dioxide is 5-30nm. Further preferably, the average particle diameter of the nano titanium dioxide is 20nm, and the manufacturer of the nano titanium dioxide is Shanghai super Wei nano technology Co., ltd, and the model is CW-TiO 2 -001, 99.9% purity.
Preferably, the zinc oxide is nano zinc oxide, and the average particle size of the nano zinc oxide is 10-50nm. Further preferably, the average particle size of the nano zinc oxide is 20nm, and the manufacturer of the nano zinc oxide is Shanghai super-Wei nano technology Co., ltd, the model is CW-ZnO-001, and the purity is 99.9%.
Preferably, the silane coupling agent is any one of gamma-aminopropyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy. Further preferably, the silane coupling agent is gamma-aminopropyl triethoxysilane, and the manufacturer is Jinan Rong chemical industry Co., ltd.
Preferably, the manufacturer of diethylene glycol is Jinan Huijian trade company, inc., and CAS is 111-46-6.
Preferably, the manufacturer of paraformaldehyde is Jinan Ming Xin chemical Co., ltd.
Preferably, the sodium bicarbonate is ground, and the average mesh number of the ground sodium bicarbonate is 2000-5000. Further preferably, the average mesh number of the sodium bicarbonate after the grinding treatment is 3000.
Preferably, the mass ratio of the pore-forming agent to the polyacrylate emulsion is (0.5-1.2) 1, and the solid content of the polyacrylate emulsion is 30-60%. Further preferably, the polyacrylate emulsion has a solids content of 52% and the manufacturer is Jinan Huijian chemical Co., ltd.
Preferably, the sodium bicarbonate is modified sodium bicarbonate, and the modified sodium bicarbonate is prepared by coating sodium bicarbonate with quaternary ammonium salt.
The preparation method of the modified sodium bicarbonate comprises the following steps:
s1: dissolving quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Preferably, the manufacturer of octadecyl dimethyl trimethyl trisilyl propyl ammonium chloride is Wu Hanka distributed to chemical industry Co.
Preferably, the polyoxyethylene ether sulfonate is sodium fatty alcohol polyoxyethylene ether sulfonate, the CAS number is 9004-82-4, and the manufacturer is Shandong Dairy poplar New Material Co.
Preferably, the polyvinyl alcohol manufacturer is a chemical industry Co., ltd. In the east, model CX336.
The utility model provides a deodorizing casual shoes of reduction peculiar smell, includes the shoes body, and shoes body includes vamp, insole and outsole, and vamp medial surface and insole top surface all are coated with antibiotic coating, and antibiotic coating is by foretell antibiotic material heat cure formation, and heating temperature is 120-180 ℃. Further preferably, the heating temperature is 150 ℃.
The main raw material information of the examples and comparative examples of the present application are shown in table 1.
Table 1 main raw material information of examples and comparative examples of the present application
Figure BDA0003118218590000041
Figure BDA0003118218590000051
Example 1
The deodorizing leisure shoes with the odor reduction function comprise shoe bodies, wherein each shoe body comprises a vamp, a midsole and an outsole, antibacterial coatings are coated on the inner side surface of each vamp and the top surface of each midsole, the thickness of each antibacterial coating is 1.5mm, and each antibacterial coating is formed by heating an antibacterial material to 150 ℃ and curing.
The antibacterial material of the embodiment is prepared from the following raw materials in parts by weight: 60kg of polyacrylate emulsion, 10kg of antibacterial agent, 5kg of cross-linking agent, 2kg of dispersing agent and 6kg of pore-forming agent.
Wherein the solid content of the polyacrylate emulsion is 52%, and the manufacturer is Jinan Huijian chemical industry Co., ltd.
The antibacterial agent consists of titanium dioxide and zinc oxide according to the mass ratio of 2:1. The titanium dioxide is nano titanium dioxide, the average grain diameter of the nano titanium dioxide is 20nm, the manufacturer of the nano titanium dioxide is Shanghai super-Wei nano technology Co., ltd, and the model is CW-TiO 2 -001, 99.9% purity. The zinc oxide is nano zinc oxide, the average grain diameter of the nano zinc oxide is 20nm, the manufacturer of the nano zinc oxide is Shanghai super-Wei nano technology Co., ltd, the model is CW-ZnO-001, and the purity is 99.9%.
The cross-linking agent is gamma-aminopropyl triethoxysilane, and the manufacturer is Jinan Rong chemical industry Co., ltd.
The dispersant is diethylene glycol, the manufacturer of diethylene glycol is Jinan Huijian Chuan trade company, and CAS is 111-46-6.
The pore-forming agent is paraformaldehyde, and the manufacturer is Jinan Ming Xin chemical Co.
Examples 2 to 5
The deodorizing leisure shoes for reducing peculiar smell of the embodiments 2-5 comprise a shoe body, wherein the shoe body comprises a vamp, a midsole and an outsole, the inner side surface of the vamp and the top surface of the midsole are coated with antibacterial coatings, the thickness of the antibacterial coatings is 1.5mm, and the antibacterial coatings are formed by heating antibacterial materials to 150 ℃ and curing.
The amounts of the respective raw materials added for the antibacterial materials of examples 2 to 5 are shown in Table 2.
TABLE 2 addition amount of raw materials for antibacterial materials in examples 2 to 5
Figure BDA0003118218590000052
Figure BDA0003118218590000061
Wherein the solid content of the polyacrylate emulsion is 52%, and the manufacturer is Jinan Huijian chemical industry Co., ltd.
The antibacterial agent consists of titanium dioxide and zinc oxide according to the mass ratio of 2:1. The titanium dioxide is nano titanium dioxide, the average grain diameter of the nano titanium dioxide is 20nm, the manufacturer of the nano titanium dioxide is Shanghai super-Wei nano technology Co., ltd, and the model is CW-TiO 2 -001, 99.9% purity. The zinc oxide is nano zinc oxide, the average grain diameter of the nano zinc oxide is 20nm, the manufacturer of the nano zinc oxide is Shanghai super-Wei nano technology Co., ltd, the model is CW-ZnO-001, and the purity is 99.9%.
The cross-linking agent is gamma-aminopropyl triethoxysilane, and the manufacturer is Jinan Rong chemical industry Co., ltd.
The dispersant is diethylene glycol, the manufacturer of diethylene glycol is Jinan Huijian Chuan trade company, and CAS is 111-46-6.
The pore-forming agent is sodium bicarbonate, the sodium bicarbonate is ground, and the average mesh number of the ground sodium bicarbonate is 3000.
Example 6
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 3 in that: the pore-forming agent in the antibacterial material consists of paraformaldehyde and sodium bicarbonate according to the mass ratio of 0.5:3. The rest is the same as in example 3.
Example 7
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 3 in that: the pore-forming agent in the antibacterial material consists of paraformaldehyde and sodium bicarbonate according to the mass ratio of 0.8:5. The rest is the same as in example 3.
Example 8
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 3 in that: the pore-forming agent in the antibacterial material consists of paraformaldehyde and sodium bicarbonate according to the mass ratio of 1.2:7. The rest is the same as in example 3.
Example 9
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 7 in that: the sodium bicarbonate in the antibacterial material raw material was modified sodium bicarbonate, and the rest was the same as in example 7.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is dodecyl ammonium chloride, and the manufacturer of the dodecyl ammonium chloride is Kang Disi chemical industry (Hubei) limited company. The molar ratio of sodium bicarbonate to dodecyl ammonium chloride was 1:3.
Example 10
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 9 in that: the sodium bicarbonate in the antibacterial material raw material was modified sodium bicarbonate, and the rest was the same as in example 9.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is octadecyl dimethyl trimethyl silylpropyl ammonium chloride, and the molar ratio of sodium bicarbonate to octadecyl dimethyl trimethyl silylpropyl ammonium chloride is 1:3.
Example 11
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 9 in that: the sodium bicarbonate in the antibacterial material raw material was modified sodium bicarbonate, and the rest was the same as in example 9.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride, and the mol ratio of sodium bicarbonate to N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride is 1:3.
Example 12
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 9 in that: the sodium bicarbonate in the antibacterial material raw material is modified sodium bicarbonate. The remainder was the same as in example 9.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is composed of octadecyl dimethyl trimethyl trisilyl propyl ammonium chloride and N, N-dimethyl dodecyl aminopropyl trimethoxy silane ammonium chloride according to the mass ratio of 5:2, and the molar ratio of sodium bicarbonate to alkyl quaternary ammonium salt is 1:3.
Example 13
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 9 in that: the sodium bicarbonate in the antibacterial material raw material is modified sodium bicarbonate. The remainder was the same as in example 9.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is composed of octadecyl dimethyl trimethyl trisilyl propyl ammonium chloride and N, N-dimethyl dodecyl aminopropyl trimethoxy silane ammonium chloride according to the mass ratio of 6.5:2.5, and the molar ratio of sodium bicarbonate to alkyl quaternary ammonium salt is 1:3.
Example 14
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 9 in that: the sodium bicarbonate in the antibacterial material raw material is modified sodium bicarbonate. The remainder was the same as in example 9.
The preparation method of the modified sodium bicarbonate of the embodiment comprises the following steps:
s1: dissolving alkyl quaternary ammonium salt in ethanol, adding sodium bicarbonate, and stirring for 10min to obtain a mixture;
s2: and (3) drying the mixture in the step S1 in an oven, wherein the temperature of the oven is set to 55 ℃.
Wherein the alkyl quaternary ammonium salt is composed of octadecyl dimethyl trimethyl trisilyl propyl ammonium chloride and N, N-dimethyl dodecyl aminopropyl trimethoxy silane ammonium chloride according to the mass ratio of 8:3, and the molar ratio of sodium bicarbonate to alkyl quaternary ammonium salt is 1:3.
Example 15
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 3 in that: the antibacterial material also comprises 0.8kg of fatty alcohol-polyoxyethylene ether sodium sulfonate, wherein the manufacturer of the fatty alcohol-polyoxyethylene ether sodium sulfonate is Shandong Populus deltoides new material Co., ltd, and the CAS number is 9004-82-4. The rest is the same as in example 3.
Example 16
The deodorizing leisure shoes with reduced bad smell of the present embodiment are different from those of embodiment 15 in that: the antibacterial material also comprises 1.5kg of polyvinyl alcohol, and the manufacturer of the polyvinyl alcohol is Shandong jun chemical industry Co., ltd, and the model is CX336. The remainder was the same as in example 15.
Comparative example
Comparative example 1
The deodorizing leisure shoes with the peculiar smell reduction function comprise shoe bodies, wherein each shoe body comprises a vamp, a midsole and an outsole, the inner side surface of each vamp and the top surface of each midsole are coated with an antibacterial coating, the thickness of each antibacterial coating is 1.5mm, and each antibacterial coating is formed by heating an antibacterial material to 150 ℃ and curing.
The antibacterial material of the comparative example is prepared from the following raw materials in parts by weight: 60kg of polyacrylate emulsion, 10kg of antibacterial agent, 5kg of cross-linking agent, 2kg of dispersing agent and 6kg of pore-forming agent.
Wherein the solid content of the polyacrylate emulsion is 52%, and the manufacturer is Jinan Huijian chemical industry Co., ltd.
The antibacterial agent consists of titanium dioxide and zinc oxide according to the mass ratio of 2:1. The titanium dioxide is nano titanium dioxide, the average grain diameter of the nano titanium dioxide is 20nm, the manufacturer of the nano titanium dioxide is Shanghai super-Wei nano technology Co., ltd, and the model is CW-TiO 2 -001, 99.9% purity. The zinc oxide is nano zinc oxide, the average grain diameter of the nano zinc oxide is 20nm, the manufacturer of the nano zinc oxide is Shanghai super-Wei nano technology Co., ltd, the model is CW-ZnO-001, and the purity is 99.9%.
The cross-linking agent is gamma-aminopropyl triethoxysilane, and the manufacturer is Jinan Rong chemical industry Co., ltd.
The dispersant is diethylene glycol.
The pore-forming agent is polyvinyl chloride powder, and the manufacturer is Beijing Tianhai Xingsheng chemical industry Co.
Comparative example 2
The deodorizing leisure shoes with the peculiar smell reduction function comprise shoe bodies, wherein each shoe body comprises a vamp, a midsole and an outsole, the inner side surface of each vamp and the top surface of each midsole are coated with an antibacterial coating, the thickness of each antibacterial coating is 1.5mm, and each antibacterial coating is formed by heating an antibacterial material to 150 ℃ and curing.
The antibacterial material of the comparative example is prepared from the following raw materials in parts by weight: 60kg of polyacrylate emulsion, 10kg of antibacterial agent, 5kg of cross-linking agent and 2kg of dispersing agent.
Wherein the solid content of the polyacrylate emulsion is 52%, and the manufacturer is Jinan Huijian chemical industry Co., ltd.
The antibacterial agent consists of titanium dioxide and zinc oxide according to the mass ratio of 2:1. The titanium dioxide is nano titanium dioxide, the average grain diameter of the nano titanium dioxide is 20nm, the manufacturer of the nano titanium dioxide is Shanghai super-Wei nano technology Co., ltd, and the model is CW-TiO 2 -001, 99.9% purity. The zinc oxide is nano zinc oxide, the average grain diameter of the nano zinc oxide is 20nm, the manufacturer of the nano zinc oxide is Shanghai super-Wei nano technology Co., ltd, the model is CW-ZnO-001, and the purity is 99.9%.
The cross-linking agent is gamma-aminopropyl triethoxysilane, and the manufacturer is Jinan Rong chemical industry Co., ltd.
The dispersant is diethylene glycol.
Performance test
Detection method
Deodorant casual shoes with reduced odor of examples 1-16 and comparative examples 1-2 were taken according to GB/T20944.3-2008, evaluation of antibacterial Properties of textiles section 3: the oscillating method was used for antibacterial test, and the antibacterial rate (%) after 30 times of washing was measured, and the test results are shown in table 3.
The uppers of deodorizing leisure shoes for reducing the odor of examples 1 to 16 and comparative examples 1 to 2 were tested for breathability according to GB/T5453-1997 determination of textile breathability, and the test results are shown in Table 4.
Table 3 results of antibacterial tests of deodorizing leisure shoes with reduced bad smell of examples 1 to 16 and comparative examples 1 to 2
Figure BDA0003118218590000091
Figure BDA0003118218590000101
Table 4 results of the vamp breathability test of the odor-reduced deodorant casual shoes of examples 1 to 16 and comparative examples 1 to 2
Figure BDA0003118218590000102
Figure BDA0003118218590000111
As can be seen from comparative examples 1-5 and comparative examples 1-2 in combination with tables 3 and 4, the pore-forming agent significantly improves the breathability of the antimicrobial coating.
Comparative examples 6-8 in combination with tables 3 and 4, it can be seen that the combination of paraformaldehyde and sodium bicarbonate at a mass ratio of 0.8:5 further improves the breathability of the antimicrobial coating.
As can be seen from comparative examples 9-11 and comparative examples 1-2 in combination with tables 3 and 4, the quaternary ammonium salt improved the breathability and bacteriostatic properties of the antimicrobial coating to some extent.
Comparative examples 12-14 in combination with tables 3 and 4, it can be seen that the combination of octadecyl dimethyl trimethyl silylpropyl ammonium chloride and N, N-dimethyl dodecyl aminopropyl trimethoxy silane ammonium chloride further improves the breathability of the antimicrobial coating.
As can be seen by comparing examples 1-5, examples 15-16, and combining tables 3 and 4, the emulsifier and polyvinyl alcohol promote uniformity of the antimicrobial coating.
In summary, the deodorizing leisure shoes for reducing peculiar smell have the advantages of good air permeability and excellent antibacterial performance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (4)

1. The utility model provides a deodorizing leisure shoes of reduction peculiar smell, its characterized in that includes the shoes body, shoes body includes vamp, insole and big end, vamp medial surface and insole top surface all are coated with antibiotic coating, antibiotic coating is by antibiotic material heat cure formation, antibiotic material is made by the raw materials including following weight portion: 60-80 parts of polyacrylate emulsion, 10-20 parts of antibacterial agent, 5-12 parts of cross-linking agent, 2-5 parts of dispersing agent and 6-15 parts of pore-forming agent; the antibacterial agent consists of (1-3) and (2-5) of titanium dioxide and zinc oxide in mass ratio, the cross-linking agent is a silane coupling agent, the dispersing agent is diethylene glycol, and the pore-forming agent consists of (0.5-1.2) and (3-7) of paraformaldehyde and sodium bicarbonate in mass ratio; the mass ratio of the pore-forming agent to the polyacrylate emulsion is 1 (5-10), and the solid content of the polyacrylate emulsion is 30-60%; the sodium bicarbonate is modified sodium bicarbonate, the modified sodium bicarbonate is prepared by coating sodium bicarbonate with alkyl quaternary ammonium salt, and the alkyl quaternary ammonium salt is composed of octadecyl dimethyl trimethyl silicon propyl ammonium chloride and N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride according to the mass ratio of (5-8) to (2-3).
2. A deodorant casual shoe with reduced odor according to claim 1, wherein: the antibacterial material is prepared from the following raw materials in parts by weight: 65-70 parts of polyacrylate emulsion, 12-17 parts of antibacterial agent, 7-10 parts of cross-linking agent, 3-4.5 parts of dispersing agent and 8-13 parts of pore-forming agent; the antibacterial agent consists of (1-3) and (2-5) of titanium dioxide and zinc oxide in mass ratio, the cross-linking agent is a silane coupling agent, the dispersing agent is diethylene glycol, and the pore-forming agent consists of (0.5-1.2) and (3-7) of paraformaldehyde and sodium bicarbonate in mass ratio; the mass ratio of the pore-forming agent to the polyacrylate emulsion is 1 (5-10), and the solid content of the polyacrylate emulsion is 30-60%; the sodium bicarbonate is modified sodium bicarbonate, the modified sodium bicarbonate is prepared by coating sodium bicarbonate with alkyl quaternary ammonium salt, and the alkyl quaternary ammonium salt is composed of octadecyl dimethyl trimethyl silicon propyl ammonium chloride and N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride according to the mass ratio of (5-8) to (2-3).
3. A deodorant casual shoe with reduced odor according to claim 1 or 2, wherein: the antibacterial material also comprises (0.5-1) emulsifying agent in parts by weight, wherein the emulsifying agent is polyoxyethylene ether sulfonate.
4. A deodorant casual shoe with reduced odor according to claim 1 or 2, wherein: the raw materials of the antibacterial material also comprise (1-2) weight parts of polyvinyl alcohol.
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* Cited by examiner, † Cited by third party
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CN202980328U (en) * 2012-12-24 2013-06-12 巨一集团有限公司 Antibacterial and deodorant boot
CN103211350A (en) * 2013-03-28 2013-07-24 范绍明 Insoles with beriberi treating function
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