CN114619793B - Method for making glass-imitated double-layer decorative picture - Google Patents
Method for making glass-imitated double-layer decorative picture Download PDFInfo
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- CN114619793B CN114619793B CN202111396587.9A CN202111396587A CN114619793B CN 114619793 B CN114619793 B CN 114619793B CN 202111396587 A CN202111396587 A CN 202111396587A CN 114619793 B CN114619793 B CN 114619793B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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Abstract
The invention relates to the field of decorative picture manufacturing, and discloses a manufacturing method of a glass-imitated double-layer decorative picture, which comprises the following steps: (1) Cutting the PS plate and then sending the PS plate into a flat printer for pattern printing; (2) coating an adhesive on one side of the printed pattern; (3) And pasting the other PS plate on the PS plate printed with the patterns through an adhesive, and curing the adhesive to obtain the glass-imitated double-layer decorative picture. The invention utilizes the excellent characteristics of the PS plate to replace glass, and the decorative picture made of the PS plate not only has the visual effect similar to that of the glass, but also has the advantages of convenient processing, lightness, durability, easy surface cleaning and optional color selection compared with the traditional glass decorative picture.
Description
Technical Field
The invention relates to the technical field of decorative picture manufacturing, in particular to a manufacturing method of a glass-imitated double-layer decorative picture.
Background
The glass decoration painting in the traditional sense refers to painting on the surface of glass by oil painting, gouache painting, acrylic painting or Chinese painting pigment. With the progress of times, the modern glass decorative painting has new development in the aspects of painting concept and drawing technology. The modern drawing techniques of glass decorative pictures comprise dyeing, frosting, acid etching and the like, various drawing techniques use different materials and drawing programs, some colored glass is directly fired, and some colored glass is fired in fire after being coated with glaze or other colors. The glass decoration picture with complex picture is made by cutting glass into many small blocks according to the drawn color blocks, and then sintering the small blocks and combining them into a whole picture by using lead bars and glue. At present, many glass decorative painting works are not drawn by one technique, but several techniques are comprehensively used.
The traditional production of double-layer glass decorative painting on the existing market generally adopts various paints or glues as adhesives, directly sticks painting pigments on the surface of glass, and can also paint after carving, so that one painting is decomposed into two paintings, one glass decorative painting is used as a painting core, the other glass decorative painting is used as the appearance of a picture frame, and the two paintings are mutually lined and supplemented to form a decorative painting with three-dimensional effect. For example, a "double-layer glass painting structure" disclosed in chinese patent literature, publication No. CN103802586A includes an upper glass plate and a lower glass plate, the upper glass plate and the lower glass plate are clamped and fixedly connected by a seal, mounting interface boards are connected to both side surfaces of the upper glass plate and the lower glass plate, the mounting interface boards are clamped and connected between the upper glass plate and the lower glass plate, a rhinestone pattern layer is connected to a lower surface of the upper glass plate, and the rhinestone pattern layer is bonded to the upper glass plate.
However, the existing glass decorative painting is fragile, a hollow product cannot be manufactured, and the decorative painting is thick and heavy; moreover, the glass surface is not easy to be cleaned, is easy to have water stain and spot, and is not beneficial to the use of decorative pictures.
Disclosure of Invention
The invention provides a method for manufacturing a glass-imitated double-layer decorative picture, aiming at overcoming the problems that the conventional glass decorative picture is fragile and heavy, the surface of glass is not easy to clean, water stain and stain are easy to occur, and the use of the decorative picture is not facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for manufacturing a glass-imitated double-layer decorative picture comprises the following steps:
(1) Cutting the PS plate and then sending the PS plate into a flat printer for pattern printing;
(2) Coating an adhesive on one side of the printed pattern;
(3) And pasting the other PS plate on the PS plate printed with the patterns through an adhesive, and curing the adhesive to obtain the glass-imitated double-layer decorative picture.
The PS (polystyrene) plate has the characteristics of light specific gravity and high light transmittance, has good transparency and physical processing performance, can be freely cut, bent, punched and welded to be made into various product components, and is flexible and convenient to use. The invention utilizes the excellent characteristics of the PS plate to replace glass, and the decorative picture made of the PS plate not only has the visual effect similar to that of the glass, but also has the advantages of convenient processing, lightness, durability, easy surface cleaning and optional color selection compared with the traditional glass decorative picture. Meanwhile, the two layers of PS plates are bonded by the adhesive to prepare the double-layer decorative picture, so that the product has a three-dimensional effect; and the picture is positioned between the two layers of PS plates and protected by the adhesive, so that the picture has good adhesive force, stability and color retention.
Preferably, the adhesive used in step (2) is an epoxy adhesive; the curing temperature of the adhesive in the step (3) is 70-80 ℃, and the curing time is 20-40 min. The epoxy resin adhesive has the characteristics of strong adhesive force, high mechanical strength of materials, good chemical resistance, small curing shrinkage and the like, is used for bonding the double-layer PS plate, has good firmness, and is beneficial to prolonging the service life of the decorative picture.
Preferably, the thickness of the PS plate is 2 to 5mm.
Preferably, the surface of the PS plate is provided with a heat insulation coating which is formed by coating heat insulation paint and has the thickness of 0.3-0.5 mm; the heat insulation coating comprises the following components in parts by weight: 30 to 40 portions of silicone-acrylic emulsion, 15 to 25 portions of double-layer hollow reflective filler, 0.3 to 0.5 portion of thickening agent, 1 to 1.5 portions of film-forming additive, 0.5 to 1 portion of dispersant, 0.3 to 0.5 portion of defoaming agent, 0.1 to 0.2 portion of pH regulator and 45 to 65 portions of water.
Because the PS material has poor heat resistance and the thermal deformation temperature is 70-80 ℃, in order to avoid the subsequent high-temperature curing process of the adhesive and the use process of the decorative picture, the PS plate is heated and deformed to influence the decorative effect and the service life of the decorative picture, the surface of the PS plate is treated by the heat-insulating coating added with the double-layer hollow reflective filler. The double-layer hollow reflective filler takes zirconium dioxide as an inner layer and titanium dioxide as an outer layer, and the two layers of hollow structures have good heat insulation effect; meanwhile, the zirconium dioxide and the titanium dioxide have high reflectivity to infrared rays, and the thermal insulation coating can be endowed with good thermal insulation performance by combining barrier thermal insulation and reflective thermal insulation, so that the PS board can be effectively protected, and the decorative picture is not easy to deform under the action of high temperature.
According to the invention, a titanium dioxide layer spaced from zirconium dioxide is coated outside the hollow zirconium dioxide, and firstly, the barrier and heat insulation effects of the hollow zirconium dioxide are improved by forming a double-layer hollow structure; secondly, the infrared reflection performance of the filler is further improved by combining the zirconium dioxide and the titanium dioxide; thirdly, the outer titanium dioxide layer has good antibacterial action, so that the decorative painting has better antifouling and anti-mildew properties, and the decorative painting is convenient to manage.
Preferably, the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing ammonia water, water and absolute ethyl alcohol to obtain a mixed solution, dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, and separating, cleaning and drying a product after reaction to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, dropwise adding a zirconium oxychloride aqueous solution under the stirring state, separating, cleaning and drying a product after reaction to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water and ammonia water, dropwise adding ethyl orthosilicate under the stirring state, separating, cleaning and drying a product after reaction to obtain SiO 2 @ZrO 2 @SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water and ammonia water, dropwise adding butyl titanate while stirring, separating, cleaning and drying a product after reaction to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 Adding the microspheres into NaOH solution, stirring for reaction, separating, cleaning, drying and calcining the product to obtain the double-layer hollow reflective filler.
In the preparation process of the double-layer hollow reflective filler, the silicon dioxide microsphere seeds are taken as cores and are sequentially coated with ZrO 2 Layer, siO 2 Layer and TiO 2 A layer; then NaOH solution is used for leading SiO of the inner core and the middle layer 2 Washing to obtain the double-layer hollow structure with zirconium dioxide as the inner layer and titanium dioxide as the outer layer.
Preferably, the mass concentration of the ammonia water in the step A) is 25-28%, and the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 20-23; the volume ratio of the ethyl orthosilicate to the ammonia water is 1.5-2.
Preferably, the mass volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol in the step B) is 0.1-0.2g; the mass concentration of the zirconium oxychloride aqueous solution is 1-3%, and the volume ratio of the absolute ethyl alcohol, the ammonia water and the zirconium oxychloride aqueous solution is (100).
Preferably, siO in step C) 2 @ZrO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100-20; the volume ratio of the ethyl orthosilicate to the ammonia water is 1-2.
Preferably, siO in step D) 2 @ZrO 2 @SiO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100-15; the volume ratio of the butyl titanate to the ammonia water is 2.5-3.5.
Preferably, the concentration of the NaOH solution in the step E) is 0.2-0.4 mol/L, and the stirring reaction time is 6-10 h; the calcining temperature is 700-800 ℃, and the calcining time is 3-5 h.
The diameter of an inner layer cavity of the prepared double-layer hollow reflective filler is 100-150 nm, and the wall thickness of the inner layer is 30-40 nm by controlling the reactant dosage and the reaction conditions; the distance between the two layers is 40-50 nm, the wall thickness of the outer layer is 40-50 nm, and the heat insulation effect is good.
Therefore, the invention has the following beneficial effects:
(1) The PS plate is used for replacing glass, the manufactured double-layer decorative painting is light and durable, the painting is convenient to manage, and the color can be selected randomly;
(2) The two layers of PS plates are bonded through the adhesive to prepare the double-layer decorative picture, so that the product has a three-dimensional effect; the picture is positioned between the two layers of PS plates and is protected by the adhesive, so that the picture has good adhesive force, stability and color retention;
(3) The PS plate is protected by the heat insulation coating added with the double-layer hollow reflective filler, so that the decorative picture is not easy to deform under the action of high temperature.
Drawings
FIG. 1 is a pictorial view of the glass-imitated double-layer decorative painting prepared in example 1.
Detailed Description
The invention is further described with reference to the following figures and embodiments.
In the present invention, all the raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
General examples:
a manufacturing method of a glass-imitated double-layer decorative picture comprises the following steps:
(1) Coating the heat insulation coating on the surface of a PS plate with the thickness of 2-5 mm to obtain the heat insulation coating with the thickness of 0.3-0.5 mm, wherein the heat insulation coating comprises the following components in parts by weight: 30-40 parts of silicone-acrylic emulsion, 15-25 parts of double-layer hollow reflective filler, 0.3-0.5 part of thickening agent, 1-1.5 parts of film-forming auxiliary agent, 0.5-1 part of dispersing agent, 0.3-0.5 part of defoaming agent, 0.1-0.2 part of pH regulator and 45-65 parts of water; the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 20-23; dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.5-2; stirring and reacting for 2-4 h, then centrifugally separating the product, washing with water and ethanol for 3-4 times, and drying at room temperature for 8-12 h to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, and dropwise adding 1-3 wt% of zirconium oxychloride aqueous solution under a stirring state, wherein the mass-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is (100-15); heating to 40-45 ℃, stirring and reacting for 20-24 h, then centrifugally separating the product, washing for 3-4 times with water and ethanol, drying for 8-12 h at room temperature to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100-20; dropwise adding tetraethoxysilane under the stirring state, wherein the volume ratio of tetraethoxysilane to ammonia water is 1-2; stirring and reacting for 1-2 h, then centrifugally separating the product, washing with water and ethanol for 3-4 times, and drying at room temperature for 8-12 h to obtain SiO 2 @ZrO 2 @SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 @SiO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100-15; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of the butyl titanate to the ammonia water is 2.5-3.5; heating to 40-45 ℃, stirring and reacting for 20-24 h, then centrifugally separating the product, washing for 3-4 times by water and ethanol, drying for 8-12 h at room temperature to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 Adding the microspheres into 0.2-0.4 mol/L NaOH solution, stirring and reacting for 6-10 h, separating, cleaning and drying the product, and calcining for 3-5 h at 700-800 ℃ to obtain the double-layer hollow reflective filler;
(2) After the heat insulation coating is cured, cutting the PS plate, and then sending the PS plate into a flat-bed printer for pattern printing;
(3) Spraying or silk-screen printing a two-component epoxy resin adhesive on one side of the printed pattern;
(4) And (3) pasting the other PS plate on the PS plate printed with the pattern through an adhesive, and curing at 70-80 ℃ for 20-40 min to obtain the glass-like double-layer decorative picture.
Example 1:
a method for manufacturing a glass-imitated double-layer decorative picture comprises the following steps:
(1) Spraying a thermal insulation coating on the surface of a PS plate with the thickness of 3mm to obtain a thermal insulation coating with the thickness of 0.4mm, wherein the thermal insulation coating comprises the following components in parts by weight: 35 parts of SD-528 silicone-acrylic emulsion (Jiangsushenda new material science and technology Co., ltd.), 20 parts of double-layer hollow reflective filler, 0.4 part of sodium carboxymethylcellulose, 1.2 parts of ethylene glycol ethyl ether, 0.6 part of dispersing agent (Silok-7191W), 0.4 part of defoaming agent (Silok-4500), 0.15 part of 25-28 wt% ammonia water and 55 parts of water; the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is (22); dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.8; stirring for reaction for 3h, then centrifugally separating the product, washing with water and ethanol for 4 times, and drying at room temperature for 10h to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, dropwise adding a 2wt% zirconium oxychloride aqueous solution under a stirring state, wherein the mass-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is 100; heating to 43 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 The mass volume ratio of the nanospheres to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding tetraethoxysilane under the stirring state, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.5; stirring for reaction for 1.5h, centrifuging, washing with water and ethanol for 4 times, and drying at room temperature for 10h to obtain SiO 2 @ZrO 2 @SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 @SiO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of the butyl titanate to the ammonia water is 3; heating to 42 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 Adding the microspheres into 0.3mol/L NaOH solution, stirring and reacting for 8 hours, separating, cleaning and drying the product, and calcining for 4 hours at 750 ℃ to obtain the double-layer hollow reflective filler;
(2) After the heat insulation coating is cured, cutting the PS plate, and then sending the PS plate into a flat-bed printer for pattern printing;
(3) Silk-screen printing a two-component epoxy resin adhesive (Araldite AY103-1 HY991) on one side of the printed pattern, wherein the thickness of a dry film is 0.2mm;
(4) And (3) sticking the other PS plate on the PS plate printed with the pattern through an adhesive, and curing for 30min at 75 ℃ to obtain the imitation glass double-layer decorative picture shown in figure 1.
Example 2:
a method for manufacturing a glass-imitated double-layer decorative picture comprises the following steps:
(1) Spraying a thermal insulation coating on the surface of a PS plate with the thickness of 2mm to obtain a thermal insulation coating with the thickness of 0.5mm, wherein the thermal insulation coating comprises the following components in parts by weight: 40 parts of SD-528 silicone-acrylic emulsion (Jiangsushenda new material science and technology Co., ltd.), 25 parts of double-layer hollow reflective filler, 0.5 part of sodium carboxymethylcellulose, 1.5 parts of ethylene glycol ethyl ether, 1 part of dispersing agent (Silok-7191W), 0.5 part of defoaming agent (Silok-4500), 0.2 part of 25-28 wt% ammonia water and 65 parts of water; the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 20; dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.5; stirring for reaction for 2h, then centrifugally separating the product, washing with water and ethanol for 4 times, and drying at room temperature for 12h to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in anhydrous BAdding ammonia water into alcohol, and dropwise adding a 1wt% zirconium oxychloride aqueous solution under a stirring state, wherein the mass-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.1g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is 100; heating to 40 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 8h to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding tetraethoxysilane under a stirring state, wherein the volume ratio of tetraethoxysilane to ammonia water is 1; stirring for reaction for 2h, centrifuging, washing with water and ethanol for 4 times, and drying at room temperature for 8h to obtain SiO 2 @ZrO 2 @SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, and adding water and ammonia water, siO 2 @ZrO 2 @SiO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of the butyl titanate to the ammonia water is 2.5; heating to 40 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, and drying at room temperature for 8h to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 Adding the microspheres into 0.2mol/L NaOH solution, stirring and reacting for 10 hours, separating, cleaning and drying the product, and calcining for 5 hours at 700 ℃ to obtain the double-layer hollow reflective filler;
(2) After the heat insulation coating is cured, cutting the PS plate, and then sending the PS plate into a flat-bed printer for pattern printing;
(3) Silk-screen printing a two-component epoxy resin adhesive (Araldite AY103-1 HY991) on one side of a printed pattern, wherein the thickness of a dry film is 0.2mm;
(4) And (3) pasting the other PS plate on the PS plate printed with the pattern through an adhesive, and curing at 70 ℃ for 40min to obtain the glass-imitated double-layer decorative picture.
Example 3:
a manufacturing method of a glass-imitated double-layer decorative picture comprises the following steps:
(1) Spraying a thermal insulation coating on the surface of a PS plate with the thickness of 5mm to obtain a thermal insulation coating with the thickness of 0.3mm, wherein the thermal insulation coating comprises the following components in parts by weight: 30 parts of SD-528 silicone-acrylic emulsion (Jiangsushenda new material science and technology Co., ltd.), 15 parts of double-layer hollow reflective filler, 0.3 part of sodium carboxymethylcellulose, 1 part of ethylene glycol ethyl ether, 0.5 part of dispersing agent (Silok-7191W), 0.3 part of defoaming agent (Silok-4500), 0.1 part of 25-28 wt% ammonia water and 45 parts of water; the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is (23); dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 2; stirring for reaction for 4h, centrifuging, washing with water and ethanol for 3 times, and drying at room temperature for 8h to obtain silica microsphere seed;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, and dropwise adding a 3wt% zirconium oxychloride aqueous solution under a stirring state, wherein the mass-to-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.2g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is (100); heating to 45 ℃, stirring for reaction for 20h, then centrifugally separating the product, washing with water and ethanol for 3 times, and drying at room temperature for 8h to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding tetraethoxysilane under a stirring state, wherein the volume ratio of tetraethoxysilane to ammonia water is 2; stirring for reaction for 1h, centrifugally separating the product, washing with water and ethanol for 3 times, and drying at room temperature for 12h to obtain SiO 2 @ZrO 2 @SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, and adding water and ammonia water, siO 2 @ZrO 2 @SiO 2 The mass-volume ratio of the nanospheres to the absolute ethyl alcohol is 0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of butyl titanate to ammonia water is 3.5; heating to 45 ℃, stirring to react for 20h, then centrifugally separating the product, washing with water and ethanol for 3 times, drying at room temperature for 12h to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 Adding the microspheres into 0.4mol/L NaOH solution, stirring and reacting for 6 hours, separating, cleaning and drying the product, and calcining for 3 hours at 800 ℃ to obtain the double-layer hollow reflective filler;
(2) After the heat insulation coating is cured, cutting the PS plate, and then sending the PS plate into a flat-bed printer for pattern printing;
(3) Silk-screen printing a two-component epoxy resin adhesive (Araldite AY103-1 HY991) on one side of the printed pattern, wherein the thickness of a dry film is 0.5mm;
(4) And (3) pasting the other PS plate on the PS plate printed with the pattern through an adhesive, and curing at 80 ℃ for 20min to obtain the glass-imitated double-layer decorative picture.
Comparative example 1 (without TiO provision) 2 Layer(s):
the components of the thermal barrier coating in comparative example 1 include, in parts by weight: 35 parts of SD-528 silicone-acrylic emulsion, 20 parts of hollow reflective filler, 0.4 part of sodium carboxymethylcellulose, 1.2 parts of ethylene glycol ethyl ether, 0.6 part of dispersing agent, 0.4 part of defoaming agent, 0.15 part of 25-28 wt% ammonia water and 55 parts of water; the preparation method of the hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is (22); dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.8; stirring for reaction for 3h, then centrifugally separating the product, washing with water and ethanol for 4 times, and drying at room temperature for 10h to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, dropwise adding a 2wt% zirconium oxychloride aqueous solution under a stirring state, wherein the mass-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is 100; heating to 43 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Adding the nanospheres into 0.3mol/L NaOH solution, stirring and reacting for 8 hours, separating, cleaning and drying the product, and calcining for 4 hours at 750 ℃ to obtain the hollow reflective filler.
The rest is the same as in example 1.
Comparative example 2 (TiO) 2 The layer being directly coated on ZrO 2 Surface):
the components of the thermal barrier coating in comparative example 2 include, in parts by weight: 35 parts of SD-528 silicone-acrylic emulsion, 20 parts of hollow reflective filler, 0.4 part of sodium carboxymethylcellulose, 1.2 parts of ethylene glycol ethyl ether, 0.6 part of dispersing agent, 0.4 part of defoaming agent, 0.15 part of 25-28 wt% ammonia water and 55 parts of water; the preparation method of the hollow reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water with water and absolute ethyl alcohol to obtain a mixed solution, wherein the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is (22); dropwise adding tetraethoxysilane into the mixed solution under the stirring condition, wherein the volume ratio of tetraethoxysilane to ammonia water is 1.8; stirring for reaction for 3h, then centrifugally separating the product, washing with water and ethanol for 4 times, and drying at room temperature for 10h to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, dropwise adding a 2wt% zirconium oxychloride aqueous solution under a stirring state, wherein the mass-volume ratio of the silicon dioxide microsphere seeds to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is (100); heating to 43 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water, ammonia water and SiO 2 @ZrO 2 The mass volume ratio of the nanospheres to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of butyl titanate to ammonia water is 3; heating to 42 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain SiO 2 @ZrO 2 @TiO 2 Microspheres;
d) Mixing SiO 2 @ZrO 2 @TiO 2 Adding the microspheres into 0.3mol/L NaOH solution, stirring and reacting for 8 hours, separating, cleaning and drying the product, and calcining for 4 hours at 750 ℃ to obtain the hollow reflective filler.
The rest is the same as in example 1.
Comparative example 3 (no hollow structure used):
the components of the thermal insulation coating in the comparative example 3 comprise the following components in parts by weight: 35 parts of SD-528 silicone-acrylic emulsion, 20 parts of reflective filler, 0.4 part of sodium carboxymethylcellulose, 1.2 parts of ethylene glycol ethyl ether, 0.6 part of dispersing agent, 0.4 part of defoaming agent, 0.15 part of 25-28 wt% ammonia water and 55 parts of water; the preparation method of the reflective filler comprises the following steps:
a) Uniformly mixing 25-28 wt% of ammonia water and absolute ethyl alcohol to obtain a mixed solution, and dropwise adding a 2wt% of zirconium oxychloride aqueous solution into the mixed solution under a stirring state, wherein the volume ratio of the absolute ethyl alcohol to the ammonia water to the zirconium oxychloride aqueous solution is 100; heating to 43 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h to obtain ZrO 2 Nanospheres;
b) Is reacted with ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water and ammonia water, zrO 2 The mass volume ratio of the nanospheres to the absolute ethyl alcohol is 0.15g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100; dropwise adding butyl titanate under the stirring state, wherein the volume ratio of the butyl titanate to the ammonia water is 3; heating to 42 ℃, stirring for reaction for 24h, then centrifugally separating the product, washing with water and ethanol for 4 times, drying at room temperature for 10h, and then calcining at 750 ℃ for 4h to obtain the reflective filler.
The rest is the same as in example 1.
The heat insulating performance of the heat insulating coating in the above examples and comparative examples was tested by the following methods: respectively coating the thermal insulation coatings in the examples and the comparative examples on an aluminum plate, wherein the thickness of the coating is 0.3mm, and heating the aluminum plate for 30min at 100 ℃; the aluminum plate was punched to the coating, thermocouples were attached to the inside and outside of the coating to measure the temperature, and the surface temperature of the aluminum plate and the outer surface temperature of the coating were measured after heating for 30min, with the results shown in table 1.
Table 1: and (5) testing the heat insulation performance of the heat insulation coating.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Skin temperature (. Degree. C.) of aluminum plate | 100 | 99 | 100 | 100 | 99 | 99 |
| Temperature (. Degree.C.) of the outer surface of the coating | 63 | 62 | 62 | 82 | 72 | 89 |
As can be seen from table 1, the thermal barrier coatings of examples 1 to 3 have good thermal insulation properties due to the addition of the double-layer hollow reflective filler of the present application; in contrast, in comparative example 1, hollow zirconium dioxide is used as a reflective filler, and no titanium dioxide outer layer is arranged on the surface of the hollow zirconium dioxide, so that a double-layer hollow structure is not provided, the heat insulation performance is reduced, and the reflective heat insulation performance is also reduced without the matching of titanium dioxide and zirconium dioxide, so that the final heat insulation performance of the heat insulation coating is obviously reduced compared with that of example 1. In comparative example 2, the titanium dioxide layer is directly coated on the surface of the hollow zirconium dioxide, a double-layer hollow structure is not formed, and the heat insulation performance of the heat insulation coating is reduced compared with that of example 1, which shows that the double-layer hollow structure can effectively improve the heat insulation effect. In the comparative example 3, the titanium dioxide layer is coated on the surface of the solid zirconium dioxide microsphere, so that the heat insulation effect of a hollow structure is not generated, and the heat insulation performance of the heat insulation coating is obviously reduced only by reflection heat insulation.
The glass-imitated double-layer decorative picture prepared by the invention is light and durable, has a three-dimensional effect, is easy to finish on the surface, and has a long service life.
Claims (8)
1. A manufacturing method of a glass-imitated double-layer decorative picture is characterized by comprising the following steps:
(1) Cutting the PS plate and then sending the PS plate into a flat printer for pattern printing;
(2) Coating an adhesive on one side of the printed pattern;
(3) Pasting the other PS plate on the PS plate printed with the patterns through an adhesive, and obtaining the glass-imitated double-layer decorative picture after the adhesive is cured;
the surface of the PS plate is provided with a heat insulation coating which is formed by coating a heat insulation coating and has a thickness of 0.3 to 0.5mm; the heat insulation coating comprises the following components in parts by weight: 30-40 parts of silicone-acrylic emulsion, 15-25 parts of double-layer hollow reflective filler, 0.3-0.5 part of thickener, 1-1.5 parts of film-forming auxiliary agent, 0.5-1 part of dispersant, 0.3-0.5 part of defoamer, 0.1-0.2 part of pH regulator and 45-65 parts of water;
the preparation method of the double-layer hollow reflective filler comprises the following steps:
a) Uniformly mixing ammonia water, water and absolute ethyl alcohol to obtain a mixed solution, dropwise adding ethyl orthosilicate into the mixed solution under the stirring condition, and separating, cleaning and drying a product after reaction to obtain silicon dioxide microsphere seeds;
b) Dispersing the silicon dioxide microsphere seeds in absolute ethyl alcohol, adding ammonia water, dropwise adding zirconium oxychloride aqueous solution under the stirring state, separating, cleaning and drying the product after reaction to obtain SiO 2 @ZrO 2 Nanospheres;
c) Mixing SiO 2 @ZrO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water and ammonia water, dropwise adding tetraethoxysilane under the stirring state, separating, cleaning and drying a product after reaction to obtain SiO 2 @ZrO 2 @ SiO 2 Nanospheres;
d) Mixing SiO 2 @ZrO 2 @SiO 2 Dispersing the nanospheres in absolute ethyl alcohol, adding water and ammonia water, dropwise adding butyl titanate while stirring, separating, cleaning and drying a product after reaction to obtain SiO 2 @ZrO 2 @SiO 2 @TiO 2 Microspheres;
e) Mixing SiO 2 @ZrO 2 @SiO 2 @TiO 2 And adding the microspheres into a NaOH solution, stirring for reaction, separating, cleaning, drying and calcining the product to obtain the double-layer hollow reflective filler.
2. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the adhesive used in the step (2) is an epoxy resin adhesive; and (3) curing the adhesive in the step (3) at the curing temperature of 70-80 ℃ for 20-40min.
3. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the thickness of the PS plate is 2 to 5mm.
4. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the mass concentration of ammonia water in the step A) is 25 to 28%, and the volume ratio of absolute ethyl alcohol to water to ammonia water is 20 to 23; the volume ratio of the ethyl orthosilicate to the ammonia water is 1.5 to 2.
5. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the mass-volume ratio of the silica microsphere seeds to the absolute ethyl alcohol in the step B) is 0.1 to 0.2g; the mass concentration of the zirconium oxychloride aqueous solution is 1 to 3%, and the volume ratio of the absolute ethyl alcohol, the ammonia water and the zirconium oxychloride aqueous solution is 100 to 10 to 15.
6. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein in the step C), siO is used 2 @ZrO 2 The mass volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is 100 to 15 to 20; the volume ratio of the ethyl orthosilicate to the ammonia water is 1 to 2.
7. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the SiO in step D) is 2 @ZrO 2 @SiO 2 The mass volume ratio of the nanospheres to the absolute ethyl alcohol is 0.1-0.2g; the volume ratio of the absolute ethyl alcohol to the water to the ammonia water is (100); the volume ratio of the butyl titanate to the ammonia water is 2.5 to 3.5.
8. The method for making the imitation glass double-layer decorative picture according to claim 1, wherein the concentration of the NaOH solution in the step E) is 0.2 to 0.4mol/L, and the stirring reaction time is 6 to 10 hours; the calcining temperature is 700 to 800 ℃, and the calcining time is 3 to 5h.
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