A skin-friendly material for one-piece toilet seat with film coating, and its preparation method and application

Abstract

The present invention discloses a skin-friendly material for a one-piece toilet seat, its preparation method, and its application. The skin-friendly material comprises a polysiloxane material, white carbon black, and modified hollow glass microspheres, wherein the modified hollow glass microspheres comprise hollow glass microspheres modified with a surfactant. The skin-friendly material is used as the outermost skin-friendly layer of the one-piece toilet seat. It exhibits pleasant tactile properties, is soft, stain-resistant, wear-resistant, antibacterial, mildew-resistant, and flame-retardant properties, significantly improving the user experience and enhancing the hygiene of the seat.

Description

Technical Field

[0001] The present invention belongs to the technical field of sanitary ware materials, and in particular relates to a skin-friendly material for a one-piece toilet seat with a membrane, and a preparation method and application thereof. Background Art

[0002] Currently, toilet seats are typically made of thermoplastics (such as PP, ABS, etc.) and thermosetting plastics (such as UF, etc.) molded through high-temperature and high-pressure processes. Whether it is thermoplastic or thermosetting plastic, the surface hardness of the product is extremely hard, which makes it cold to use in winter, resulting in a poor user experience. In related technologies, a layer of fabric is usually attached to the surface of the seat to improve the user experience, but conventional fabrics are easily stained and breed bacteria, and the hygiene conditions are poor. Summary of the Invention

[0003] The present invention aims to address at least one of the technical problems existing in the aforementioned prior art. To this end, the present invention proposes a skin-friendly material for a one-piece toilet seat. The material is soft, stain-resistant, wear-resistant, and antibacterial and mildew-resistant. Application as the surface material for a one-piece toilet seat can significantly enhance the user experience and improve the hygiene of the seat.

[0004] The present invention also provides a method for preparing a skin-friendly material for a membrane-coated seat ring of a one-piece toilet.

[0005] The present invention also provides a film-coated seat ring.

[0006] The invention also provides a method for preparing the film-coated seat ring.

[0007] The present invention also provides a one-piece toilet.

[0008] The present invention also proposes the application of the skin-friendly material and the film-coated seat ring in bathroom products.

[0009] In a first aspect of the present invention, a skin-friendly material for a one-piece toilet seat is proposed, comprising a polysiloxane material, white carbon black and modified hollow glass microspheres, wherein the modified hollow glass microspheres comprise hollow glass microspheres modified with a surfactant.

[0010] The skin-friendly material according to the embodiment of the present invention has at least the following beneficial effects:

[0011] The skin-friendly material of the present invention uses white carbon black as a reinforcing filler and includes polysiloxane materials and modified hollow glass microspheres. The surface-modified hollow glass microspheres, due to their small particle size, large specific surface area, and numerous unpaired atoms, have a relatively large number of free bonds, which can effectively bond and fill the microporous gaps on the surface of the silica gel (polysiloxane material), thereby making the product surface smoother and flatter, and improving the stain resistance and wear resistance. The skin-friendly material of the present invention is used in the skin-friendly layer of the outermost layer of the coated seat ring of a one-piece toilet, which has the characteristics of good touch, softness, stain resistance, wear resistance, antibacterial and mildew resistance, and flame retardancy, which can greatly improve the user experience and enhance the hygiene of the toilet seat ring.

[0012] In some embodiments of the present invention, the raw materials for preparing the skin-friendly material include siloxane monomer, white carbon black, modified hollow glass microspheres, hydrogen-containing polysiloxane and zinc oxide. Optionally, the polysiloxane material includes a product obtained by polymerization of siloxane monomer.

[0013] In some embodiments of the present invention, the raw materials for preparation include, by mass, 5-200 parts of siloxane monomer, 2-80 parts of white carbon black, 1-100 parts of modified hollow glass microspheres, 1-50 parts of hydrogen-containing polysiloxane and 0-10 parts of zinc oxide material.

[0014] In some embodiments of the present invention, the preparation raw materials include, by mass, 10-80 parts of siloxane monomer, 5-60 parts of white carbon black, 1-60 parts of modified hollow glass microspheres, 1-30 parts of hydrogen-containing polysiloxane and 0.1-2 parts of zinc oxide material.

[0015] In some embodiments of the present invention, the preparation raw materials include, by mass, 30-50 parts of siloxane monomer, 10-40 parts of white carbon black, 5-40 parts of modified hollow glass microspheres, 5-15 parts of hydrogen-containing polysiloxane and 0.5-1 part of zinc oxide material.

[0016] In some embodiments of the present invention, the preparation raw materials include, by mass, 30-50 parts of siloxane monomer, 15-25 parts of white carbon black, 10-25 parts of modified hollow glass microspheres, 5-15 parts of hydrogen-containing polysiloxane and 0.5-1 part of zinc oxide material.

[0017] In some embodiments of the present invention, the siloxane monomer comprises fluorovinylsiloxane.

[0018] In some embodiments of the present invention, the method for preparing the fluorine-based vinyl siloxane comprises the following steps: taking vinyl siloxane, fluorine-containing acrylate and an initiator, mixing, heating and stirring, to obtain the fluorine-based vinyl siloxane.

[0019] In some embodiments of the present invention, the mass ratio of the vinyl siloxane, fluorinated acrylate and initiator is selected from (50-150):(1-20):(0.01-3), such as (90-95):(5-10):(0.05-0.1).

[0020] In some embodiments of the present invention, the heating temperature is 50-100°C, such as 70-80°C.

[0021] In some embodiments of the present invention, the heating and stirring time is 5-100 min, such as 10-30 min.

[0022] In some embodiments of the present invention, the mass percentage of vinyl groups in the vinyl siloxane is 0.1-3%, such as 0.3-1.0%.

[0023] In some embodiments of the present invention, the viscosity of the vinyl siloxane at 25° C. is 1000-50000 mPa.s, such as 5000-10000 mPa.s.

[0024] In some embodiments of the present invention, the fluorine-containing acrylate includes at least one of fluoroalkyl (meth)acrylate or perfluoropolyether (meth)acrylate.

[0025] In some embodiments of the present invention, the fluoroalkyl (meth)acrylate includes at least one of octafluoropentyl acrylate, tridecafluorooctyl methacrylate, or heptadecafluorodecyl methacrylate; the perfluoropolyether (meth)acrylate includes PFPE-CH2-R, wherein PFPE is a perfluoropolyether chain and the R group is a methacryloyloxy group or an acryloyloxy group.

[0026] In some embodiments of the present invention, the initiator comprises azobisisobutyronitrile.

[0027] In some embodiments of the present invention, the method for preparing the fluorinated vinyl siloxane comprises the following steps:

[0028] Add 90-95 parts by mass of vinyl siloxane, 5-10 parts by mass of fluorinated acrylate, and 0.05-0.1 parts by mass of azobisisobutyronitrile into a reaction kettle, stir uniformly at a high speed of 2000-2500 rpm, heat to 70-80° C., and then stir at a constant speed of 1000-1200 rpm for 10-30 minutes to obtain the fluorinated vinyl siloxane.

[0029] In some embodiments of the present invention, the silica is fumed silica.

[0030] In some embodiments of the present invention, the mass fraction of silicon dioxide (SiO2) in the fumed silica is greater than 95%.

[0031] In some embodiments of the present invention, the particle size D of the fumed silica is 90 It is 3-50nm, such as 8-17nm.

[0032] In some embodiments of the present invention, the specific surface area of ​​the fumed silica is 50-500 m 2 / g, such as 150-300m 2 / g.

[0033] In some embodiments of the present invention, the zinc oxide material is a nano zinc oxide material.

[0034] In some embodiments of the present invention, the particle size D of the zinc oxide material is 90 It can be 1-50nm, such as 5-20nm.

[0035] In some embodiments of the present invention, the specific surface area of ​​the zinc oxide material is 70 m 2 / g or less, such as 50m 2 / g or less.

[0036] In some embodiments of the present invention, the method for preparing the zinc oxide material comprises the following steps:

[0037] S ZnO -1, carbonate, water and glyceryl monostearate are mixed, and then mixed with zinc salt to obtain a precipitate;

[0038] S ZnO -2. After washing the precipitate, it is dried and calcined at 800-1000° C. to obtain the zinc oxide material.

[0039] In some embodiments of the present invention, step S ZnO -1: the carbonate is sodium carbonate; and / or the zinc salt is zinc sulfate.

[0040] In some embodiments of the present invention, step S ZnO -1, comprising: dissolving sodium carbonate in water to a concentration of 1.0-2.5 mol / L; then adding glyceryl monostearate to a concentration of 0.8 x 10 - 4 mol / L; zinc sulfate was added under continuous stirring to obtain a mixed material II, and finally a white precipitate was obtained; wherein the ratio of the added amount of zinc sulfate to the mixed material II was (0.5-1.0) mol:1L.

[0041] In some embodiments of the present invention, step S ZnO -2, the white precipitate is continuously filtered and washed three times with ethanol, and then the precipitate is baked in an oven at 40-60°C for 3-4 hours to obtain a linear precursor; the dried linear precursor is placed in a tube furnace, and the temperature of the tube furnace is raised to 800-1000°C in an air atmosphere, and the temperature is kept and calcined for 0.5-2 hours to obtain a nano zinc oxide material.

[0042] In some embodiments of the present invention, the hydrogen-containing polysiloxane is a low-hydrogen-containing polysiloxane, wherein the mass percentage of hydrogen in the hydrogen-containing polysiloxane is 0.01-5%, such as 0.05-1%.

[0043] In some embodiments of the present invention, the method for preparing the modified hollow glass microspheres comprises the following steps: taking hollow glass microspheres, deoxidizing them, coating their surfaces with surfactants, grinding them, and drying them to obtain the modified hollow glass microspheres.

[0044] In some embodiments of the present invention, the true density of the hollow glass microspheres is 0.01-2 g / cm 3 , such as 0.1-1.0g / cm 3 .

[0045] In some embodiments of the present invention, the bulk density of the hollow glass microspheres is 0.01-2 g / cm 3 , such as 0.1-0.5g / cm 3 .

[0046] In some embodiments of the present invention, the particle size D of the hollow glass microspheres is 90 It is 0.1-10 μm, such as 1-5 μm.

[0047] In some embodiments of the present invention, the particle size D of the modified hollow glass microspheres is 90 It is 10-100nm, such as 50nm.

[0048] In some embodiments of the present invention, the method for preparing the modified hollow glass microspheres specifically comprises the following steps:

[0049] Sa-1, hollow glass microspheres are deoxidized by heat preservation at high temperature under vacuum conditions above 5 Pa;

[0050] Sa-2, mixing the deoxygenated hollow glass microspheres with a suspending solvent, adjusting the pH to 6-8, adding a surfactant, and ultrasonically treating to obtain slurry I;

[0051] Sa-3, ball milling the slurry I and vacuum drying it to obtain modified hollow glass microspheres.

[0052] In some embodiments of the present invention, in step Sa-1, the high temperature insulation temperature is 700-1400°C, such as 900-1200°C.

[0053] In some embodiments of the present invention, in step Sa-1, the high temperature insulation time is 0.5-5 hours, such as 0.5-1.5 hours.

[0054] In some embodiments of the present invention, in step Sa-1, the temperature is raised to the high temperature holding temperature at a rate of 5-20°C / min under a vacuum degree higher than 5 Pa.

[0055] In some embodiments of the present invention, in step Sa-2, the suspending solvent includes ethanol, which may be anhydrous ethanol.

[0056] In some embodiments of the present invention, in step Sa-2, the mass ratio of the suspending solvent to the hollow glass microspheres is (2-10):1.

[0057] In some embodiments of the present invention, in step Sa-2, the pH value is adjusted to 6-8 using formic acid and aqueous ammonia.

[0058] In some embodiments of the present invention, in step Sa-2, the surfactant includes polyoxyethylene dioleate.

[0059] In some embodiments of the present invention, in step Sa-2, the ultrasonic treatment time is 5-100 min, such as 15-30 min.

[0060] In some embodiments of the present invention, in step Sa-3, the rotation speed of the ball milling treatment is 50-800 r / min, such as 200-400 r / min.

[0061] In some embodiments of the present invention, in step Sa-3, the ball milling treatment time is 5-35 hours, such as 10-20 hours.

[0062] In some embodiments of the present invention, in the ball milling process of step Sa-3, the grinding balls used are zirconium beads, specifically, ultrafine hard zirconium beads with a diameter of 5 mm.

[0063] In some embodiments of the present invention, in the ball milling process of step Sa-3, the weight ratio of balls to materials is (30-120):1, such as (50-80):1.

[0064] In some embodiments of the present invention, in step Sa-3, the vacuum drying temperature is 50-150°C, such as 80-120°C.

[0065] In some embodiments of the present invention, in step Sa-3, the vacuum degree of vacuum drying is 0.5-50 Pa, such as 1-5 Pa.

[0066] In some embodiments of the present invention, the preparation raw materials further include a silane coupling agent.

[0067] In some embodiments of the present invention, the raw materials for preparation include 0.1-10 parts by mass of a silane coupling agent, such as 1-2 parts by mass.

[0068] In some embodiments of the present invention, the silane coupling agent includes at least one of dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylcyclosiloxane or hexamethyldisilazane.

[0069] In some embodiments of the present invention, the raw materials further include a pigment. A suitable pigment can be selected based on actual needs. By weight, the raw materials include 0-10 parts of pigment, such as 0.001-1 part.

[0070] In some embodiments of the present invention, the pigment includes but is not limited to polycyclic pigments, aromatic methane pigments, etc. Specifically, the pigment includes but is not limited to azo pigments, phthalocyanine pigments, anthraquinone, indigo pigments, quinacridone, dioxazine, titanium dioxide, etc.

[0071] In some embodiments of the present invention, the pigment includes but is not limited to one or more of white toner, yellow toner, green toner, purple toner, orange toner or cyan toner.

[0072] In some embodiments of the present invention, the preparation raw materials further include a platinum catalyst.

[0073] In some embodiments of the present invention, the raw materials for preparation include 0.01-5 parts by mass of platinum catalyst, such as 0.2-0.8 parts by mass.

[0074] In some embodiments of the present invention, the mass fraction of the platinum element contained in the platinum catalyst is 50-5000 ppm, such as 500-1500 ppm.

[0075] In some embodiments of the present invention, the platinum catalyst comprises at least one of a tetramethyldivinyldisiloxane chloroplatinic acid complex, a platinum-alkyne complex, or an isopropanol solution of chloroplatinic acid.

[0076] In some embodiments of the present invention, the preparation raw materials further include an inhibitor.

[0077] In some embodiments of the present invention, the raw materials for preparation include 0.01-3 parts of the inhibitor by mass, such as 0.1-0.6 parts.

[0078] In some embodiments of the present invention, the inhibitor comprises at least one of polyvinyl polysiloxane, an acetylenic alcohol compound, an amide compound, or a cyano compound.

[0079] In some embodiments of the present invention, the alkynol compound includes at least one of 3-trimethylsilyl-2-propyn-1-ol, 2-propyn-1-ol, methyl butynol, ethynyl cyclohexanol, tert-butyl cyclohexanol, phenyl butynol or 3,5-dimethyl-1-hexyn-3-ol.

[0080] In some embodiments of the present invention, the thickness of the skin-friendly material is 0.01-20 mm, such as 0.1-10 mm, 0.1-2 mm, 0.1-0.6 mm, etc.

[0081] The second aspect of the present invention provides a method for preparing a skin-friendly material for a one-piece toilet seat, comprising the following steps:

[0082] S1, taking siloxane monomer, silane coupling agent, white carbon black, modified hollow glass microspheres, and zinc oxide material, mixing them, heat-treating them under vacuum conditions, and adding platinum catalyst to obtain mixed material I;

[0083] Taking hydrogen-containing polysiloxane and an inhibitor, mixing them to obtain a mixed material II;

[0084] S2, mixing the mixed material I and the mixed material II to obtain a skin-friendly slurry; and baking to obtain a skin-friendly material.

[0085] In some embodiments of the present invention, in step S1, siloxane monomer, silane coupling agent, white carbon black, modified hollow glass microspheres, zinc oxide material and pigment are mixed.

[0086] In some embodiments of the present invention, in step S1, the mixing method includes stirring, and optionally, the stirring time is 0.2-10 hours, and further optionally 1-3 hours. Optionally, the stirring temperature is selected from 15-35°C.

[0087] In some embodiments of the present invention, in step S1, after the mixing treatment, the temperature is raised to 110-170° C., stirred for 0.2-10 h under vacuum conditions, the vacuum is stopped, a platinum catalyst is added, and stirred to obtain a mixed material I.

[0088] In some embodiments of the present invention, in step S2, the baking temperature is 50-110°C, such as 70-100°C.

[0089] In some embodiments of the present invention, in step S2, the baking time is 1-20 minutes, such as 3-8 minutes.

[0090] In some embodiments of the present invention, in step S2, mixed material I and mixed material II are mixed to obtain a skin-friendly slurry; the skin-friendly slurry is applied to the surface of the object to be covered, and baked to form the skin-friendly material on the surface of the object to be covered.

[0091] In some embodiments of the present invention, in step S2, the object to be covered includes cloth.

[0092] In a third aspect, the present invention provides a membrane-coated seat ring comprising the above-mentioned skin-friendly material.

[0093] In some embodiments of the present invention, the membrane seat ring includes a skin-friendly layer, and the skin-friendly layer is the skin-friendly material.

[0094] In some embodiments of the present invention, the film-coated seat ring includes a support layer, a heat-conducting layer, a base fabric layer, and the skin-friendly layer stacked in sequence.

[0095] In some embodiments of the present invention, the support layer comprises at least one of thermoplastic plastic or thermosetting plastic. Alternatively, the support layer may be a base layer of the seat ring, formed from thermoplastic plastic and / or thermosetting plastic under high temperature and high pressure.

[0096] In some embodiments of the present invention, the thermoplastic plastic includes but is not limited to PP, ABS, etc.

[0097] In some embodiments of the present invention, the thermosetting plastic includes but is not limited to UF and the like.

[0098] In some embodiments of the present invention, the thickness of the support layer is 0.2-20 mm, such as 1.5-4.0 mm.

[0099] In some embodiments of the present invention, the thickness of the heat conductive layer is 0.01-5 mm, such as 0.05-0.6 mm.

[0100] In some embodiments of the present invention, the thermal conductivity of the heat-conducting layer is 5-2000 W / (m·K), such as 5-1000 W / (m·K).

[0101] In some embodiments of the present invention, the thermally conductive layer comprises at least one of graphene, boron nitride, thermally conductive silicon, TPU, or a metal. In some embodiments of the present invention, the thermally conductive layer comprises a graphene thermally conductive film, a boron nitride thermally conductive film, a thermally conductive silicone sheet, a TPU thermally conductive film, or a metal thermally conductive film. Optionally, the metal includes, but is not limited to, copper, aluminum, and the like. For example, the thermally conductive layer may be copper foil, aluminum foil, or the like.

[0102] In some embodiments of the present invention, the base fabric layer has a thickness of 0.01-3 mm, such as 0.1-0.5 mm.

[0103] In some embodiments of the present invention, the thickness of the skin-friendly layer is 0.01-20 mm, such as 0.1-10 mm, 0.1-2 mm, 0.1-0.6 mm, etc.

[0104] In some embodiments of the present invention, the shape of the surface of the skin-friendly layer facing away from the base fabric layer is not limited, and can be, for example, a flat surface, a curved surface, a flat surface or a curved surface with a partially recessed area, etc. In some embodiments of the present invention, the skin-friendly layer has a convex curved surface structure. Optionally, the longitudinal cross-section of the skin-friendly layer has a symmetrical structure.

[0105] In some embodiments of the present invention, the film-coated seat ring is a multifunctional film-coated seat ring.

[0106] In the above embodiment, the skin-friendly layer is the outermost layer (surface layer) of the membrane seat ring. It is made of a skin-friendly material and has pleasant tactile properties, is soft, stain-resistant, wear-resistant, antibacterial, mildew-proof, and flame-retardant. The base fabric layer provides a coating load layer and can be made of materials such as polyester. The thermal conductive layer, located between the support layer and the base fabric, has a high thermal conductivity and provides thermal conductivity, making the multifunctional membrane seat ring more skin-friendly and shortening heating time.

[0107] In a fourth aspect, the present invention provides a method for preparing a film-coated seat ring, comprising the following steps:

[0108] Take the stacked base fabric layer and the skin-friendly layer, apply adhesive or melt-adhesive film on the side of the base fabric layer facing away from the skin-friendly layer to obtain component I; after applying adhesive or melt-adhesive film on one side of the thermal conductive layer, stack component I, the thermal conductive layer and the support layer, and press to obtain the coated seat ring.

[0109] In some embodiments of the present invention, the support layer is heated to a temperature of 110-170° C. before being covered with the heat-conducting layer and component I.

[0110] In some embodiments of the present invention, the pressing time is 1-20 min, such as 0.5-5 min.

[0111] In some embodiments of the present invention, the temperature during the pressing process is 110-170° C.; and / or the pressure is 0.1-1.0 MPa.

[0112] In a fifth aspect, the present invention provides a one-piece toilet comprising the above-mentioned coated seat ring.

[0113] The sixth aspect of the present invention proposes the application of the above-mentioned skin-friendly material and film-coated seat ring in bathroom products. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0115] Figure 1 Schematic diagram of the structure of the membrane seat ring in Example 1 of the present invention;

[0116] Figure 2 This is the SEM image of the skin-friendly layer of the film-coated seat ring in Comparative Example 2;

[0117] Figure 3 This is an SEM image of the skin-friendly layer of the film-coated seat ring of Example 4 of the present invention;

[0118] Figure 4 Schematic diagram of the thermal conductivity test of the film-coated seat ring in the test example of the present invention. DETAILED DESCRIPTION

[0119] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0120] The experimental methods in the following examples, for which specific conditions are not specified, are generally performed in accordance with conventional conditions in the art or conditions recommended by the manufacturers; the raw materials and reagents used, unless otherwise specified, are all commercially available from conventional markets.

[0121] Fumed silica: The mass fraction of silicon dioxide (SiO2) is greater than 95%; the particle size of fumed silica is D 90 The surface area is 15nm and the specific surface area is 250m 2 / g;

[0122] Hydrogen-containing silicone oil: hydrogen-containing polysiloxane, the mass percentage of hydrogen in the hydrogen-containing polysiloxane is 0.05-1%; Dow Corning (DOW), MHX-1107 (hydrogen-containing silicone oils can also be purchased from other manufacturers);

[0123] Pigment: Titanium dioxide ZR-940, available from Jiangsu Zhenti Chemical Co., Ltd. (titanium dioxide can also be purchased from other manufacturers);

[0124] Platinum catalyst: tetramethyldivinyldisiloxane chloroplatinic acid complex, platinum content of 1200 ppm, Guangdong Dinglisen New Materials Co., Ltd. (Platinum catalysts can also be purchased from other manufacturers);

[0125] Inhibitor: 3-trimethylsilyl-2-propyn-1-ol, available from Chengdu Sitiande Biotechnology Co., Ltd. (also available from other manufacturers);

[0126] Thermally conductive film: Graphene thermally conductive film, model LWS-G070, with a horizontal thermal conductivity of 1200 W / mK, from Desco Electronic Technology (Kunshan) Co., Ltd. (graphene thermally conductive film can also be purchased from other manufacturers);

[0127] Silane coupling agent: dimethyldiethoxysilane, available from Shandong Shenglilong New Materials Co., Ltd. (also available from other manufacturers);

[0128] Siloxane monomer I: a polysiloxane containing a vinyl end group, which can be purchased from Hubei Longsheng Sihai New Materials Co., Ltd. as JP-02V-1000 (polysiloxane containing a vinyl end group can also be purchased from other manufacturers).

[0129] Zinc oxide material: the mass fraction of zinc oxide is greater than 95%; the particle size of zinc oxide material is D 90 The surface area is 10-15nm and the specific surface area is 50-70m 2 / g, can be prepared by the following preparation method, comprising the following steps:

[0130] At room temperature, chemically pure sodium carbonate was dissolved in deionized water to a concentration of 1.5 mol / L; then the surfactant glyceryl monostearate was added to a concentration of 0.8 x 10 -4 mol / L; slowly adding analytical pure zinc sulfate (ZnSO4) under constant stirring to make its concentration in the reaction system 0.8 mol / L, and finally obtaining a white precipitate; the white precipitate was continuously filtered and washed three times with a 95 wt% pure ethanol aqueous solution, and then the precipitate was placed in a 50°C oven for 3.5 hours to remove the solvent to obtain a linear precursor; the dried linear precursor was placed in a tube furnace, and the tube furnace was heated to 950°C in an air atmosphere, and the heat was kept and calcined for 1 hour to obtain a nano zinc oxide material.

[0131] Modified hollow glass microspheres (surface-modified hollow glass microsphere powder) are prepared by the following preparation method:

[0132] (1) Take the true density as 0.8g / cm 3 , the bulk density is 0.4g / cm 3 , particle size D 90 Hollow glass microspheres with a diameter of 5 μm were placed in a ceramic crucible with a lid, heated at a rate of 10 ° C / min, the treatment temperature was 1000 ° C, the holding time was 1 h, and the vacuum degree was higher than 5 Pa for deoxidation treatment;

[0133] (2) The deoxygenated hollow glass microsphere powder is prepared into a suspension using anhydrous ethanol, wherein the mass ratio of anhydrous ethanol to hollow glass microspheres is 3:1 (any value between 2 and 10:1 is acceptable), the pH value of the suspension is adjusted to 7.5 using formic acid and aqueous ammonia, a polyoxyethylene dioleate surfactant is added for surface coating, and then ultrasonic treatment is performed for 25 minutes;

[0134] (3) The hollow glass microbead powder slurry with the above surface treatment was subjected to high-energy ball milling in a planetary ball mill. The ball milling speed was 300 r / min, the grinding time was 15 h, the grinding balls were ultrafine hard zirconium beads with a diameter of Φ5 mm, and the ball-to-material weight ratio was 70:1;

[0135] (4) After ball milling, the slurry was vacuum dried. The vacuum drying temperature was 110℃, the vacuum degree was 4Pa, and the processing time was 3h. After ball milling, the particle size was tested and the particle size D 90 is 50nm.

[0136] Polyoxyethylene dioleate: purchased from Hubei Jushun Chemical Co., Ltd. O20 (polyoxyethylene dioleate can also be purchased from other manufacturers).

[0137] Fluorovinylsiloxane is prepared by the following preparation method:

[0138] In a reaction kettle, 92 parts by mass of vinyl siloxane (0.5% vinyl mass percentage, viscosity of 8000 mPa.s at 25°C), 6 parts by mass of fluoroalkyl (meth) acrylate (octafluoropentyl acrylate), and 0.08 parts by mass of azobisisobutyronitrile were added and stirred uniformly at a high speed of 2300 rpm, heated to 75°C, and then stirred at a constant speed of 1100 rpm for 20 minutes. In some other embodiments of the present invention, in the preparation of fluorovinyl siloxane, the fluoroalkyl methacrylate can also be selected from tridecafluorooctyl methacrylate or heptadecafluorodecyl methacrylate; perfluoropolyether (meth) acrylate can also be used instead of the fluoroalkyl (meth) acrylate in the above embodiment. Specifically, the molecular formula of the perfluoropolyether acrylate can be PFPE-CH2-R, wherein PFPE is a perfluoropolyether chain and the R group is a methacryloyloxy group or an acryloyloxy group.

[0139] Examples 1 to 6

[0140] The embodiment discloses a series of film-coated seats for one-piece toilets, the preparation process of which includes:

[0141] (I) Preparation of skin-friendly layer components A and B:

[0142] Preparation of skin-friendly layer component A: Fluorovinylsiloxane, silane coupling agent, fumed silica, modified hollow glass microspheres (surface-modified hollow glass microsphere powder), zinc oxide, and pigment were added to a kneader and stirred at room temperature for 1.5 hours (stirring speed: 2500 rpm). The mixture was heated to 140°C and stirred under vacuum for 1-4 hours (stirring speed: 2000 rpm). The vacuum was then removed, and a platinum catalyst was added. Stirring was continued at high speed (stirring speed: 250 rpm for 3 hours) to obtain component A. The zinc oxide acts as an antibacterial and antifungal agent.

[0143] Preparation of component B of the skin-friendly layer: hydrogen-containing polysiloxane (hydrogen-containing silicone oil) and an inhibitor were added to a blender and stirred at high speed (stirring speed 250 rpm, stirring time 3 h) to obtain component B.

[0144] (II) Coating and forming of the skin-friendly layer: Components A and B of the skin-friendly layer were mixed uniformly in a high-speed disperser (stirring speed 250 rpm, stirring time 3 h), coated on the base fabric, and then baked at 85°C for 6 min to form a skin-friendly layer on the surface of the base fabric.

[0145] (III) A mold suitable for the seat ring support layer is prepared using aluminum alloy or stainless steel, and the seat ring support layer is placed on the mold and heated to 150°C. A layer of EVA hot melt adhesive film (thickness of 0.1-0.3mm, or adhesive coating method can also be used) is attached to the bottom surface of the thermal conductive layer and the bottom surface of the base fabric away from the skin-friendly layer, respectively. Then, they are applied on the support layer in sequence, namely the support layer, thermal conductive layer, base fabric and skin-friendly layer. A certain pressure (pressure of 200Pa) is applied, and the seat ring is taken out after constant temperature and pressure maintenance at 150°C for 4 minutes to obtain a multifunctional coated seat ring.

[0146] Among them, in the coated seat ring, the support layer is PP with a thickness of 3.5mm; the thermal conductive layer is 0.4mm thick; the base fabric is PET material with a thickness of 0.5mm; the skin-friendly layer has a width of 7-12cm and a thickness of 0.1-0.6mm (the skin-friendly layer is a convex arc surface structure, with a maximum protruding thickness of 0.6mm and a minimum thickness of 0.1mm, and a symmetrical longitudinal section).

[0147] The embodiment further discloses a series of one-piece toilets, each comprising any one of the above-mentioned membrane-coated seats.

[0148] In some other embodiments of the present invention, the side of the skin-friendly layer facing away from the base fabric layer may be flat, and the thickness of the skin-friendly layer may be 0.1-0.6 mm.

[0149] Example 7

[0150] This embodiment discloses a film-coated seat ring, which differs from the embodiment 4 in that the film-coated seat ring of this embodiment does not contain a heat-conductive film.

[0151] This embodiment also discloses a one-piece toilet, including the film-coated seat ring of this embodiment.

[0152] Comparative Example 1

[0153] This comparative example discloses a film-coated seat ring, which differs from Example 1 in that: this comparative example does not use surface-modified hollow glass microbead powder, and uses 40 parts by mass of fumed silica.

[0154] This comparative example also discloses a one-piece toilet, including the film-coated seat ring in this comparative example.

[0155] Comparative Example 2

[0156] This comparative example discloses a coated seat ring, which differs from Example 1 in that: this comparative example does not use surface-modified hollow glass microsphere powder, and uses 20 parts by mass of fumed silica and 20 parts by mass of hollow glass microspheres (without surface modification) in this comparative example.

[0157] Comparative Example 3

[0158] This comparative example discloses a coated seat ring, which differs from Example 1 in that: in this comparative example, zinc oxide of equal mass fraction is used to replace the zinc oxide material in Example 1, wherein the particle size of the zinc oxide in this comparative example is 1-10 μm.

[0159] This comparative example also discloses a one-piece toilet, including the film-coated seat ring in this comparative example.

[0160] Comparative Example 4

[0161] This comparative example discloses a film-coated seat ring, which differs from Example 1 in that the fluorinated vinyl siloxane in Example 1 is replaced by an equal mass fraction of siloxane monomer I in this comparative example.

[0162] This comparative example also discloses a one-piece toilet, including the film-coated seat ring in this comparative example.

[0163] The raw material dosage of the skin-friendly layer material and whether it contains a thermal conductive film in each embodiment and comparative example are shown in Table 1 below:

[0164] Table 1

[0165]

[0166] Test example

[0167] This test example conducted performance tests on the materials and film-coated seat rings obtained in the examples and comparative examples, specifically including:

[0168] 1. SEM morphology analysis: The SEM image of the skin-friendly layer prepared in Example 2 (without modified hollow glass microspheres) is as follows: Figure 2 As shown, the SEM image of the skin-friendly layer (modified hollow glass microspheres) prepared in Example 4 is as follows Figure 3 shown.

[0169] 2. Test on the anti-fouling performance of the skin-friendly layer of the coated seat of one-piece toilets

[0170] 1) Water Contact Angle Test: This test is conducted in accordance with GB / T 30693-2014, "Measurement of the Contact Angle of Water with Plastic Films." The contact angle is measured using a water contact angle analyzer and used as a basis for evaluating the sample's anti-fouling properties. A larger water contact angle indicates better hydrophobicity.

[0171] 2) Anti-fouling performance test: According to GB / T17657-2013 "Test methods for physical and chemical properties of wood-based panels and veneered wood-based panels", pollutants such as cola, soy sauce, and ketchup are placed on the surface of the coated seat of a one-piece toilet for 24 hours. The seat is then cleaned with an organic solvent and the surface appearance, shape, gloss, and color of the coated seat are observed to see if there are any changes. The more severe the changes, the worse the material's anti-fouling performance. Conversely, slight changes or no traces of changes indicate better anti-fouling performance.

[0172] Level 5: No significant changes;

[0173] Grade 4: Slight changes in gloss and / or color;

[0174] Level 3: Moderate changes in gloss and / or color;

[0175] Level 2: There is a noticeable change in gloss and / or color;

[0176] Level 1: Surface deformation and / or blistering

[0177] 3. Test on the antibacterial and mildew-proof performance of the skin-friendly layer of the coated seat of one-piece toilet

[0178] 1) Antibacterial performance test: Determined according to the method of GB / T 31402-2015.

[0179] 2) Mold resistance test: Determined according to the method of GB / T 1741-2020. Mold resistance level: 0: no growth; 1: trace growth (the moldy area of ​​the test sample accounts for less than 10%); 2: slight growth (the moldy area of ​​the test sample accounts for less than 30% and greater than or equal to 10%); 3: moderate growth (the moldy area of ​​the test sample accounts for less than 60% and greater than or equal to 30%); 4: severe growth (the moldy area of ​​the test sample accounts for greater than or equal to 60%).

[0180] 4. Wear resistance test

[0181] The abrasion resistance of the coated seat surface (skin-friendly layer) of one-piece toilets was tested according to GB / T 21996.3-2007, "Textiles - Determination of the Abrasion Resistance of Fabrics by the Martindale Method - Part 3: Determination of Mass Loss." A load of 795g was applied, and the surface layer was rubbed 4000 times. The abrasion resistance index was then calculated.

[0182] A i =n / Δm

[0183] Where:

[0184] A i - Wear resistance index, in times per milligram (times / mg);

[0185] n-total number of frictions, in times;

[0186] Δm-mass loss of the sample under the total number of friction times, in milligrams (mg).

[0187] A i The larger the value, the better the wear resistance of the product.

[0188] 5. Thermal conductivity test

[0189] Test methods include: Figure 4 As shown in the figure, several thermocouples are arranged at the top of the coated seat ring of the one-piece toilet (L in the figure represents the length of the empty space in the seat ring, the horizontal line marked with L is a schematic diagram of the thermocouple arrangement, and the black dot on the horizontal line is the location of the thermocouple). Use aluminum foil tape with a size of 10x10cm (model: M425) to cover the thermocouple. The aluminum foil tape and the thermocouple should be tightly fitted without any bubbles in the middle. The center of the tape is the top point of the thermocouple, and the thermocouple wire except the one covered by the aluminum foil tape should be upright and away from the surface of the seat ring. Place the coated seat ring in a constant temperature box and set the ambient temperature in the constant temperature box to 0℃. After the temperature of the coated seat ring reaches 0℃, add 220V voltage to the thermal conductive layer in the coated seat ring (the top surface area of ​​the graphene thermal conductive film away from the supporting layer is about 920 square centimeters) to make it turn on and heat up. Use a stopwatch to record the time it takes for the skin-friendly layer of the coated seat ring at each thermocouple measurement point to rise from 0℃ to 40℃, and calculate the average value t of the obtained time.

[0190] In particular, no heat-conducting layer is provided in Example 7. In the absence of an external heat source, the skin-friendly layer of the film seat ring of Example 7 in the constant temperature box is always approximately 0°C.

[0191] 6. Skin feel test

[0192] The test involves touching the one-piece toilet's coated seat to assess its smoothness. A skin-friendly toilet seat will feel very smooth and fine. The test also involves sitting on the one-piece toilet's coated seat to assess its elasticity.

[0193] Multiple parallel experiments were conducted, with 6 people selected for testing in each group. Among the 6 people, testers were selected according to the age groups of old (55-65 years old), middle-aged (35-45 years old), and young (20-30 years old). There were 2 people in each age group, 1 male and 1 female. They scored the skin feel and calculated the average score. The full score for each person is 10 points. The higher the score, the better the skin feel effect / elasticity.

[0194] The test results are shown in Table 2:

[0195]

[0196] From the above-mentioned Examples 1-5, when the contents of other components remain unchanged, as the content of surface-modified hollow glass microspheres increases, the surface water contact angle and anti-fouling performance gradually improve; compared with Comparative Examples 1-2, it can be seen that the water contact angle and anti-fouling performance of the coated seat rings of Examples 1-5 are significantly improved.

[0197] Comparing Example 4 with Example 5, when the content of surface-modified hollow glass microspheres is increased to a certain level, the antifouling performance is not improved much. This is because the Si-O bond length of silica gel is long, the Si-O-Si bond angle is large, the distance between atoms is long, and the degree of freedom is large. The free space is increased, resulting in many micropores on the surface of the polymer (polysiloxane material), showing many "pits" (such as Figure 2 As shown in Figure 2); Silica is used as the main reinforcing filler, but because the surface of fumed silica contains a large number of hydroxyl groups, it can react with the end groups of silica molecules (polysiloxane materials) to undergo condensation reactions, thereby hardening the rubber and making processing difficult; Surface-modified hollow glass microspheres, due to their small particle size, large specific surface area, many unpaired atoms, and many idle bonds, can bond well to fill the micropores on the surface of silica gel (as shown in Figure 2). Figure 3 As shown, the product surface becomes smoother and flatter, while stain resistance is enhanced. While the product hardness remains relatively unchanged, its wear resistance is also significantly improved. When the amount of surface-modified hollow glass microspheres added reaches a certain range, further additions yield no significant improvement. Compared to Example 6 (where the content of surface-modified hollow glass microspheres is further increased), the coated seat rings of Examples 1-5 exhibit a better skin feel, greater elasticity, and greater smoothness.

[0198] From Examples 1-5 and 7, it can be seen that after adding a layer of heat-conducting film between the base fabric layer and the support layer, the thermal conductivity of the product is greatly improved, and the effect of instant heating and use can be achieved.

[0199] In summary, the multifunctional one-piece toilet coated seat ring in the present invention includes a skin-friendly layer, a base fabric layer, a heat-conducting layer and a support layer which are stacked in sequence, wherein the skin-friendly layer and the heat-conducting layer can be respectively produced by a coating process on the upper and lower sides of the base fabric layer, and the skin-friendly layer has good touch, softness, stain resistance, wear resistance, antibacterial and mildew-proof and flame retardant functions; the base fabric layer provides a coating load layer, which can be a material such as polyester; the heat-conducting layer is sandwiched between the base fabric layer and the support layer, covered with a heat-conducting material, has a high thermal conductivity coefficient, and has a heat-conducting function; the support layer is the base layer of the seat ring, which can be formed by high temperature and high pressure of thermoplastic plastics such as PP, ABS, etc. and thermosetting plastics such as UF.

[0200] Unless otherwise specified, the term "about" herein means that the tolerance is within a range of ±2%. For example, "about 100" is actually 100 ± 2% × 100. "Normal temperature" or "room temperature" herein, unless otherwise specified, means approximately 20-30°C. "Between" herein is inclusive; for example, "between 2-3" includes both the endpoints 2 and 3.

[0201] While the embodiments of the present invention have been described in detail above with reference to the accompanying drawings, the present invention is not limited to the embodiments described above. Various modifications may be made within the scope of knowledge possessed by a person skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof may be combined with one another unless there is a conflict.

Claims

1. A skin-friendly material for a one-piece toilet seat, characterized in that: The invention comprises polysiloxane materials, white carbon black and modified hollow glass microspheres, wherein the modified hollow glass microspheres comprise hollow glass microspheres modified by a surfactant; the particle size D of the modified hollow glass microspheres is 90 10-100nm; The modified hollow glass microspheres are prepared by a preparation method comprising the following steps: taking hollow glass microspheres, deoxidizing them, coating their surfaces with a surfactant, grinding them, and drying them to obtain the modified hollow glass microspheres; The raw materials for preparing the skin-friendly material include, by mass, 5-200 parts of siloxane monomer, 2-80 parts of white carbon black, 5-30 parts of modified hollow glass microspheres, 1-50 parts of hydrogen-containing polysiloxane and 0-10 parts of zinc oxide material, wherein the siloxane monomer includes fluorine-based vinyl siloxane, and the zinc oxide material is not 0.

2. The skin-friendly material according to claim 1, characterized in that The raw materials for the preparation include, by weight, 10-80 parts of siloxane monomer, 5-60 parts of white carbon black, 5-30 parts of modified hollow glass microspheres, 1-30 parts of hydrogen-containing polysiloxane and 0.1-2 parts of zinc oxide material.

3. The skin-friendly material according to claim 2, characterized in that The fluorine-based vinyl siloxane is prepared by a preparation method comprising the following steps: taking vinyl siloxane, fluorine-containing acrylate and an initiator, mixing, heating and stirring to obtain the fluorine-based vinyl siloxane.

4. The skin-friendly material according to claim 3, characterized in that The mass ratio of the vinyl siloxane, the fluorinated acrylate and the initiator is selected from (50-150): (1-20): (0.01-3).

5. The skin-friendly material according to claim 3, characterized in that The vinyl mass percentage of the vinyl siloxane is 0.1-3%; and / or the viscosity of the vinyl siloxane at 25° C. is 1000-50000 mPa.s.

6. The skin-friendly material according to claim 3, characterized in that The heating temperature is 50-100° C.; and / or the heating and stirring time is 5-100 min.

7. The skin-friendly material according to claim 3, characterized in that The fluorine-containing acrylate includes at least one of fluoroalkyl (meth)acrylate and perfluoropolyether (meth)acrylate; and / or the initiator includes azobisisobutyronitrile.

8. The skin-friendly material according to claim 1, characterized in that The white carbon black is fumed white carbon black; and / or the zinc oxide material is a nano zinc oxide material; and / or the mass percentage of hydrogen in the hydrogen-containing polysiloxane is 0.01-5%.

9. The skin-friendly material according to claim 8, characterized in that The mass fraction of silicon dioxide in the fumed silica is greater than 95%; and / or the particle size D of the fumed silica is greater than 95%. 90 3-50nm; and / or, the specific surface area of ​​the fumed silica is 50-500m 2 / g; and / or, the particle size D of the zinc oxide material 90 1-50nm; and / or, the specific surface area of ​​the zinc oxide material is 70m 2 / g or less.

10. The skin-friendly material according to claim 8, characterized in that The zinc oxide material is prepared by a preparation method comprising the following steps: S ZnO -1, carbonate, water and glyceryl monostearate are mixed, and then mixed with zinc salt to obtain a precipitate; S ZnO -2. After washing the precipitate, drying it, and calcining it at 800-1000° C. to obtain the zinc oxide material.

11. The skin-friendly material according to claim 1, characterized in that The true density of the hollow glass microspheres is 0.01-2 g / cm 3 ; and / or, the bulk density of the hollow glass microspheres is 0.01-2g / cm 3 ; and / or, the particle size D of the hollow glass microspheres 90 0.1-10μm.

12. The skin-friendly material according to claim 1, characterized in that The modified hollow glass microspheres are prepared by a preparation method comprising the following steps: Sa-1, hollow glass microspheres are deoxidized by heat preservation at high temperature under vacuum conditions above 5 Pa; Sa-2, mixing the deoxygenated hollow glass microspheres with a suspending solvent, adjusting the pH to 6-8, adding a surfactant, and ultrasonically treating to obtain slurry I; Sa-3, ball milling the slurry I and vacuum drying it to obtain modified hollow glass microspheres.

13. The skin-friendly material according to claim 12, characterized in that In step Sa-1, the temperature of the high-temperature insulation is 700-1400° C.; and / or the insulation time of the high-temperature insulation is 0.5-5 hours.

14. The skin-friendly material according to claim 12, characterized in that In step Sa-2, the pH value is adjusted to 6-8 using formic acid and ammonia water; and / or, in step Sa-2, the surfactant includes polyoxyethylene dioleate.

15. The skin-friendly material according to claim 1, characterized in that The raw materials for preparation further include a silane coupling agent; and / or, the raw materials for preparation further include a pigment; and / or, the raw materials for preparation further include a platinum catalyst; and / or, the raw materials for preparation further include an inhibitor.

16. The skin-friendly material according to claim 15, characterized in that The silane coupling agent includes at least one of dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylcyclosiloxane or hexamethyldisilazane; and / or, the mass fraction of the platinum element contained in the platinum catalyst is 50-5000 ppm; and / or, the platinum catalyst includes at least one of a chloroplatinic acid tetramethyldivinyldisiloxane complex, a platinum-alkyne complex or an isopropanol solution of chloroplatinic acid; and / or, the inhibitor includes at least one of polyvinyl polysiloxane, an acetylenic alcohol compound, an amide compound or a cyano compound.

17. The skin-friendly material according to claim 16, characterized in that The alkynol compound includes at least one of 3-trimethylsilyl-2-propyn-1-ol, 2-propyn-1-ol, methyl butynol, ethynyl cyclohexanol, tert-butyl cyclohexanol, phenyl butynol or 3,5-dimethyl-1-hexyn-3-ol.

18. A method for preparing a skin-friendly material for a one-piece toilet seat according to any one of claims 1 to 17, characterized in that: The steps include: S1, taking siloxane monomer, silane coupling agent, white carbon black, modified hollow glass microspheres, and zinc oxide material, mixing them, heat-treating them under vacuum conditions, and adding platinum catalyst to obtain mixed material I; Taking hydrogen-containing polysiloxane and an inhibitor, mixing them to obtain a mixed material II; S2, mixing the mixed material I and the mixed material II to obtain a skin-friendly slurry; and baking to obtain a skin-friendly material.

19. The preparation method according to claim 18, characterized in that In step S2, the baking temperature is 50-110° C. and the baking time is 1-20 minutes.

20. A film-coated seat ring, characterized in that: The skin-friendly material comprises the skin-friendly material according to any one of claims 1 to 17 or the skin-friendly material prepared by the preparation method according to any one of claims 18 to 19.

21. The film-coated seat ring according to claim 20, characterized in that: The membrane seat ring includes a skin-friendly layer, and the skin-friendly layer is the skin-friendly material.

22. The film-coated seat ring according to claim 21, characterized in that: The film-coated seat ring comprises a supporting layer, a heat-conducting layer, a base fabric layer and the skin-friendly layer which are stacked in sequence.

23. The film-coated seat ring according to claim 22, characterized in that: The thickness of the support layer is 0.2-20 mm; and / or the thickness of the heat-conducting layer is 0.01-5 mm; and / or the thickness of the base fabric layer is 0.01-3 mm; and / or the thickness of the skin-friendly layer is 0.01-20 mm.

24. The film-coated seat ring according to claim 22, characterized in that: The thermal conductivity of the heat-conducting layer is 5-2000 W / (m·K).

25. The film-coated seat ring according to claim 22, characterized in that: The heat-conducting layer includes a graphene heat-conducting film, a boron nitride heat-conducting film, a heat-conducting silicone sheet, a TPU heat-conducting film or a metal heat-conducting film.

26. A one-piece toilet, characterized in that: Including the coated seat ring according to any one of claims 20 to 25.

27. Use of the skin-friendly material according to any one of claims 1 to 17, or the skin-friendly material prepared by the preparation method according to any one of claims 18 to 19, or the film-coated seat ring according to any one of claims 20 to 25 in sanitary products.

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