CN112029332A - Water-based antibacterial coating and preparation method thereof - Google Patents
Water-based antibacterial coating and preparation method thereof Download PDFInfo
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- CN112029332A CN112029332A CN202010923458.XA CN202010923458A CN112029332A CN 112029332 A CN112029332 A CN 112029332A CN 202010923458 A CN202010923458 A CN 202010923458A CN 112029332 A CN112029332 A CN 112029332A
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
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Abstract
The invention relates to a water-based antibacterial coating and a preparation method thereof, in particular to a water-based antibacterial real-color paint for children toys. The water-based antibacterial coating comprises the following components: 50 parts of aqueous emulsion; 20 to 34 parts by weight of flower-shaped nano titanium dioxide-acrylic resin composite particles; 1 to 4 parts by weight of a film-forming assistant; 1 to 6 parts by weight of an aqueous auxiliary agent; 1 to 4 parts of water-based color paste; deionized water, 2 to 50 parts by weight. The flower-shaped nano titanium dioxide-acrylic resin composite particles have a core-shell structure, wherein silane modified flower-shaped nano titanium dioxide is used as a core layer, and an organosilicon modified acrylic polymer is used as a shell layer. The water-based antibacterial coating has excellent antibacterial property and excellent heat transfer property.
Description
Technical Field
The invention relates to a water-based antibacterial coating and a preparation method thereof, in particular to a water-based antibacterial solid paint for children toys and a preparation method thereof.
Background
With the improvement of environmental protection consciousness and the attention of people on self health, people aggravate how to effectively reduce bacteria in daily behaviors to cause adverse effects on life and reduce the probability of diseases. Therefore, the antibacterial material products, particularly the antibacterial materials which are easy to directly touch gradually come into the vision of people, and the antibacterial coating is produced. Compared with paint, the water-based paint is safer and more environment-friendly in raw material selection, production process and consumption use process. Therefore, under the development trend of the market and the vigorous promotion of national policies, the water paint which is more environment-friendly and healthier meets huge development space, and the water paint with the antibacterial effect also receives great attention.
The children toy solid color paint not only involves skin contact during use, but also may be placed in mouth to contact with mucous membrane tissues, and both the contact can induce bacterial growth. Therefore, the rapid bactericidal performance and the long-acting bacteriostatic ability are very critical. More severe than other coatings. In addition, the children toy solid color paint has good adhesive force and excellent heat transfer printing performance and flexibility to various woods under the condition of ensuring low VOC. The heat transfer printing performance is better in the aspect of color, and rich and colorful colors can be embodied. At present, a part of water-based children paints replace solvent-based paints, the harm to the bodies of children is reduced in the aspects of environmental protection and low VOC, but the problems of low adhesive force, insufficient heat transfer printing performance, insufficient long-acting antibacterial capacity and the like of most of water-based solid-color paints sprayed on toys are still very obvious.
CN106085181B discloses a water-based children toy colored paint and a preparation method thereof, which realizes good adhesion, good wear resistance, high gloss and other performances on toy balls such as PVC, PU and the like by blending two aromatic water-based polyurethane resins and adding a wear-resistant additive in the formula. But does not solve the rapid sterilization and long-acting bacteriostasis performance of the paint film.
The CN103304762B patent discloses that an organosilicon quaternary ammonium salt modified polyurethane resin combines the double effects of low surface energy and poisoning, and can be used as a film-forming substance of a marine antifouling paint to inhibit the adsorption of marine organisms and kill bacteria adsorbed on the surface of a ship body. The antibacterial mechanism of the quaternary ammonium salt is mainly to destroy the cell membrane and a protein synthesis system through the reaction of an antibacterial group and a sulfhydryl on the surface of a microorganism, so that the integrity of the cell is destroyed, and the cell wall is broken. When the number of the residual dead cell walls on the surface of the paint film is too large, the antibacterial groups of the quaternary ammonium salt can not be in direct contact with bacteria, so that the antibacterial capability is obviously weakened. Therefore, the quaternary ammonium salt antibacterial substance has low concentration of taking effect, quick effect and good bactericidal capacity on bacteria and mould, but cannot have long-acting antibacterial capacity.
Therefore, a new formula of the water-based antibacterial toy paint for children is required to be found, and the functions of safe and nontoxic paint film, quick sterilization and long-acting bacteriostasis can be realized; but also can ensure good adhesive force to various base materials, has excellent heat transfer printing performance and embodies rich colors.
Disclosure of Invention
The invention aims to provide a water-based antibacterial coating, in particular to a water-based antibacterial toy solid-color paint which has the functions of safety, no toxicity, quick sterilization and long-acting bacteriostasis; can ensure good adhesive force to various base materials, particularly wood, has excellent heat transfer printing performance and embodies rich colors.
The flower-shaped nano titanium dioxide-acrylic resin composite particles are used for replacing the traditional water-based white slurry, and due to the combination of the flower-shaped nano titanium dioxide and the acrylic resin, the whole particles have stronger hydrophilicity, are more stable and difficult to settle in water, can be better dispersed in the resin in the paint preparation process, and have better stability compared with the water-based white slurry. In addition, the antibacterial mechanism of the nano titanium dioxide is the oxidation damage mechanism of active oxygen (ROS), and oxygen vacancies caused by the surface defects of the titanium dioxide can promote O dissolved in water2Reduction to O2 –、·OH、H2O2ROS have strong oxidizing properties to peroxidate lipid, damage bacterial cell membranes and finally kill bacteria. Compared with the conventional nano titanium dioxide, the flower-shaped nano titanium dioxide has larger specific surface area, increased surface oxygen defects, increased surface OH < - >, and increased O2 –The easier the enrichment and the stability are, the stronger the antibacterial activity is. The acrylic resin coated on the surface can fully disperse flower-shaped nano titanium dioxide, and has the advantages of low toxicity, high safety, broad-spectrum antibacterial property, good thermal stability, long acting time and the like in a paint film. The heat transfer printing is a new method for printing patterns on various material commodities, and because the surface of the children toy paint has the performance requirement of transferring colorful patterns, the patterns can be easily and completely transferred to the surface of a paint film and have good adhesive force on the surface of the paint film, which is very necessary. The quality of the heat transfer printing performance is not only related to the hardness and softness of the resin in the paint film, but also greatly related to the type of the filler. Common titanium dioxide has rigidity, yellowing, pulverization and other properties are easy to appear when the common titanium dioxide is added into water paint, but the partial surface of flower-shaped nano titanium dioxide is coated with acrylic resin, so that titanium dioxide particles have better flexibility, can play a role of a film forming substance in a film forming process and can provide better adhesive force, when transfer printing is carried out at high temperature, the acrylic resin on the outer layer can be softened to provide certain viscosity, patterns are easier to transfer to the surface of a paint film, the bonding capacity of the resin on the outer layer of the composite particles and the patterns is stronger, and therefore the patterns are on the surface of the paint film after coolingStill has excellent adhesion. The flower-like nano titanium dioxide-acrylic resin composite particles are applied to Wanhua aqueous resins such as Lacper4506, Lacper4501, Lacper4219 and other emulsions to prepare solid color paint which has good antibacterial performance, adhesive force and thermal transfer printing performance.
The invention also aims to provide a method for preparing the flower-shaped nano titanium dioxide-acrylic resin composite particles.
The invention also aims to provide a preparation method of the water-based antibacterial coating, which has simple and feasible steps.
According to a first aspect of the present invention, there is provided an aqueous antimicrobial coating, in particular an aqueous antimicrobial children's toy solid color paint, comprising the following components:
the flower-shaped nano titanium dioxide-acrylic resin composite particles have a core-shell structure, wherein silane modified flower-shaped nano titanium dioxide is used as a core layer, and an organosilicon modified acrylic polymer is used as a shell layer.
Preferably, the weight ratio of the core layer to the shell layer of the flower-shaped nano titanium dioxide-acrylic resin composite particle is 12: 1 to 5: 1, more preferably 10: 1 to 5: 1. if the ratio is larger than this range, the shell layer becomes too thin, and it becomes difficult to achieve a good transfer effect. If the ratio is less than this range, the shell layer becomes too thick, and the bactericidal effect of titanium dioxide may be impaired.
Preferably, the aqueous emulsion is one or a mixture of more than two selected from acrylate emulsion, polyvinyl acetate emulsion, silicone-acrylic emulsion, styrene-acrylic emulsion, polyurethane dispersion, polyvinyl acetate-acrylic emulsion, ethylene acrylic emulsion and ethylene vinyl acetate emulsion. The solid content in the aqueous emulsion is 30-60 wt% based on the total weight of the aqueous emulsion.
The aqueous emulsion may be, for example, an aqueous resin product of Wanhua chemical group Co., Ltd., such as emulsions of Lacper4506, Lacper4501, and Lacper 4219.
Preferably, the film forming aid is selected from one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether and ethylene glycol hexyl ether, preferably one or two of dipropylene glycol methyl ether and dipropylene glycol butyl ether.
Preferably, the aqueous auxiliary agent includes, but is not limited to, an antifoaming agent, a substrate wetting agent, a leveling agent, a pH adjuster, a thickener.
Preferably, the defoamer is used in an amount of 0 to 1, preferably 0.1 to 0.6 parts by weight; the amount of the substrate wetting agent is 0 to 1, preferably 0.3 to 0.6 parts by weight; the leveling agent is used in an amount of 0 to 1.5, preferably 0.1 to 1 part by weight; the amount of the pH regulator is 0 to 1.5 parts by weight; the thickeners are used in amounts of 0 to 1.5 parts by weight, preferably 0.2 to 1.5 parts by weight.
Preferably, the defoaming agent is a silicone defoaming agent, more preferably one or more selected from Tego-805, Tego-810, Tego-815, Tego-825, Tego-902w or Tego-1488 from the winning industry.
Preferably, the substrate wetting agent is a polyether siloxane copolymer, more preferably one or more selected from Byk-346, Byk-348 in Pico chemical, Surfgnol-104BC in gas chemical, or Surfgnol-104E in gas chemical.
Preferably, the leveling agent is organic modified polydimethylsiloxane, and more preferably one or more selected from Tego-410, Tego-450, Tego-245 or Tego-270 in the winning industry.
Preferably, the pH adjuster is one or more of ammonia, ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol, sodium hydroxide or potassium hydroxide.
Preferably, the thickener is one or more of an alkali swelling thickener, a polyurethane associative thickener or hydroxyethyl cellulose, preferably a polyurethane associative thickener.
Preferably, the aqueous antibacterial coating is a coating for a wooden material.
In the invention, the flower-shaped nano titanium dioxide-acrylic resin composite particles have a core-shell structure design, and silane modified flower-shaped nano titanium dioxide is used as a core layer, so that the rapid bactericidal performance and the long-acting bacteriostatic ability are provided; the acrylic polymer emulsion modified by organic silicon as a shell layer has good hydrophilicity, good adhesive force to various base materials and good heat transfer printing performance.
According to a second aspect of the present invention, there is provided a method for preparing the flower-like nano titanium dioxide-acrylic resin composite particles, comprising the steps of:
(A) preparation of silane modified flower-shaped nano titanium dioxide
Dispersing 75 parts by weight of flower-shaped nano titanium dioxide in a mixed solvent of 90-150 parts by weight, preferably 120-150 parts by weight of ethanol and 90-150 parts by weight, preferably 90-120 parts by weight of water, then adding 0.3-1.5 parts by weight, preferably 0.6-1.2 parts by weight of silane coupling agent, after full dispersion, transferring the obtained suspension into a microwave hydrothermal kettle, reacting under the microwave hydrothermal condition of 30-80 ℃, preferably 50-80 ℃, so that the silane coupling agent is rapidly hydrolyzed and bonded on the surface of the flower-shaped nano titanium dioxide, cooling to room temperature, filtering the suspension, and washing with deionized water to obtain silane-modified flower-shaped nano titanium dioxide;
(B) preparation of Shell Pre-emulsion
35 parts by weight of an alkyl methacrylate; 5 to 20, preferably 15 to 18 parts by weight of an alkyl acrylate; 1.5 to 5, preferably 1.5 to 4 parts by weight of a carboxylic acid crosslinking monomer; 1.5 to 5, preferably 1.5 to 3 parts by weight of a vinyl group-containing silicone monomer; 1 to 5, preferably 3 to 5 parts by weight of an emulsifier; 15 to 100, preferably 25 to 80 parts by weight of deionized water, and stirring to fully emulsify the deionized water to obtain a shell layer pre-emulsion;
(C) preparing flower-shaped nano titanium dioxide-acrylic resin composite particles
Adding 15 to 46, preferably 15 to 30 parts by weight of deionized water and 1 to 5 parts by weight of emulsifier into 60 parts by weight of the silane modified flower-shaped nano titanium dioxide obtained in the step (A) and stirring to obtain a core-layer pre-emulsion, when the temperature is raised to 50 ℃ to 90 ℃, dropwise adding an initiator solution containing 0.1 to 3 parts by weight of initiator and 5 to 15, preferably 7 to 10 parts by weight of the shell-layer pre-emulsion prepared in the step (B) into the system for 1 to 3 hours, and controlling the reaction temperature of the emulsion to be 50 ℃ to 90 ℃, preferably 80 ℃ to 85 ℃; after the dropwise addition, keeping the temperature for 0.5 to 3 hours; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization, regulating the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles.
Preferably, the silane coupling agent is a coupling agent containing a double bond in the molecular chain, preferably one or more selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane (KH-570) and 3-aminotriethoxysilane (KH-550).
Preferably, the flower-like nano titanium dioxide is anatase type, and has stronger bactericidal effect compared with the conventional titanium dioxide.
Preferably, the alkyl methacrylate monomer is one or more selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or n-octyl methacrylate.
Preferably, the alkyl acrylate monomer is acrylic acid C1-C10The alkyl ester monomer is more preferably one or more selected from methyl acrylate, ethyl acrylate, butyl acrylate or n-pentyl acrylate.
Preferably, the carboxylic acid crosslinking monomer is one or more selected from acrylic acid or methacrylic acid.
Preferably, the organosilicon monomer containing vinyl is any one selected from vinyltrimethoxysilane, vinyltrimethyltriethoxysilane or vinyltriisopropoxysilane.
Preferably, the emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether and salts thereof or fatty alcohol ether phosphate and salts thereof.
Preferably, the initiator may be, but is not limited to, one or more of ammonium persulfate, sodium persulfate, or potassium persulfate.
Preferably, the neutralizing agent used may be, but is not limited to, one or more of amines (e.g., ammonia) or alkali metal hydroxides (e.g., sodium hydroxide).
Preferably, the initiator concentration in the initiator solution is from 1 wt% to 50 wt%, more preferably from 1 wt% to 20 wt%, based on the total weight of the initiator solution.
According to a third aspect of the present invention, there is provided a method for preparing the water-based antibacterial coating of the present invention, comprising the steps of:
1) adding the aqueous emulsion into a container, then sequentially adding the flower-shaped nano titanium dioxide-acrylic resin composite particles, the film-forming aid, the aqueous aid (selected from one or more of a defoaming agent, a base material wetting agent, a flatting agent and a thickening agent), the aqueous color paste and deionized water under stirring, and continuously stirring to uniformly disperse the aqueous color paste and the deionized water. Preferably, the dispersion is continued for at least 15-30 min after the addition with the dispersion speed unchanged.
Preferably, the stirring speed in the step 1) is 600-900 r/min.
Preferably, the method further comprises the steps of:
2) and (3) filtering the mixture obtained in the step (1) by using a 100-400-mesh filter screen to obtain the water-based antibacterial coating.
The water-based antibacterial coating has the positive effects that: the flower-shaped nano titanium dioxide-acrylic resin composite particle not only can keep the antibacterial performance of the flower-shaped nano titanium dioxide, but also can be stably dispersed in water; the pigment is used as water-based white slurry with an antibacterial function and is added into a commercially available water-based emulsion such as acrylic emulsion, so that the pigment has good color development property on water-based color paste; the water-based antibacterial children toy solid-color paint is prepared by matching with a film-forming assistant, a water-based assistant and the like, and shows excellent adhesive force and flexibility and excellent heat transfer printing performance on the surfaces of various substrates, particularly the surfaces of wood.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the following embodiments, which should be construed as limiting the scope of the present invention.
< sources of raw materials >
KH-570, nanjing nender new materials technologies ltd;
flower-like nano titanium dioxide with the particle size of 30-50 nm and the particle size of 130-180m2(ii)/g, Shanghai Huizi Xiannao New Material Co., Ltd;
methyl methacrylate from winning (Shanghai) Limited liability company;
butyl acrylate, Vanhua chemical group, Inc.;
acrylic acid, Vanhua chemical group, Inc.;
sodium lauryl sulfate, national pharmaceutical group chemical agents limited;
ammonium persulfate, national pharmaceutical group chemical agents ltd.
Preparation of example 1
Preparation of silane modified flower-like nano titanium dioxide
Dispersing 75g of flower-shaped nano titanium dioxide in a mixed solution of 135g of ethanol and 100g of deionized water, carrying out ultrasonic treatment for 15min, adding 0.8g of gamma-methacryloxypropyltrimethoxysilane (KH-570) and continuing ultrasonic treatment for 30min, transferring the obtained suspension into a microwave hydrothermal kettle, carrying out microwave hydrothermal treatment at 50 ℃ for 30min to enable a silane coupling agent to be rapidly hydrolyzed and combined on the surface of the flower-shaped nano titanium dioxide, cooling to room temperature, filtering the suspension, and washing with deionized water to obtain the silane-modified flower-shaped nano titanium dioxide.
Preparation of a Shell Pre-emulsion
Obtained by controlling the dropping process in the preparation method of the water-based acrylic polymer emulsion. 30g of methyl methacrylate, 18g of butyl acrylate, 4g of acrylic acid, 5g of vinyltrimethoxysilane, 5g of sodium dodecyl benzene sulfonate and 72g of deionized water are weighed and stirred for pre-emulsification for 60min to obtain a shell layer pre-emulsion.
Preparation of flower-like nano titanium dioxide-acrylic resin composite particle A
Weighing 0.1g of initiator, and dissolving the initiator in 10g of deionized water to obtain an initiator solution;
stirring 16.6g of deionized water and 3.4g of sodium dodecyl benzene sulfonate, fully stirring 60g of silane modified flower-shaped nano titanium dioxide to be used as a core-layer pre-emulsion, dropwise adding an initiator solution and 15.6g of a shell-layer pre-emulsion into the system for 3 hours when the temperature is raised to 80 ℃, and controlling the reaction temperature of the emulsion to be 80 ℃; preserving the heat for 2 hours after the dropwise adding is finished; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization to adjust the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles A, wherein the weight ratio of the core layer to the shell layer is 9.0: 1.
preparation of example 2
Preparation of flower-like nano titanium dioxide-acrylic resin composite particle B
Silane-modified flower-like nano-titania was prepared according to preparation example 1.
Preparation of a Shell Pre-emulsion
Obtained by controlling the dropping process in the preparation method of the water-based acrylic polymer emulsion. 30g of methyl methacrylate, 15g of butyl acrylate, 3g of acrylic acid, 2.5g of vinyltrimethoxysilane, 4g of sodium dodecyl benzene sulfonate and 64g of deionized water are weighed and stirred for pre-emulsification for 60min to obtain a shell layer pre-emulsion.
Weighing 0.4g of initiator, and dissolving the initiator in 10g of deionized water to obtain an initiator solution;
stirring 24.4g of deionized water and 2.6g of sodium dodecyl benzene sulfonate, fully stirring 60g of silane modified flower-shaped nano titanium dioxide to be used as a core-layer pre-emulsion, dropwise adding an initiator solution and 19.1g of a shell-layer pre-emulsion into the system for 3 hours when the temperature is raised to 80 ℃, and controlling the reaction temperature of the emulsion to be 80 ℃; preserving the heat for 2 hours after the dropwise adding is finished; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization to adjust the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles B, wherein the weight ratio of the core layer to the shell layer is 7.4: 1.
preparation of example 3
Preparation of flower-like nano titanium dioxide-acrylic resin composite particle C
Silane-modified flower-like nano-titania was prepared according to preparation example 1.
Preparation of a Shell Pre-emulsion
Obtained by controlling the dropping process in the preparation method of the water-based acrylic polymer emulsion. 30g of methyl methacrylate, 5g of butyl acrylate, 1.5g of acrylic acid, 1.5g of vinyl trimethoxy silane, 1.5g of sodium dodecyl benzene sulfonate and 50g of deionized water are weighed and stirred for pre-emulsification for 60min to obtain a shell layer pre-emulsion.
Weighing 0.75 g of initiator, and dissolving the initiator in 10g of deionized water to obtain an initiator solution;
stirring 22.4g of deionized water and 2.6g of sodium dodecyl sulfate, fully stirring 60g of silane modified flower-shaped nano titanium dioxide to be used as a core-layer pre-emulsion, dropwise adding an initiator solution and 23g of shell-layer pre-emulsion into the system for 3 hours when the temperature is raised to 80 ℃, and controlling the reaction temperature of the emulsion to be 80 ℃; preserving the heat for 2 hours after the dropwise adding is finished; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization to adjust the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles C, wherein the weight ratio of the core layer to the shell layer is 6.1: 1.
preparation of comparative example 1
Preparation of flower-like nano titanium dioxide-acrylic resin composite particle D
Silane-modified flower-like nano titanium dioxide and shell pre-emulsion were prepared according to preparation example 1.
Weighing 0.75 g of initiator, and dissolving the initiator in 10g of deionized water to obtain an initiator solution;
stirring 22.4g of deionized water and 2.6g of sodium dodecyl sulfate, fully stirring 55g of silane modified flower-shaped nano titanium dioxide to be used as a core-layer pre-emulsion, dropwise adding an initiator solution and 9g of shell-layer pre-emulsion into the system for 3 hours when the temperature is raised to 80 ℃, and controlling the reaction temperature of the emulsion to be 80 ℃; preserving the heat for 2 hours after the dropwise adding is finished; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization to adjust the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles D, wherein the weight ratio of the core layer to the shell layer is 14.4: 1.
preparation of comparative example 2
Preparation of flower-like nano titanium dioxide-acrylic resin composite particle E
Silane-modified flower-like nano titanium dioxide and shell pre-emulsion were prepared according to preparation example 2.
Weighing 0.75 g of initiator, and dissolving the initiator in 10g of deionized water to obtain an initiator solution;
stirring 22.4g of deionized water and 2.6g of sodium dodecyl sulfate, fully stirring 55g of silane modified flower-shaped nano titanium dioxide to be used as a core-layer pre-emulsion, dropwise adding an initiator solution and 30g of shell-layer pre-emulsion into the system for 3 hours when the temperature is raised to 80 ℃, and controlling the reaction temperature of the emulsion to be 80 ℃; preserving the heat for 2 hours after the dropwise adding is finished; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization to adjust the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles E, wherein the weight ratio of the core layer to the shell layer is 4.3: 1.
example 1:
aqueous antibacterial children's toy solid color paint was prepared using the formulations shown in table 1. The preparation method comprises the following specific steps: adding the aqueous emulsion into a container, adjusting the dispersion speed to 800r/min, then sequentially adding flower-shaped nano titanium dioxide-acrylic resin composite particles, a film-forming aid, an aqueous aid (comprising a defoaming agent, a base material wetting agent, a flatting agent and a thickening agent), an aqueous color paste and deionized water, keeping the dispersion speed unchanged after the addition, continuing to disperse for at least 30min, and filtering by using a 100-mesh filter screen to obtain the aqueous antibacterial wooden toy paint.
TABLE 1
Example 2:
an aqueous antibacterial wooden toy paint was prepared in the same procedure as in example 1, except that the formulation shown in table 2 below was followed.
TABLE 2
Example 3:
an aqueous antibacterial wooden toy paint was prepared in the same procedure as in example 1, except that the formulation shown in table 3 below was followed.
TABLE 3
Comparative example 1
The composition of the waterborne wood coating is basically the same as that of the preparation method and the example 3, and the difference is only in the flower-shaped nano titanium dioxide-acrylic resin composite particle D of the comparative example 1.
The formulations were prepared according to the following formulations shown in Table 4, wherein the specific gravities mentioned below are all in weight percent
TABLE 4
Comparative example 2
The composition of the waterborne wood coating is basically the same as that of the preparation method and the embodiment 3, and the difference is only in the flower-shaped nano titanium dioxide-acrylic resin composite particle E adopted in the comparative example 2.
The formulations were prepared according to the following formulation shown in Table 5, wherein the specific gravities mentioned below are all in weight percent
TABLE 5
Comparative example 3
The composition of the waterborne wood coating is basically the same as that of the preparation method and the embodiment 3, and the difference is that the commercial titanium dioxide white pulp is adopted in the comparative example 3 to replace the flower-shaped nano titanium dioxide-acrylic resin composite particles C in the embodiment 3.
The formulations were prepared according to the following formulation shown in Table 6, wherein the specific gravities mentioned below are all in weight percent
TABLE 6
| Item | Dosage (g) | Composition (I) | Suppliers of goods |
| Lacper 4219 | 50 | Film-forming material | Wanhua chemistry |
| Commercially available titanium dioxide white | 25 | White pulp | Chemical engineering of blue |
| DP paste M | 1 | Film forming aid | Dow |
| DPnB | 1 | Film forming aid | Dow |
| Tego-825 | 0.5 | Defoaming agent | Winning and creating industry |
| Surfgnol-104E | 0.6 | Substrate wetting agent | Gas chemical industry |
| Tego-450 | 0.3 | Leveling agent | Winning and creating industry |
| U605 | 0.5 | Polyurethane associative thickener | Wanhua chemistry |
| Water-based color paste | 2 | Water-based color paste | Rainbow of color |
| Deionized water | 19.1 | / | / |
The waterborne antibacterial children's toy solid-color paints prepared in examples 1-3 and comparative examples 1-3 were tested for adhesion, water resistance, sanding property, antibacterial durability and heat transferability according to GB/T23999-2009 waterborne wood coatings for interior decoration, GB/T21866-2008 antibacterial coating (paint film) assay and antibacterial effect, and HG/T2453-1993 alkyd varnish, respectively, and the performance test results are shown in Table 7:
TABLE 7
It is apparent from table 8 that, when the core-shell ratio of the flower-like nano titanium dioxide-acrylic resin composite particles is within a certain range, each embodiment of the water-based antibacterial children toy solid-color paint of the present invention has good adhesion, excellent heat transfer printing performance, fast sterilization and long-term bacteriostasis performance.
Claims (10)
1. An aqueous antibacterial coating, in particular to an aqueous antibacterial children toy solid-color paint, which comprises the following components:
the flower-shaped nano titanium dioxide-acrylic resin composite particles have a core-shell structure, wherein silane modified flower-shaped nano titanium dioxide is used as a core layer, and an organosilicon modified acrylic polymer is used as a shell layer.
2. The aqueous antimicrobial coating of claim 1,
in the flower-like nano titanium dioxide-acrylic resin composite particle, the weight ratio of the core layer to the shell layer is 12: 1 to 5: 1, more preferably 10: 1 to 5: 1;
the water-based emulsion is one or a mixture of more than two of acrylate emulsion, polyvinyl acetate emulsion, silicone-acrylic emulsion, styrene-acrylic emulsion, polyurethane dispersion, polyvinyl acetate-acrylic emulsion, ethylene acrylic emulsion and ethylene vinyl acetate emulsion;
the water-based auxiliary agent is one or more selected from a defoaming agent, a base material wetting agent, a leveling agent, a pH regulator or a thickening agent;
the film forming assistant is selected from one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether and ethylene glycol hexyl ether, and preferably one or two of dipropylene glycol methyl ether and dipropylene glycol butyl ether.
3. The aqueous antimicrobial coating of claim 2,
the amount of the antifoaming agent is 0 to 1, preferably 0.1 to 0.6 parts by weight;
the amount of the substrate wetting agent is 0 to 1, preferably 0.3 to 0.6 parts by weight;
the leveling agent is used in an amount of 0 to 1.5, preferably 0.1 to 1 part by weight;
the amount of the pH regulator is 0 to 1.5 parts by weight;
the thickeners are used in amounts of 0 to 1.5, preferably 0.2 to 1.5 parts by weight.
4. The aqueous antimicrobial coating of claim 2,
the defoaming agent is a silicone defoaming agent, preferably one or more of Tego-805, Tego-810, Tego-815, Tego-825, Tego-902w or Tego-1488 in winning industry;
the substrate wetting agent is polyether siloxane copolymer, preferably selected from Byk-346, Byk-348 of Pico chemical, Surfgnol-104BC or Surfgnol-104E of gas chemical;
the leveling agent is organic modified polydimethylsiloxane, preferably one or more of Tego-410, Tego-450, Tego-245 or Tego-270 in winning industry;
the pH regulator is one or more selected from ammonia water, ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol, sodium hydroxide or potassium hydroxide;
the thickener is one or more selected from alkali swelling thickener, polyurethane associated thickener or hydroxyethyl cellulose, and is preferably polyurethane associated thickener.
5. The aqueous antibacterial paint according to claim 1, wherein the flower-like nano titania in the flower-like nano titania-acrylic resin composite particles is anatase.
6. The aqueous antimicrobial coating according to any one of claims 1 to 5, wherein the aqueous antimicrobial coating is a coating for a wood material.
7. A preparation method of flower-shaped nano titanium dioxide-acrylic resin composite particles comprises the following steps:
(A) preparation of silane modified flower-shaped nano titanium dioxide
Dispersing 75 parts by weight of flower-shaped nano titanium dioxide in a mixed solvent of 90-150 parts by weight, preferably 120-150 parts by weight of ethanol and 90-150 parts by weight, preferably 90-120 parts by weight of water, then adding 0.3-1.5 parts by weight, preferably 0.6-1.2 parts by weight of silane coupling agent, after full dispersion, transferring the obtained suspension into a microwave hydrothermal kettle, reacting under the microwave hydrothermal condition of 30-80 ℃, preferably 50-80 ℃, so that the silane coupling agent is rapidly hydrolyzed and bonded on the surface of the flower-shaped nano titanium dioxide, cooling to room temperature, filtering the suspension, and washing with deionized water to obtain silane-modified flower-shaped nano titanium dioxide;
(B) preparation of Shell Pre-emulsion
30 parts by weight of an alkyl methacrylate; 5 to 20, preferably 15 to 18 parts by weight of an alkyl acrylate; 1.5 to 5, preferably 1.5 to 4 parts by weight of a carboxylic acid crosslinking monomer; 1.5 to 5, preferably 1.5 to 3 parts by weight of a vinyl group-containing silicone monomer; 1 to 5, preferably 3 to 5 parts by weight of an emulsifier; 15 to 100, preferably 25 to 80 parts by weight of deionized water, and stirring to fully emulsify the deionized water to obtain a shell layer pre-emulsion;
(C) preparing flower-shaped nano titanium dioxide-acrylic resin composite particles
Adding 15 to 46, preferably 15 to 30 parts by weight of deionized water and 1 to 5 parts by weight of emulsifier into 60 parts by weight of the silane modified flower-shaped nano titanium dioxide obtained in the step (A) and stirring to obtain a core-layer pre-emulsion, when the temperature is raised to 50 ℃ to 90 ℃, dropwise adding an initiator solution containing 0.1 to 3 parts by weight of initiator and 5 to 15, preferably 7 to 10 parts by weight of the shell-layer pre-emulsion prepared in the step (B) into the system for 1 to 3 hours, and controlling the reaction temperature of the emulsion to be 50 ℃ to 90 ℃, preferably 80 ℃ to 85 ℃; after the dropwise addition, keeping the temperature for 0.5 to 3 hours; cooling the system to below 45 ℃, adding a neutralizing agent for neutralization, regulating the pH value to 7-8, cooling to room temperature, filtering and discharging to obtain the flower-shaped nano titanium dioxide-acrylic resin composite particles.
8. The production method according to claim 7, wherein,
the silane coupling agent is a coupling agent with double bonds on a molecular chain, and is preferably selected from one or more of gamma-methacryloxypropyltrimethoxysilane and 3-amino triethoxysilane;
preferably, the flower-like nano titanium dioxide is in anatase type;
preferably, the alkyl methacrylate monomer is methacrylic acid C1-C10An alkyl ester monomer, more preferably one or more selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate or n-octyl methacrylate;
preferably, the alkyl acrylate monomer is acrylic acid C1-C10Alkyl ester monomers, more preferably one or more selected from methyl acrylate, ethyl acrylate, butyl acrylate or n-pentyl acrylate;
preferably, the carboxylic acid crosslinking monomer is one or more selected from acrylic acid or methacrylic acid;
preferably, the organosilicon monomer is any one selected from vinyltrimethoxysilane, vinyltrimethyltriethoxysilane or vinyltriisopropoxysilane;
preferably, the emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether and salts thereof or fatty alcohol ether phosphate and salts thereof;
preferably, the initiator is one or more selected from ammonium persulfate, sodium persulfate or potassium persulfate;
preferably, the neutralizing agent used is selected from one or more of amines or alkali metal hydroxides.
9. A method for preparing the aqueous antibacterial coating material according to any one of claims 1 to 6, which comprises the steps of:
1) adding the aqueous emulsion into a container, then sequentially adding the flower-shaped nano titanium dioxide-acrylic resin composite particles, the film-forming aid, the aqueous color paste and the deionized water under stirring, and stirring to uniformly disperse the aqueous emulsion.
10. The method of manufacturing of claim 9, wherein the method of manufacturing further comprises the steps of:
2) filtering the mixture obtained in the step 1) by using a 100-400-mesh filter screen to obtain the water-based antibacterial coating.
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