CN111763415A - Ultrathin anti-cracking toilet accessory and material and preparation method thereof - Google Patents
Ultrathin anti-cracking toilet accessory and material and preparation method thereof Download PDFInfo
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- 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
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- 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
- A47K13/00—Seats or covers for all kinds of closets
- A47K13/14—Protecting covers for closet seats
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- C08K3/36—Silica
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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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The invention discloses an ultrathin anti-cracking toilet accessory, a material and a preparation method thereof. The invention adopts the reinforced fiber reinforced polyester material, and realizes the performances of high impact resistance, no cracking and low temperature environment resistance of ultrathin toilet accessories (such as seat rings/cover plates) through the structural design modification and material optimization of microspheres. The toilet accessory disclosed by the invention is high in strength and good in toughness, the thickness can be reduced to 1.0-5.0mm, the ultrathin structural design is realized, the material texture is similar to urea formaldehyde, the urea formaldehyde seat ring/cover plate can be well replaced, and the problem of cracking resistance under impact in a low-temperature drying environment of a conventional accessory is fundamentally solved.
Description
Technical Field
The invention relates to the technical field of bathrooms, in particular to an ultrathin anti-cracking closestool accessory, and a material and a preparation method thereof.
Background
Toilet accessories, such as toilet seat rings, cover plates and other materials, mainly comprise urea formaldehyde, PP, ABS, PVC and other materials, wherein the thermoplastic PP, ABS and PVC materials have the defects of poor texture (low density), strong plastic feeling, easiness in scratching, easiness in aging and the like, and the ultrathin and simple design cannot be realized; the urea-formaldehyde seat ring has good texture, but is easy to crack/burst under a low-temperature environment, so that the use and safety of users are influenced, and meanwhile, the thickness of the product is large for ensuring the safety and strength; in order to solve the problems, urea formaldehyde toughening treatment is mostly adopted in the market at present, the urea formaldehyde material cracking probability is reduced, the effect is not obvious, the urea formaldehyde cracking problem cannot be fundamentally solved, meanwhile, the product thickness is large (a cover plate is generally larger than or equal to 4.0mm, a seat ring is generally larger than or equal to 5mm), the weight is large, and the product ultrathin concept cannot be realized. Other thermosetting reinforced materials have the defects of high brittleness, high rigidity, high density, poor toughness and poor impact resistance, are easy to crack due to poor toughness when in use, and are difficult to reduce in thickness;
at present, no material capable of solving urea-formaldehyde cracking or replacing urea-formaldehyde seat ring/cover plate in a better scheme exists in the market, and known replacement materials and defects thereof are as follows: 1) rubber toughening urea formaldehyde: poor toughening effect, easy cracking, poor impact resistance, influence on appearance quality, heavy product, large addition amount of the antibacterial additive, poor safety and high cost; 2) alloy material/inorganic reinforced thermoplastic material: PPS and the like have high cost, poor appearance quality, certain plastic texture, slightly poor impact resistance and low thickness, and the problem of cracking cannot be fundamentally solved; 3) general thermosetting materials: the mechanical property is improved through product thickening, the weight is large, the brittleness is large, and a series of problems of obviously increased cost, low production efficiency, high hinge requirement and the like can occur.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an ultrathin anti-cracking toilet accessory, a material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a material applied to toilet accessories comprises raw materials of 30-50 parts by weight of organic silicon modified unsaturated polyester, 1-8 parts by weight of inorganic modified filler, 2-10 parts by weight of modified zirconia hollow microspheres, 10-30 parts by weight of organic modified montmorillonite, 30-50 parts by weight of reinforcing fiber, 0.8-1.2 parts by weight of first antibacterial agent and an auxiliary agent; the modified zirconia hollow microsphere has an open pore structure which can enable the organic silicon modified unsaturated polyester to be filled into an inner cavity.
Optionally, the raw materials comprise, by mass: 30-50% of organic silicon modified unsaturated polyester, 1-8% of inorganic modified filler, 2-10% of modified zirconia hollow microspheres, 10-30% of organic modified montmorillonite, 30-50% of reinforcing fibers, 0.8-1.2% of first antibacterial agent and the balance of auxiliary agents, wherein the auxiliary agents comprise thickening agents, low-shrinkage agents, polymerization inhibitors and initiators.
Further, the content of the auxiliary agent is 2% -4.5%.
Optionally, the inorganic modified filler comprises CaCO3，BaSO4One or more of hydrated alumina and nano ceramic powder with the grain diameter of 200 meshes to 800 meshes; the inorganic modified filler is modified by organosilane.
Optionally, the particle size of the modified zirconia hollow microsphere is 5 um-20 um, and the modified zirconia hollow microsphere is modified by a coupling agent.
Optionally, the length of the reinforcing fiber is 4mm-30mm, and the reinforcing fiber is modified by organosilane.
An ultrathin cracking-resistant toilet fitting comprises a fitting body, wherein the fitting body is made of the material.
Optionally, the accessory further comprises an antibacterial surface layer arranged on the surface of the accessory body, and the thickness of the antibacterial surface layer is less than 1 mm; the raw materials of the antibacterial surface layer comprise: 60-90 parts of unsaturated polyester, 0.2-1 part of second antibacterial agent, 0.5-1.5 parts of fumed silica, 0.1-1.5 parts of defoaming agent and 0.1-1.5 parts of flatting agent.
Optionally, the first antibacterial agent and the second antibacterial agent respectively comprise a metal antibacterial agent, a rare earth antibacterial agent or an organic antibacterial agent.
Optionally, the toilet accessory comprises a seat and/or a cover plate, wherein the seat is 2.0mm to 5.0mm thick, and the cover plate is 1.0mm to 4.5mm thick.
The preparation method of the toilet accessory comprises the following steps:
1) placing the modified zirconia hollow microspheres in part of organic silicon modified unsaturated polyester and uniformly dispersing, extracting vacuum to remove air and impurities in the microspheres, and then boosting pressure and maintaining pressure until the organic silicon modified unsaturated polyester uniformly coats the surfaces of the microspheres to obtain a microsphere polyester system;
2) dispersing organic modified montmorillonite with solvent, adding the rest organic silicon modified unsaturated polyester, stirring uniformly and vacuumizing to obtain organic montmorillonite modified unsaturated polyester;
3) mixing organic montmorillonite modified unsaturated polyester, a microsphere polyester system and a solvent, adding an inorganic modified filler, a reinforcing fiber, a first antibacterial agent and an auxiliary agent, mixing and kneading to obtain a bulk resin composite material, performing preforming on the bulk resin composite material, and extracting gas to obtain a bulk molding compound;
4) and putting the bulk molding compound into a hot-pressing forming die, wherein the die pressure is 150 MPa-500 MPa, the primary hot-pressing temperature is 140-180 ℃, and the pressure maintaining and shaping are carried out for 40-140 s, so as to obtain the accessory body.
Optionally, before the step 4), the method further comprises the steps of uniformly mixing unsaturated polyester, a second antibacterial agent, fumed silica, a defoaming agent and a flatting agent to form an unsaturated polyester composite material, spraying the unsaturated polyester composite material on the inner surface of the hot-press forming die and curing to form an antibacterial surface layer, and in the step 4), placing the massive molding compound in the hot-press forming die with the antibacterial surface layer on the inner surface for hot-press forming to compound the antibacterial surface layer on the surface of the accessory body.
Optionally, the process for spraying the unsaturated polyester composite material on the inner surface of the hot-press forming die specifically comprises the following steps: spraying the m-benzene unsaturated polyester composite material for multiple times, controlling the thickness of each spraying to be less than 0.2mm, thickening the spraying in sequence, and spraying the next time after each curing, wherein the spraying pressure is less than or equal to 4 bar.
Optionally, the modified zirconia hollow microsphere is prepared by the following method: to form ZrO2The PS core-shell microspheres quickly flow and suspend in a closed boxAnd uniformly spraying concentrated sulfuric acid or hydrofluoric acid to the closed box for 3-5min through an atomization spraying device, cleaning the surface of the microsphere and removing residual acid on the surface of the microsphere, and drying and then carrying out coupling agent modification treatment.
The invention has the beneficial effects that:
(1) the polyester material is modified and toughened through the reinforced fibers and the zirconia hollow microspheres, so that the performances of high impact resistance, no cracking and low-temperature environment resistance under an ultrathin structure are realized, the limitations of heavy feeling and easy cracking of accessories such as a traditional toilet seat/cover plate and the like are avoided, the total quality is reduced, the texture is good, and a urea-formaldehyde seat/cover plate can be well replaced;
(2) the antibacterial surface layer and the body are made of the same material and are formed by hot pressing, no obvious boundary exists, no layering phenomenon exists, and the antibacterial surface layer and the body are not easy to fall off; the density of the surface of the body is improved by the antibacterial surface layer, the stain resistance is strong, the antibacterial effect is good, the high and low temperature resistance and the impact resistance are realized, the cracking is avoided, and the integral toughness of the toilet fittings is enhanced;
(3) simple process, low cost and is suitable for practical production and application.
Drawings
FIG. 1 is a schematic view of the construction of a seat ring and cover plate of an embodiment.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments.
The material applied to the toilet accessories comprises, by weight, 30-50 parts of organic silicon modified unsaturated polyester, 1-8 parts of inorganic modified filler, 2-10 parts of modified zirconia hollow microspheres, 10-30 parts of organic modified montmorillonite, 30-50 parts of reinforcing fibers, 0.8-1.2 parts of a first antibacterial agent and an auxiliary agent. Preferably, the raw materials comprise the following components in percentage by mass: 30-50% of organic silicon modified unsaturated polyester, 1-8% of inorganic modified filler, 2-10% of modified zirconia hollow microsphere, 10-30% of organic modified montmorillonite, 30-50% of reinforcing fiber, 0.8-1.2% of first antibacterial agent and 2-4.5% of auxiliary agent.
The auxiliary agent comprises a thickening agent, a low shrinkage agent, a polymerization inhibitor, an initiator and other conventional auxiliary agents, wherein the thickening agent can be calcium hydroxide and magnesium oxide, and the content of the thickening agent is 0.05-0.1%; the low shrinkage agent can be selected from PMMA, PE and PS; the polymerization inhibitor can be selected from o-methyl hydroquinone (methyl hydroquinone); the accelerator/initiator may be selected from peroxides; the content of other conventional additives is 1.5-3%.
The inorganic modified filler comprising CaCO3，BaSO4One or more of hydrated alumina and nano ceramic powder with the grain diameter of 200 meshes to 800 meshes; the inorganic modified filler is modified by organosilane. For example, with a vinyl silane coupling agent or a titanate coupling agent, by a dry surface coating modification process: and drying the inorganic powder, mixing the coupling agent and the inert solvent, and mixing the mixture and the inorganic powder at a high speed.
The modified zirconia hollow microsphere is modified by a coupling agent, and the particle size is 5-20 um; the modified zirconia hollow microsphere has an open pore structure which can enable the organic silicon modified unsaturated polyester to be filled into an inner cavity.
The reinforcing fiber comprises organic fiber, inorganic fiber and the like, can be natural fiber or artificial fiber, and is further preferably glass fiber, carbon fiber, aramid fiber and the like, the fiber length is 4mm-30mm, and the organic silane modification treatment is carried out on the fiber. For example, the coupling agent is uniformly sprayed after the fiber is dried by using a vinyl silane coupling agent, and the fiber is uniformly stirred.
The first antimicrobial agent includes a metallic antimicrobial agent, an organic antimicrobial agent, or a rare earth antimicrobial agent.
The organic silicon modified unsaturated polyester is one or the combination of two of ortho-benzene type, meta-benzene type, bisphenol A type and neopentyl glycol type. For example, the vinyl silicone prepolymer is added into unsaturated polyester for condensation reaction, and the mixture is stirred uniformly and transparently to obtain the silicone modified unsaturated polyester.
The organic modified montmorillonite can be commercially available product, such as DK-2 type produced by Zhejiang Fenghong clay chemical Co.
An ultrathin anti-cracking toilet accessory comprises an accessory body made of the material and an antibacterial surface layer arranged on the surface of the accessory body, wherein the thickness of the antibacterial surface layer is less than 1 mm; the raw material of the antibacterial surface layer is an unsaturated polyester composite material, and the antibacterial surface layer comprises the following components: 60-90 parts of unsaturated polyester, 0.2-1 part of second antibacterial agent, 0.5-1.5 parts of fumed silica, 0.1-1.5 parts of defoaming agent and 0.1-1.5 parts of flatting agent. Wherein, the size of the fumed silica is 10-500 nm, the viscosity and the strength of a system can be increased, the shear thinning phenomenon is caused, the viscosity is reduced in the processing process, and the defects of sagging and the like are not easy to occur after spraying. The second antibacterial agent comprises a metal antibacterial agent, a rare earth antibacterial agent or an organic antibacterial agent, wherein the metal antibacterial agent comprises a pure metal antibacterial material and a load type antibacterial material.
The unsaturated polyester is one or the combination of two of ortho-benzene type, meta-benzene type, bisphenol A type and neopentyl glycol type.
Referring to fig. 1, the toilet accessories include a seat 1 and a cover 2, wherein the seat 1 includes a seat body 11 and a first antibacterial surface layer 12 on an upper surface layer of the seat body 11, the cover 2 includes a cover body 21 and a second antibacterial surface layer 22 on a lower surface layer of the cover body 21, and the seat body 11 and the cover body 21 are made of the material applied to the toilet accessories. The thickness of the seat ring 1 is 2.0 mm-5.0 mm, and the thickness of the cover plate 2 is 1.0 mm-4.5 mm.
The preparation method of the toilet accessory of the embodiment comprises the following specific steps:
1. antibacterial surface layer
Preheating a hot-pressing forming die, wherein the unsaturated polyester composite material adopts m-benzene unsaturated polyester and a zirconium phosphate silver-loaded nano antibacterial material with the size of 15nm-80nm, the inner surface of the die is uniformly sprayed with the unsaturated polyester composite material for three times to form an antibacterial surface layer, the thickness of each time is controlled to be about 0.2mm (sequentially thickened) through factors such as flow/pressure/nozzle size/pump pressure, the next layer of spraying is carried out after each curing, the total thickness is controlled to be less than 1mm, the optimal thickness is 0.5mm, the spraying pressure is less than or equal to 4bar, and when the viscosity of the material is overlarge, 2-5% of styrene is used for diluting;
2. preparation of microspherical polyester system
Using micro-nano-sized ZrO2Performing surface area structure modification on/PS core-shell microspheres, and obtaining ZrO2The hollow structure of the PS core-shell microsphere is provided by PS, ZrO2Surface negativeAnd (4) loading. ZrO 2 is mixed with2The preparation method comprises the following steps of (1) enabling PS (polystyrene) core-shell microspheres to quickly flow and suspend in a closed box through a closed internal circulation air cooling device, uniformly spraying concentrated sulfuric acid or hydrofluoric acid to the closed box through an atomization spraying device to enable the microspheres to be corroded into a porous/open-pore structure from original closed pores and to be similar to a honeycomb shape, closing the air cooling circulation device after spraying for 3-5min, closing the atomization spraying device, cleaning the surfaces of the microspheres with a large amount of distilled water, cleaning the microspheres with the distilled water, performing ultrasonic cleaning again by adopting absolute ethyl alcohol to remove residual acid on the surfaces of the microspheres, drying the cleaned microspheres in a drying box at 120 ℃ for 2h, performing coupling agent modification treatment on the dried microspheres, specifically spraying vinyl silane coupling agent to the surfaces of the microspheres, uniformly mixing and drying to obtain core;
quantitatively placing the core-shell zirconia modified microspheres in organic silicon modified unsaturated polyester for ultrasonic dispersion for 2-5min, vacuumizing, removing air and impurities in the open-cell microspheres, boosting and maintaining pressure of the microsphere/polyester system again, ensuring that the organic silicon modified unsaturated polyester uniformly coats the surfaces of the microspheres, and preparing a microsphere polyester system;
3. organic modified montmorillonite modified unsaturated polyester:
weighing quantitative organic montmorillonite, dispersing with acetone solvent, further dispersing uniformly for 30min by ultrasonic wave, adding quantitative organic silicon modified unsaturated polyester, stirring uniformly, and vacuumizing for later use to prepare organic montmorillonite modified unsaturated polyester;
4. prefabricating and shaping a seat ring/cover plate body molding compound:
uniformly mixing and stirring an organic montmorillonite modified unsaturated polyester, styrene and microsphere polyester system for 4-6h, adding an inorganic modified filler (the water content is less than or equal to 0.1%), an auxiliary agent, a reinforcing fiber (the water content is less than or equal to 0.1%), a second antibacterial agent and the like, mixing and kneading for 5-15min, controlling the temperature to be less than or equal to 30 ℃, and preparing uniform bulk resin; placing the quantitative bulk resin composite material in a normal-temperature closed die for prefabricating and molding, and extracting gas to manufacture a bulk molding compound with a seat ring/cover plate shape (the thickness of a prefabricated blank is larger than the thickness of a finished product, and the width of the prefabricated blank is smaller than the thickness of the finished product);
5. one-time hot-press molding:
after the surface of the antibacterial surface layer in the hot-press forming die is dried and cured, taking out the seat ring/cover plate body molding compound, putting the seat ring/cover plate body molding compound into the hot-press forming die, and performing quick one-step hot-press forming: keeping the pressure of the mold controlled at 250MPa, rapidly opening the mold for 1s after closing the mold for 0.1cm, exhausting for 1-2s, then carrying out pressure maintaining and shaping for 100s, controlling the temperature of the mold at 140-180 ℃, compounding the antibacterial surface layer on the surface of the seat ring/cover plate body and having no obvious boundary;
6. removing flash and post-treating:
and taking out the seat ring and the cover plate, removing the flash, and polishing according to the requirement.
The resulting performance of the seat/cover plate versus a conventional urea formaldehyde material seat/cover plate is as follows:
in the invention:
the thermosetting polyester material is adopted, the material has a three-dimensional net structure after being cured and molded, the material has high crosslinking degree and large brittleness, and is easy to crack under impact, the crosslinking continuity of the material in a macroscopic degree is obviously reduced by adopting the reinforcing fibers and the inorganic modified filler for filling and modifying, when the material is impacted, the brittleness of the material is reduced through a large amount of silver grains and the toughness of the reinforcing fibers, the internal stress is released, meanwhile, the strength of the material is further improved through the net structure of the reinforcing fibers in a macroscopic view, and the material is ensured to have certain strength and toughness in an ultrathin structure; microcosmically modifying by adopting organic modified montmorillonite, utilizing a lamellar structure of the montmorillonite, intercalating resin between lamellar montmorillonite layers, and after curing, forming an ultra-large contact area and an ultra-strong adhesive force with a resin system, wherein when a large external force is applied, the lamellar montmorillonite is easy to serve as a stress concentration point to form large-range uniform silver stripes, and rapidly stopping or transferring microcracks by utilizing the strength and rigidity of an inorganic silicate lamellar crystal of the montmorillonite;
the method comprises the steps of treating hollow zirconia microspheres with acid, carrying out discontinuous partial reaction and dissolution on zirconia on the surface, preparing modified zirconia hollow microspheres with open pore structures, uniformly dispersing the microspheres in an unsaturated polyester system, carrying out vacuum and high-pressure treatment, coating and filling a microsphere inner cavity structure with a low-viscosity resin system, and compared with the traditional filling material, wherein the resin system can be well combined with a zirconia structure, the macroscopic cross-linking degree of polyester is reduced, the open pore microsphere structure serves as an internal reinforcing and toughening structure, when a product is stressed (particularly impact force), a large amount of dispersible silver stripes are generated on the surface of the zirconia structure, the zirconia absorbs and further disperses the dispersible silver stripes through the self strength and toughness, so that the product is prevented from cracking, meanwhile, the constructed zirconia structure provides a three-dimensional reinforcing effect for the product, and the strength and toughness of the product are obviously improved, the ultrathin effect of the product is realized;
the anti-bacterial surface layer is formed by curing m-benzene unsaturated polyester through three-layer stepped spraying, the first layer and the second layer provide smooth surface layers, the third layer is sprayed or brushed after curing, compression molding is carried out after surface drying, the material system of the seat ring/cover plate is the same as that of the anti-bacterial surface layer, the prepared anti-bacterial surface layer and the seat ring/cover plate have no obvious boundary line, the phenomenon that the anti-bacterial surface layer and the seat ring/cover plate are layered or fall off in the traditional post-spraying or post-surface treatment is avoided, the anti-bacterial surface layer forms a compact net-shaped structure through a cross-linking reaction, the anti-pollution performance is strong and easy to handle, and the phenomenon; meanwhile, the antibacterial surface layer has a lasting antibacterial effect, and the safety and the health of the human body contact layer are ensured.
The above embodiments are only used to further illustrate the ultrathin cracking-resistant toilet accessories of the present invention, the materials and the preparation method thereof, but the present invention is not limited to the embodiments, and any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention fall within the protection scope of the technical solution of the present invention.
Claims (13)
1. A material for use in toilet accessories, comprising: the raw materials comprise 30-50 parts by weight of organic silicon modified unsaturated polyester, 1-8 parts by weight of inorganic modified filler, 2-10 parts by weight of modified zirconia hollow microspheres, 10-30 parts by weight of organic modified montmorillonite, 30-50 parts by weight of reinforcing fiber, 0.8-1.2 parts by weight of first antibacterial agent and auxiliary agent; the modified zirconia hollow microsphere has an open pore structure which can enable the organic silicon modified unsaturated polyester to be filled into an inner cavity.
2. The material of claim 1, wherein: the raw materials comprise the following components in percentage by mass: 30-50% of organic silicon modified unsaturated polyester, 1-8% of inorganic modified filler, 2-10% of modified zirconia hollow microspheres, 10-30% of organic modified montmorillonite, 30-50% of reinforcing fibers, 0.8-1.2% of first antibacterial agent and the balance of auxiliary agents, wherein the auxiliary agents comprise thickening agents, low-shrinkage agents, polymerization inhibitors and initiators.
3. The material of claim 1, wherein: the inorganic modified filler comprises CaCO3，BaSO4One or more of hydrated alumina and nano ceramic powder with the grain diameter of 200 meshes to 800 meshes; the inorganic modified filler is modified by organosilane.
4. The material of claim 1, wherein: the particle size of the modified zirconia hollow microsphere is 5-20 um, and the modified zirconia hollow microsphere is modified by a coupling agent.
5. The material of claim 1, wherein: the length of the reinforced fiber is 4mm-30mm, and the reinforced fiber is modified by organosilane.
6. The utility model provides an ultra-thin anti fracture's closestool accessory which characterized in that: comprises a fitting body made of the material according to any one of claims 1 to 5.
7. The toilet accessory of claim 6, wherein: the accessory further comprises an antibacterial surface layer arranged on the surface of the accessory body, and the thickness of the antibacterial surface layer is less than 1 mm; the raw materials of the antibacterial surface layer comprise: 60-90 parts of unsaturated polyester, 0.2-1 part of second antibacterial agent, 0.5-1.5 parts of fumed silica, 0.1-1.5 parts of defoaming agent and 0.1-1.5 parts of flatting agent.
8. The toilet accessory of claim 7, wherein: the first antibacterial agent and the second antibacterial agent respectively comprise a metal antibacterial agent, a rare earth antibacterial agent or an organic antibacterial agent.
9. The toilet accessory of claim 6, wherein: the toilet accessories comprise a seat ring and/or a cover plate, wherein the thickness of the seat ring is 2.0-5.0 mm, and the thickness of the cover plate is 1.0-4.5 mm.
10. A method of manufacturing a toilet fitting according to any one of claims 6 to 9, comprising the steps of:
1) placing the modified zirconia hollow microspheres in part of organic silicon modified unsaturated polyester and uniformly dispersing, extracting vacuum to remove air and impurities in the microspheres, and then boosting pressure and maintaining pressure until the organic silicon modified unsaturated polyester uniformly coats the surfaces of the microspheres to obtain a microsphere polyester system;
2) dispersing organic modified montmorillonite with solvent, adding the rest organic silicon modified unsaturated polyester, stirring uniformly and vacuumizing to obtain organic montmorillonite modified unsaturated polyester;
3) mixing organic montmorillonite modified unsaturated polyester, a microsphere polyester system and a solvent, adding an inorganic modified filler, a reinforcing fiber, a first antibacterial agent and an auxiliary agent, mixing and kneading to obtain a bulk resin composite material, performing preforming on the bulk resin composite material, and extracting gas to obtain a bulk molding compound;
4) and putting the bulk molding compound into a hot-pressing forming die, wherein the die pressure is 150 MPa-500 MPa, the primary hot-pressing temperature is 140-180 ℃, and the pressure maintaining and shaping are carried out for 40-140 s, so as to obtain the accessory body.
11. The method of manufacturing according to claim 10, characterized in that: before the step 4), the method further comprises the steps of uniformly mixing unsaturated polyester, a second antibacterial agent, fumed silica, a defoaming agent and a flatting agent to form an unsaturated polyester composite material, spraying the unsaturated polyester composite material on the inner surface of the hot-press forming die and curing to form an antibacterial surface layer, and in the step 4), placing the massive molding compound in the hot-press forming die with the antibacterial surface layer on the inner surface for hot-press forming to compound the antibacterial surface layer on the surface of the accessory body.
12. The method of claim 11, wherein: the process for spraying the unsaturated polyester composite material on the inner surface of the hot-press forming die specifically comprises the following steps: and spraying the unsaturated polyester composite material for multiple times, controlling the thickness of each spraying to be less than 0.2mm, thickening the spraying in sequence, and spraying the composite material for the next time after each curing, wherein the spraying pressure is less than or equal to 4 bar.
13. The method of manufacturing according to claim 10, wherein: the modified zirconia hollow microsphere is prepared by the following method: to form ZrO2And (3) suspending the PS core-shell microspheres in a closed box in a fast flowing manner, uniformly spraying concentrated sulfuric acid or hydrofluoric acid to the closed box for 3-5min through an atomization spraying device, cleaning the surfaces of the microspheres, removing residual acid on the surfaces of the microspheres, and performing coupling agent modification treatment after drying.
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