CN111944201A - Nano antibacterial agent and preparation method thereof, stain-resistant antibacterial resin composition, sheet molding compound and stain-resistant antibacterial bathtub - Google Patents

Nano antibacterial agent and preparation method thereof, stain-resistant antibacterial resin composition, sheet molding compound and stain-resistant antibacterial bathtub Download PDF

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CN111944201A
CN111944201A CN202010776678.4A CN202010776678A CN111944201A CN 111944201 A CN111944201 A CN 111944201A CN 202010776678 A CN202010776678 A CN 202010776678A CN 111944201 A CN111944201 A CN 111944201A
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nano
antibacterial
stain
molding compound
resin composition
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CN111944201B (en
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胡福涛
陈忠义
张雪霞
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Wuhu Keyi Building Materials Co ltd
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Suzhou Cozy House Equipment Co ltd
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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K3/00—Baths; Douches; Appurtenances therefor
    • A47K3/02—Baths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a nano antibacterial agent and a preparation method thereof, a stain-resistant antibacterial resin composition, a sheet molding compound and a stain-resistant antibacterial bathtub. The nano high stain-resistant antibacterial sheet molding compound comprises glass fibers in the middle and polyethylene films on the upper and lower surfaces, and further comprises a resin layer which is arranged between the polyethylene films on the upper and lower surfaces and used for impregnating the glass fibers in the middle, wherein the resin layer is formed by a resin composition for the nano high stain-resistant antibacterial sheet molding compound; the resin composition also comprises a nano antibacterial agent accounting for 1-3% of the total weight of the raw materials of the resin composition. The bathtub prepared by the sheet molding compound added with the nano antibacterial agent has good high stain-resistant antibacterial performance.

Description

Nano antibacterial agent and preparation method thereof, stain-resistant antibacterial resin composition, sheet molding compound and stain-resistant antibacterial bathtub
The application is a divisional application of an invention patent application with the application date of 2018, 3 and 9, and the application number of 201810193313.1, wherein the invention name is 'a nano high-stain-resistance antibacterial resin composition, a sheet molding compound and a high-stain-resistance antibacterial bathtub'.
Technical Field
The invention relates to a nano antibacterial agent and a preparation method thereof, a resin composition for a nano high-stain-resistance antibacterial sheet molding compound containing the nano antibacterial agent, a sheet molding compound containing the resin composition and a high-stain-resistance antibacterial bathtub made of the sheet molding compound.
Background
Sheet Molding Compound (SMC) is prepared by mixing unsaturated polyester resin, low shrinkage additive, filler, thickener, initiator, cross-linking agent, internal release agent, colorant and other raw materials into resin paste, impregnating chopped fiber roving or glass fiber felt, impregnating glass fiber into Sheet by Sheet Molding Compound Sheet making machine to make Sheet, coating the Sheet with polyethylene or polypropylene film on both sides, rolling, thickening to achieve the state of non-sticky, and using for compression Molding. The sheet molding compound is a molding compound for manufacturing fiber reinforced plastics by a dry method developed in the 60 th year of the 20 th century, the process is developed in Europe for the first time, then the America, Japan and other countries, and the sheet molding compound compression molding process is developed gradually into a process which is the most mature and widely applied in the field of composite materials after more than 40 years of development.
With the continuous expansion of the application range of the sheet molding compound, the performance of the sheet molding compound needs to be further improved, and particularly, when the sheet molding compound is used as a bathtub material, higher requirements on the stain resistance and the antibiosis of the sheet molding compound are met.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a nano antibacterial agent, a preparation method thereof and a resin composition containing the nano antibacterial agent for preparing a nano highly stain-resistant antibacterial sheet molding compound.
The invention also provides a nano high-stain-resistance antibacterial sheet molding compound and a preparation method thereof, and a high-stain-resistance antibacterial bathtub can be obtained by adopting the nano high-stain-resistance antibacterial sheet molding compound.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nano highly fouling-resistant antibacterial sheet molding compound comprising glass fibers in the middle and polyethylene films on upper and lower sides, the nano highly fouling-resistant antibacterial sheet molding compound further comprising a resin layer disposed between the polyethylene films on the upper and lower sides and impregnating the glass fibers in the middle, the resin layer being formed of a resin composition for a nano highly fouling-resistant antibacterial sheet molding compound; the resin composition is prepared by mixing the following components in parts by weight:
Figure BDA0002618683280000021
the resin composition also comprises a nano antibacterial agent accounting for 1-3% of the total weight of the raw materials of the resin composition.
The nano antibacterial agent is prepared by mixing the following components in parts by weight:
Figure BDA0002618683280000022
the nano titanium sol is used as a carrier, the silane coupling agent is used as a vector, and the clustering phenomenon among the nano silver, the nano titanium dioxide and the nano silver and the nano titanium dioxide is effectively reduced, so that the nano silver can fully play an antibacterial role.
Preferably, the silane coupling agent is one or more of a methyl silane coupling agent, an ethyl silane coupling agent or a phenyl silane coupling agent.
Preferably, the internal mold release agent is zinc stearate or calcium stearate or a mixture of the two.
Preferably, the filler is aluminum hydroxide micro powder or calcium carbonate micro powder with the particle size of less than or equal to 10 microns or a combination of the two.
Preferably, the initiator is tert-butyl peroxybenzoate or tert-butyl peroxy2-ethyl hexanoate or a combination of the two.
Wherein, the unsaturated polyester resin is one or more of o-benzene unsaturated resin, m-benzene unsaturated resin, epoxy vinyl ester unsaturated resin and vinyl resin.
The low shrinkage agent is saturated Polyester (PES), and specifically may be, for example, polystyrene (PSt), polymethyl methacrylate (PMMA), or the like.
According to the present invention, the unsaturated polyester resin may be commercially available. The surface modifier can be PE powder and the like; the thickener can be magnesium oxide, magnesium hydroxide, calcium hydroxide, etc.
The invention also provides a preparation method of the nano high-stain-resistant antibacterial sheet molding compound, which comprises the following steps:
1) preparing an antibacterial agent: adding a silane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain a nano antibacterial agent;
2) preparation of the resin composition: firstly, adding unsaturated polyester resin, a low-shrinkage additive, an initiator, an internal release agent, a surface modifier and a thickening agent according to a formula, stirring for 10-30min, then adding the nano antibacterial agent prepared in the step 1), stirring for 30-50min to fully disperse the nano antibacterial agent in a resin solution, adding a filler, and uniformly stirring to prepare a resin composition;
3) uniformly coating the resin composition uniformly mixed with the nano antibacterial agent on the upper and lower polyethylene films by a scraper; cutting glass fibers by adjusting a cutter, controlling the length of the glass fibers to be 18-30mm, and then uniformly scattering the glass fibers on the polyethylene film coated with the resin composition, wherein the mass content of the glass fibers in the stain-resistant antibacterial sheet molding compound is 22-28%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, pressing the sheet by a compactor to fully impregnate the glass fiber and the resin composition, forming the sheet, and then rolling the sheet;
4) and (3) conveying the rolled sheet material to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 40-50 ℃, and the thickening time is 12-36 hours, so as to obtain the nano high-stain-resistance antibacterial sheet molding compound.
Wherein the stirring speed is 400-800r/min, and the temperature is 20-60 ℃.
The invention also provides a high stain-resistant antibacterial bathtub which is prepared by the nano high stain-resistant antibacterial sheet molding compound through mould pressing, and the specific steps are as follows: weighing the nano high-stain-resistance antibacterial sheet molding compound, tearing off the polyethylene films on the upper surface and the lower surface of the sheet molding compound, and putting the sheet molding compound into a preheated mold for mold pressing.
Wherein, the temperatures of the front and back surfaces of the die during the die pressing are respectively 140-150 ℃ and 130-140 ℃, and the die pressing is carried outThe force is: 50-80kg/cm2The forming time is 180-one-time for 300s, and trimming is carried out after the mould pressing is finished, so that the high stain-resistant antibacterial bathtub is obtained
Compared with the prior art, the invention has the advantages that: according to the invention, the nano titanium sol is used as a carrier, the silane coupling agent is used as a vector, the cluster phenomenon among nano silver, nano titanium dioxide and nano silver and nano titanium dioxide is effectively reduced, so that the nano silver can fully play an antibacterial role, the nano titanium dioxide well plays a role of nano particles in materials, and the conventional mould pressing process is adopted to obtain the high-pollution-resistant antibacterial integral bathroom bathtub with good pollution-resistant antibacterial performance; meanwhile, due to the action of the nano titanium dioxide particles and the sol, the comprehensive properties of the integral bathroom bathtub, such as strength, scrubbing resistance and the like, are improved.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment provides a nano antibacterial agent, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000041
the preparation steps are as follows: adding a methylsilane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain the nano antibacterial agent. The stirring speed is 400r/min and the temperature is 60 ℃.
Example two
The embodiment provides a nano antibacterial agent, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000042
the preparation steps are as follows: adding an ethyl silane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain the nano antibacterial agent. The stirring speed is 500r/min and the temperature is 50 ℃.
EXAMPLE III
The embodiment provides a nano antibacterial agent, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000043
Figure BDA0002618683280000051
the preparation steps are as follows: adding phenyl silane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain the nano antibacterial agent. The stirring speed is 600r/min and the temperature is 40 ℃.
Example four
The embodiment provides a nano antibacterial agent, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000052
the preparation steps are as follows: and adding the mixed methyl silane coupling agent and phenyl silane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain the nano antibacterial agent. The stirring speed is 800r/min and the temperature is 20 ℃.
EXAMPLE five
The embodiment provides a resin composition for a nano high-stain-resistance antibacterial sheet molding compound, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000053
firstly, adding unsaturated polyester resin, low-shrinkage additive, initiator, internal release agent, surface modifier and thickener according to the formula, stirring for 10-30min, then adding filler, and uniformly stirring to obtain the resin composition.
EXAMPLE six
The embodiment provides a resin composition for a nano high-stain-resistance antibacterial sheet molding compound, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000061
firstly, adding unsaturated polyester resin, a low-shrinkage additive, an initiator, an internal release agent, a surface modifier and a thickening agent according to the formula, stirring for 10-30min, then adding the nano antibacterial agent prepared in the first embodiment, stirring for 30-50min to fully disperse the nano antibacterial agent in a resin solution, adding a filler, and uniformly stirring to prepare the resin composition.
EXAMPLE seven
The embodiment provides a resin composition for a nano high-stain-resistance antibacterial sheet molding compound, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000062
firstly, adding unsaturated polyester resin, low shrinkage additive, initiator, internal release agent, surface modifier and thickener according to the formula, stirring for 10-30min, then adding the nano antibacterial agent prepared in the second embodiment, stirring for 30-50min to fully disperse the nano antibacterial agent in the resin solution, then adding filler, and stirring uniformly to prepare the resin composition.
Example eight
The embodiment provides a resin composition for a nano high-stain-resistance antibacterial sheet molding compound, which is prepared by mixing the following raw materials in parts by weight:
Figure BDA0002618683280000071
firstly, adding unsaturated polyester resin, low shrinkage additive, initiator, internal release agent, surface modifier and thickener according to the formula, stirring for 10-30min, then adding the nano antibacterial agent prepared in the third embodiment, stirring for 30-50min to fully disperse the nano antibacterial agent in resin solution, then adding filler, and stirring uniformly to prepare the resin composition.
Example nine
This example provides a method for preparing a sheet molding compound using the resin composition of example five, which is specifically performed as follows:
1) the resin composition of example five was uniformly coated on the upper and lower polyethylene films by means of a doctor blade; cutting the glass fiber by adjusting a cutter, controlling the length of the glass fiber to be 18mm, and then uniformly scattering the glass fiber on the polyethylene film coated with the resin composition, wherein the mass content of the glass fiber in the stain-resistant antibacterial sheet molding compound is 28%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, squeezing the sheet by a compactor to fully impregnate the glass fibers and the resin composition, forming the sheet, and then rolling the sheet;
2) and (3) conveying the rolled sheet to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 40 ℃, and the thickening time is 36 hours, so as to obtain the sheet molding compound.
Example ten
This example provides a method for preparing a nano-sized highly fouling-resistant antibacterial sheet molding compound by using the resin composition of example six, which comprises the following steps:
1) uniformly coating the resin composition of example six, in which the nano antibacterial agent was uniformly mixed, on the upper and lower polyethylene films by a doctor blade; cutting the glass fiber by adjusting a cutter, controlling the length of the glass fiber to be 18mm, and then uniformly scattering the glass fiber on the polyethylene film coated with the resin composition, wherein the mass content of the glass fiber in the stain-resistant antibacterial sheet molding compound is 28%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, squeezing the sheet by a compactor to fully impregnate the glass fibers and the resin composition, forming the sheet, and then rolling the sheet;
2) and (3) conveying the rolled sheet material to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 40 ℃, and the thickening time is 36 hours, so as to obtain the nano high-pollution-resistance antibacterial sheet molding compound.
EXAMPLE eleven
This example provides a method for preparing nano-sized highly fouling resistant antibacterial sheet molding compound by using the resin composition of example seven, which is specifically implemented as follows:
1) uniformly coating the resin composition of example seven, in which the nano antibacterial agent was uniformly mixed, on the upper and lower polyethylene films by a doctor blade; cutting the glass fiber by adjusting a cutter, controlling the length of the glass fiber to be 30mm, and then uniformly scattering the glass fiber on the polyethylene film coated with the resin composition, wherein the mass content of the glass fiber in the stain-resistant antibacterial sheet molding compound is 22%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, squeezing the sheet by a compactor to fully impregnate the glass fibers and the resin composition, forming the sheet, and then rolling the sheet;
2) and (3) conveying the rolled sheet material to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 50 ℃, and the thickening time is 12 hours, so as to obtain the nano high-stain-resistance antibacterial sheet molding compound.
Example twelve
This example provides a method for preparing nano-sized highly fouling resistant antibacterial sheet molding compound by using the resin composition of example eight, which is specifically implemented as follows:
1) uniformly coating the resin composition of example eight, in which the nano antibacterial agent was uniformly mixed, on the upper and lower polyethylene films by a doctor blade; cutting the glass fiber by adjusting a cutter, controlling the length of the glass fiber to be 25mm, and then uniformly scattering the glass fiber on the polyethylene film coated with the resin composition, wherein the mass content of the glass fiber in the stain-resistant antibacterial sheet molding compound is 25%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, squeezing the sheet by a compactor to fully impregnate the glass fibers and the resin composition, forming the sheet, and then rolling the sheet;
2) and (3) conveying the rolled sheet material to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 45 ℃, and the thickening time is 24 hours, so as to obtain the nano high-pollution-resistance antibacterial sheet molding compound.
EXAMPLE thirteen
This example provides a bathtub made from the sheet molding compound of example nine. The specific preparation process of the bathtub is as follows:
the sheet molding compound of example nine was weighed, the polyethylene film on the sheet was peeled off, and the sheet was placed in a preheated mold and molded using a 3000T press at 145 ℃ and 136 ℃ on the front and back sides, respectively, at the following molding pressures: 50kg/cm2And (4) forming for 180s, wherein the thickness of the final product is 3mm, trimming after die pressing is finished, and finishing the flash on the periphery of the product to obtain the bathtub.
Example fourteen
This example provides a highly stain resistant, antimicrobial bathtub made from the nano highly stain resistant, antimicrobial sheet molding compound of example ten. The specific preparation process of the high stain-resistant antibacterial bathtub is as follows:
weighing the sheet molding compound of example ten, tearing off the polyethylene film on the sheet, putting the sheet into a preheated mold, and molding by using a 3000T press, wherein the temperatures of the front and back sides of the mold are 145 ℃ and 136 ℃ respectively, and the molding pressure is as follows: 50kg/cm2And the forming time is 180s, the thickness of the final product is 3mm, trimming is carried out after the die pressing is finished, and flash on the periphery of the product is finished, so that the high-stain-resistant antibacterial bathtub is obtained.
Example fifteen
This example provides a highly stain resistant, antimicrobial bathtub made from the nano highly stain resistant, antimicrobial sheet molding compound of example eleven. The specific preparation process of the high stain-resistant antibacterial bathtub is as follows:
the sheet molding compound of example eleven was weighed, the polyethylene film on the sheet was peeled off, and the sheet was placed in a preheated mold and molded using a 3000T press at 140 ℃ and 130 ℃ on the front and back sides, respectively, at the following molding pressures: 80kg/cm2And the forming time is 300s, the thickness of the final product is 3mm, trimming is carried out after the die pressing is finished, and flash on the periphery of the product is finished, so that the high-stain-resistant antibacterial bathtub is obtained.
Example sixteen
This example provides a highly stain resistant, antimicrobial bathtub made from the nano highly stain resistant, antimicrobial sheet molding compound of example twelve. The specific preparation process of the high stain-resistant antibacterial bathtub is as follows:
the sheet molding compound of example twelve was weighed, the polyethylene film on the sheet was peeled off, and the sheet was placed in a preheated mold and molded using a 3000T press at 150 ℃ and 140 ℃ on the front and back sides, respectively, at the following molding pressures: 50kg/cm2And the forming time is 300s, the thickness of the final product is 3mm, trimming is carried out after the die pressing is finished, and flash on the periphery of the product is finished, so that the high-stain-resistant antibacterial bathtub is obtained.
Example seventeen
In this example, the bathtub prepared in the thirteenth to sixteenth examples was tested for contamination resistance and antibacterial property, wherein the material of the bathtub in the thirteenth example was not added with the nano antibacterial agent, and is a comparative example. The test results are shown in Table 1.
Table 1 results of stain-resistant antibacterial tests for bathtubs of thirteen to sixteenth embodiments
Content of antibacterial powder Antibacterial rate Bending strength
EXAMPLE thirteen 0 55.70％ 123MPa
Example fourteen 1％ 85.80％ 150MPa
Example fifteen 2％ 91.80％ 162MPa
Example sixteen 3％ 92.30％ 132MPa
From table 1, it can be derived: the high stain-resistant antibacterial rate prepared by the sheet molding compound added with the nano antibacterial agent is obviously improved.
According to the invention, the nano titanium sol is used as a carrier, and the silane coupling agent is used as a vector, so that the clustering phenomena of nano silver, nano titanium dioxide and nano silver and nano titanium dioxide are effectively reduced. So that the nano silver can fully exert the antibacterial action, and the nano titanium dioxide can well exert the action of nano particles in the material, thereby preparing the integral bathroom bathtub with high stain resistance and antibacterial property; meanwhile, due to the action of the nano titanium dioxide particles and the sol, the comprehensive properties of the integral bathroom bathtub, such as strength, scrubbing resistance and the like, are improved.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. The nano antibacterial agent is characterized by comprising nano titanium sol, nano silver, nano titanium dioxide and a silane coupling agent, wherein the nano titanium sol is used as a carrier, and the silane coupling agent is used as a vector.
2. The nano antibacterial agent according to claim 1, wherein the nano antibacterial agent is prepared by mixing the following components in parts by weight:
Figure FDA0002618683270000011
3. the nano antibacterial agent according to claim 1, wherein the silane coupling agent is one or more of a methyl silane coupling agent, an ethyl silane coupling agent or a phenyl silane coupling agent.
4. A method for preparing the nano antibacterial agent according to any one of claims 1 to 3, characterized in that the silane coupling agent is mixed with the nano titanium sol, and nano silver and nano titanium dioxide are added under stirring to obtain the nano antibacterial agent.
5. The method for preparing nano antibacterial agent according to claim 4, wherein the silane coupling agent and the nano titanium sol are mixed, after stirring for 30-50min, nano silver is added, after stirring for 30-50min, nano titanium dioxide is added, and then stirring is carried out for 30-50min, so as to obtain the nano antibacterial agent.
6. The method for preparing a nano antibacterial agent according to claim 4, wherein the stirring speed is 400 to 800r/min and the stirring temperature is 20 to 60 ℃.
7. A nano highly stain-resistant antibacterial sheet molding compound comprising glass fibers in the middle and polyethylene films on the upper and lower sides, characterized in that the nano highly stain-resistant antibacterial sheet molding compound further comprises a resin layer disposed between the polyethylene films on the upper and lower sides and impregnating the glass fibers in the middle, the resin layer being formed of a resin composition for a nano highly stain-resistant antibacterial sheet molding compound; the resin composition comprising the nano antibacterial agent as set forth in any one of claims 1 to 3.
8. The nano high stain-resistant antibacterial sheet molding compound as claimed in claim 7, wherein the resin composition is prepared by mixing the following components in parts by weight:
Figure FDA0002618683270000012
Figure FDA0002618683270000021
the resin composition also comprises a nano antibacterial agent accounting for 1-3% of the total weight of the raw materials of the resin composition.
9. The preparation method of the nano high stain-resistant antibacterial sheet molding compound as claimed in claim 7 or 8, characterized by comprising the following steps:
1) preparing an antibacterial agent: adding a silane coupling agent into the nano titanium sol, stirring for 30-50min, adding nano silver, stirring for 30-50min, adding nano titanium dioxide, and stirring for 30-50min to obtain a nano antibacterial agent;
2) preparation of the resin composition: firstly, adding unsaturated polyester resin, a low-shrinkage additive, an initiator, an internal release agent, a surface modifier and a thickening agent according to a proportion, stirring for 10-30min, then adding the nano antibacterial agent prepared in the step 1), stirring for 30-50min to fully disperse the nano antibacterial agent in a resin solution, adding a filler, and uniformly stirring to prepare a resin composition;
3) uniformly coating the resin composition uniformly mixed with the nano antibacterial agent on the upper and lower polyethylene films by a scraper; cutting glass fibers by adjusting a cutter, controlling the length of the glass fibers to be 18-30mm, and then uniformly scattering the glass fibers on the polyethylene film coated with the resin composition, wherein the mass content of the glass fibers in the stain-resistant antibacterial sheet molding compound is 22-28%; adhering upper and lower polyethylene films to each other to form a sheet with upper and lower surfaces covered with polyethylene films, pressing the sheet by a compactor to fully impregnate the glass fiber and the resin composition, forming the sheet, and then rolling the sheet;
4) and (3) conveying the rolled sheet material to a thickening chamber for thickening, wherein the temperature of the thickening chamber is set to be 40-50 ℃, and the thickening time is 12-36 hours, so as to obtain the nano high-stain-resistance antibacterial sheet molding compound.
10. A high stain-resistant antibacterial bathtub, characterized in that, the high stain-resistant antibacterial bathtub is made by the nano high stain-resistant antibacterial sheet molding compound of claim 7 or 8 through mould pressing, the concrete steps are: weighing the nano high-stain-resistance antibacterial sheet molding compound, tearing off the polyethylene films on the upper surface and the lower surface of the sheet molding compound, and putting the sheet molding compound into a preheated mold for mold pressing.
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