WO2018210111A1 - 3d decorative glass and manufacturing method thereof - Google Patents

Abstract

A 3D decorative glass and manufacturing method thereof. The 3D decorative glass comprises: a 3D glass substrate, a decorative ink layer that is partially hollowed-out, a metallic mirror filling layer and a light-shielding black ink layer, wherein the decorative ink layer is attached to a side surface of the 3D glass substrate, the metallic mirror filling layer is attached to the side surface of the 3D glass substrate and fills the hollowed-out region of the decorative ink layer, and the light-shielding black ink layer covers exposed surfaces of the decorative ink layer and the metallic mirror filling layer.

Description

3D decorative glass and preparation method thereof

Cross-reference to related applications

The present application claims priority to and the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit.

Technical field

The present application relates to the field of 3D glass surface decoration, in particular to 3D decorative glass, and to a method for preparing 3D decorative glass.

Background technique

With the improvement of living standards, consumers are increasingly demanding the appearance of electronic products; and can improve the window effect of electronic products, making them crystal clear, and the 3D glass with strong perspective is more and more widely used.

At present, the surface decoration method of 3D glass mainly includes a screen printing method and a film thermal transfer method. The former prints the ink by using a mesh screen of about 300 mesh to stencil the pattern; the latter prints the pattern in advance on PET or PMMA. On the film, the film sheet is placed in a grinder during use, and the pattern is transferred onto the glass after heating. However, for the screen printing method, due to the structure of the 3D glass, when the hyperboloid glass is used, the film thickness and the effect of the printed curved surface portion are difficult to control uniformity, affecting the pattern precision; for the film thermal transfer method, Since the sheet film is stretched and deformed and transferred onto the curved glass, the pattern is stretched, and the decorative effect is deteriorated; and the method is highly demanding on the mold, and the sheet needs to be heated and softened to completely conform to the glass.

Summary of the invention

The purpose of the present application is to overcome one of the problems existing in the prior art, and to provide a 3D decorative glass and a method of preparing the same to optimize the accuracy of the pattern in the 3D decorative glass.

In order to achieve the above object, according to an aspect of the present application, a 3D decorative glass is provided, the 3D decorative glass comprising: a 3D glass substrate, a partially hollow decorative ink layer, a metal mirror filling layer, and a black light-shielding ink layer, a decorative ink layer attached to one side surface of the 3D glass substrate, the metal mirror filling layer being attached on the one side surface of the 3D glass substrate and filled in a hollow region of the decorative ink layer, The black light-shielding ink layer covers the exposed surface of the decorative ink layer and the metal mirror-filled layer; wherein the partially hollow decorative ink layer is dried and solidified by spraying the light-absorbing ink on one side surface of the 3D glass substrate to form a light-absorbing ink. The layer is formed by laser etching the light absorbing ink layer from the other side of the 3D glass substrate.

Meanwhile, according to another aspect of the present application, there is provided a method of preparing a 3D decorative glass, the method comprising the steps of: S1, spraying a light absorbing ink on one side surface of a 3D glass substrate, and drying and solidifying to form a light absorbing ink layer S2, injecting a laser from the other side of the 3D glass substrate, etching the light absorbing ink layer to form a partially hollow decorative ink layer; S3, filling the decorative ink layer on the one side surface of the 3D glass substrate The hollow region forms a metal mirror filling layer; S4, a black light-shielding ink layer is formed on a surface of the decorative ink layer and the metal mirror filling layer away from the 3D glass substrate.

Further, according to still another aspect of the present application, there is also provided a 3D decorative glass formed by the preparation method according to the present application.

Applying the 3D decorative glass of the present application and the preparation method thereof, by using the light absorbing ink, the ink layer formed by the light absorbing ink has good light absorption effect and is easy to be processed by laser engraving, and the laser is used to etch one side (front side) of the 3D glass substrate. The light absorbing ink layer on the other side (back side) of the 3D glass substrate is used to form a partially hollowed out (having a specific pattern) decorative ink layer, thereby preparing a 3D decorative glass. The 3D decorative glass and the preparation method thereof have the following beneficial effects:

(1) The 3D decorative glass of the present application is based on the incident direction of the laser so that the burr on the surface of the decorative ink layer is formed on the side of the decorative ink layer away from the 3D glass substrate, and at this time, by forming one or more layers of background ink later The side of the decorative ink layer away from the 3D glass substrate (surface burr) is masked, so that the edge of the decorative ink layer is smooth and smooth without sharp protrusions, thereby facilitating obtaining a higher precision pattern and making the 3D decorative glass more Beautiful.

(2) Compared with the screen printing method and the film thermal transfer method, the 3D decorative glass of the present application and the preparation method thereof are convenient for pattern conversion by using a laser etching light absorbing ink layer to form a partial hollow (with a specific pattern) decorative ink layer. The design effect is immediately visible, and the formed pattern has higher precision, which makes the decorative effect of the 3D glass better.

(3) Preparation method of the 3D decorative glass of the present application The surface decoration of the 3D glass can be realized by the spraying process combined with the laser etching process and the optional coating process, and the high-precision mold development required for various printing and coating can be avoided. Conducive to saving equipment costs; and because there is no need to develop the mold required for printing press, greatly reducing new products, shortening the new pattern development cycle and improving production efficiency.

DRAWINGS

1 is a three-view view of a 3D glass substrate applied in accordance with an embodiment of the present application;

2 is a scanning electron micrograph of a 3D glass forming a partially hollow decorative ink layer obtained according to the step S2 of Embodiment 1 of the present application at a magnification of 100 times;

3 is a scanning electron micrograph of a 3D glass forming a partially hollow decorative ink layer obtained by the step S2 of the first embodiment of the present application at a magnification of 200 times;

4 is a schematic view showing a product image of a 3D decorative glass prepared according to Embodiment 1 of the present application;

5 is a schematic view showing a product image of a 3D decorative glass prepared according to Comparative Example 1;

Figure 6 is a scanning electron micrograph of the 3D glass forming the partially hollow decorative ink layer obtained according to the step 3 of Comparative Example 3 at a magnification of 100 times;

Fig. 7 is a scanning electron micrograph of the 3D glass forming the partially hollow decorative ink layer obtained according to Comparative Example 3, step S2, at a magnification of 200 times.

Description of the reference numerals

11 is the flat area, 12 is the curved area

21 is a decorative ink layer, and 22 is a metal mirror filling layer.

detailed description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.

In the present application, the term "blackness value My" means the degree of blackness of carbon black, which can be determined according to the test of DIN 55979-1989 pigment. The method for determining the black value of carbon black pigment; the term "oil absorption" means per 100 g. The mass of DOP (di-n-octyl phthalate) consumed by precipitated silica (ie, the mass of DOP required for the absolute surface of the precipitated silica to be completely wetted by the oil), which can be obtained by DOP titration.

As described in the background section of the present application, the conventional 3D decorative glass generally has a problem of insufficient precision of the decorative pattern. In response to this technical problem, a 3D decorative glass is provided in the present application, the 3D decorative glass comprising: a 3D glass substrate, a partially hollow decorative ink layer, a metal mirror filling layer, and a black shading ink layer, the decoration An ink layer is attached on one side surface of the 3D glass substrate, the metal mirror filling layer is attached on the one side surface of the 3D glass substrate, and is filled in a hollow region of the decorative ink layer, The black shading ink layer covers the exposed surface of the decorative ink layer and the metal mirror filling layer; wherein the partially hollow decorative ink layer is dried and solidified by spraying the light absorbing ink on one side surface of the 3D glass substrate to form a light absorbing ink layer And forming a light-absorbing ink layer by laser etching from the other side of the 3D glass substrate.

In the present application, "a partially hollow decorative ink layer" means a structure formed by removing a part of the light-absorbing ink layer by laser etching to expose the surface of the 3D glass; 3D glass in the hollowed portion of the decorative ink layer Exposed to the outside, it can be directly in contact with the metal mirror filling layer.

According to some embodiments of the present application, the 3D decorative glass includes carbon black and precipitated silica, and the carbon black content is based on the dry weight of the oil-absorbing ink (weight without solvent). The content of precipitated silica is from 3 to 6% by weight, and the content of precipitated silica is from 6 to 12% by weight; in some embodiments of the present application, the blackness value My of the carbon black is greater than 250.

The above-mentioned light absorbing ink provided by the present application can increase the degree of light absorption of the ink layer formed by selecting a carbon black having a specific blackness value and a specific content; and by selecting a specific content of precipitated silica, it can be increased by The diffuse reflection phenomenon in the formed ink layer; by combining the light absorption degree and the diffuse reflection phenomenon of the ink layer reasonably, the ink layer has the advantages of better light absorption effect and easier laser laser engraving, so that even if it is separated The glass can still form a decorative ink layer with a specific structure by laser laser engraving; thereby, the method of etching the light-absorbing ink layer by laser transmission of the 3D glass substrate is performed to change the direction of the surface burr of the decorative ink layer formed by etching. The edge of the decorative ink layer is smooth and smooth, and has no pointed protrusions, thereby facilitating obtaining a pattern with higher precision and making the 3D decorative glass more beautiful.

According to the 3D decorative glass of some embodiments of the present application, in order to further optimize the degree of light absorption of the formed ink layer, the laser engraving (laser etching) effect of the ink layer is optimized to obtain a 3D decorative glass with higher pattern accuracy, The blackness value My of carbon black in the light absorbing ink is 250-350. The optional carbon black products include, but are not limited to, FW200 and FW285 which are commercially available from Evonik, or MONARCH 1400 which is commercially available from Cabot Corporation.

According to the 3D decorative glass of some embodiments of the present application, in order to further optimize the diffuse reflection effect of the formed ink layer, the specular reflection of the ink layer is reduced, thereby optimizing the laser engraving (laser etching) effect of the ink layer to obtain a pattern. a more accurate 3D decorative glass, wherein the oil absorption of the precipitated silica in the light absorbing ink is less than 250 g/100 g. In some embodiments of the present application, the oil absorption of the precipitated silica in the light absorbing ink is (100-240) g/100g. Optional precipitated silica products include, but are not limited to, OK607, OK520, or OK412, commercially available from Degussa; or E-1011, E200A, or E1009, commercially available from East Grass.

According to some embodiments of the present application, in order to avoid the occurrence of a coarsening phenomenon of the formed ink layer, the edge of the decorative ink layer formed by laser laser engraving is optimized, and the particle size of the carbon black in the light absorbing ink is optimized. In some embodiments of the present application, the particle size distribution of the carbon black in the light absorbing ink is in the range of 4-16 nm, and the particle size distribution can be obtained by a laser diffraction particle size analyzer; in some embodiments of the present application, The particle size D90 of the precipitated silica in the light absorbing ink is greater than 5 μm. In some embodiments of the present application, the particle size D90 of the precipitated silica in the light absorbing ink is 5-10 μm, wherein the particle diameter D90 is a volume average. The diameter, which is the equivalent diameter of the largest particle when the cumulative distribution in the particle size distribution curve is 90 vol%.

According to some embodiments of the present application, the 3D decorative glass is prepared by mixing a light-absorbing ink composition with an organic solvent, taking into consideration the adhesion of the formed light-absorbing ink layer and the characteristics of easy laser engraving. The light absorbing ink composition comprises, based on the total weight thereof, 45 to 72% by weight of a saturated polyester resin, 15 to 30% by weight of an amino resin, 3 to 6% by weight of carbon black, and 6 to 12% by weight of a precipitated dioxide. Silicon, 0.1-2% by weight of silane coupling agent, 0.1-10% by weight of functional auxiliary. More preferably, the light absorbing ink composition comprises, based on the total weight thereof, 50 to 65 wt% of a saturated polyester resin, 18 to 26 wt% of an amino resin, 3 to 6 wt% of carbon black, and 8 to 12% by weight. Precipitated silica, 0.5-1% by weight of silane coupling agent, 0.1-10% by weight of functional auxiliary.

According to the 3D decorative glass of some embodiments of the present application, in order to optimize the adhesion of the formed ink layer, the saturated polyester resin in the light-absorbing ink composition is a saturated polyester resin having a glass transition temperature Tg of 20 to 70 °C. The saturated polyester resin which can be used in the present application is, for example, commercially available as SIPKYD 8204 resin (Tg is 47 ° C) or SIPKYD 8208 resin (Tg is 67 ° C) from Xipu Chemical Co., Ltd.; for example, BECKOLITE is commercially available from Lixinxin Company. K-5329 resin (Tg is 60 ° C) or BECKerOLITE BLF-5017 HV resin (Tg is 40 ° C).

In accordance with some embodiments of the present application, in order to optimize the high temperature (100 ° C) water resistance of the formed light absorbing ink layer, the amino resin in the light absorbing ink composition is a methyl etherified melamine formaldehyde resin (for example, commercially available Newps-138, or Lixinxin MR-625) or butyl etherified melamine formaldehyde resin (for example, the commercially available American INEOS Resimene BM-5901).

According to some embodiments of the present application, the 3D decorative glass, the silane coupling agent in the light absorbing ink composition is an amino group or an epoxy silane coupling agent, and commercially available products such as Z-6040, KH- commercially available from Dow Corning Corporation. 550, KH-560.

According to some embodiments of the present application, the 3D decorative glass, the functional additive in the light-absorbing ink composition can be reasonably added according to the use requirements or production requirements, for example, the functional auxiliary is selected from the group consisting of organic dispersants, leveling agents, One or more of an antifoaming agent and a thixotropic agent, and specifically, the functional auxiliary agent may contain any one of an organic dispersing agent, a leveling agent, an antifoaming agent and a thixotropic agent, any two, and any three Species or all four. In some embodiments of the present application, the functional auxiliary comprises: 3-6 wt% of an organic dispersant, 0.5-1 wt% of a leveling agent, 0.5-1 wt%, based on the total weight of the ink composition. % defoamer, and 0-1% by weight of a thixotropic agent. Among them, optional organic dispersants are commercially available, for example, from BYK-2000, BYK-2051 or BYK-163 from BYK, Germany, and, for example, from Afcona-4000 from Evkona. Optional leveling agents such as Digao 600, commercially available from Deco, Germany, F-41, commercially available from Corning Chemicals, or BYK-358N, commercially available from Decobike; optional The foaming agent may be commercially available from Digo 900 of the German company Digao or BYK-054 commercially available from the German company BYK; the optional thixotropic agent may be BYK410 or BYK430 commercially available from the German company BYK.

According to the 3D decorative glass of some embodiments of the present application, in order to make the preparation process of the light absorbing ink relatively environmentally friendly, the organic solvent added in the process of formulating the light absorbing ink is an environmentally friendly dibasic acid ester. In some specific embodiments of the present application, organic The solvent includes one or more selected from the group consisting of propylene glycol ether acetate, dibutyl carbonate, dimethyl carbonate, dimethyl glutarate, and dimethyl adipate. Specifically, the organic solvent may include one selected from the group consisting of propylene glycol ethers. Any one, any two, any three, any four or all five of acetate, dibutyl carbonate, dimethyl carbonate, dimethyl glutarate and dimethyl adipate.

According to the 3D decorative glass of some embodiments of the present application, in order to optimize the etching effect of the light absorbing ink layer, the edge of the formed decorative ink layer is more clear, and the transmittance of the 3D glass substrate is greater than 90%. In some embodiments, the transmittance of the 3D glass substrate is greater than 95%. In still other embodiments of the present application, the transmittance of the 3D glass substrate is greater than 98%.

The 3D glass substrate generally includes a flat plate region (a region extending along the same plane) and a curved region (a portion deviated from the flat plate region), and the step of surface decorating the 3D glass substrate by applying the existing screen printing method and the film thermal transfer method The maximum bending degree of the curved region in the 3D glass substrate relative to the plane of the flat plate region is required to be no more than 60°. Compared with the current state of the art, the 3D decorative glass provided by the present application, due to the particularity of the method for forming the decorative ink layer, has overcome the prior art limitation of the maximum bending degree in the 3D glass substrate, and can be realized. Surface decoration of a 3D glass substrate having a maximum curvature of more than 60°; however, in order to be more suitable for laser etching, in some embodiments of the present application, the bending region of the 3D glass substrate is the largest relative to the plane of the flat plate region. The curvature is not more than 90°. Wherein the curvature refers to an angle between a tangent of a curved region in the 3D glass substrate and a plane of the flat region, wherein when the curved region exhibits an arc curved structure, the tangent is the corresponding position of the curved curved structure. The outer tangential line is a straight line parallel to the bending plane when the curved region is bent to exhibit bending.

A 3D decorative glass according to some embodiments of the present application, wherein the decorative ink layer, the metal mirror fill layer, and the black light-shielding ink layer may be arranged according to conventional requirements in the art; however, in order to better reflect the stereoscopic effect of the formed pattern, In some embodiments of the present application, the decorative ink layer has a thickness of 5-7 μm, and the metal mirror filling layer has a thickness smaller than the decorative ink layer, for example, less than 1-3 μm; in some embodiments of the present application, the metal The thickness of the mirror-filled layer is 2.5-6 μm; in some embodiments of the present application, the black light-shielding ink layer has a thickness of 5-7 μm.

According to some embodiments of the present application, the 3D decorative glass, wherein the metal mirror filling layer functions as a metal texture, forms a sharp contrast with the decorative ink layer to form a three-dimensional pattern. In some embodiments of the present application, the metal mirror filling layer may be a mirror silver ink filling layer. In some embodiments of the present application, the mirror silver ink filling layer has a thickness of 2.5-6 μm; other embodiments of the present application The metal mirror filling layer may also include a transparent ink filling layer formed on the surface of the 3D glass substrate and an indium or tin plating layer formed on the transparent ink filling layer. In some embodiments of the present application, the transparent ink The thickness of the filling layer is 2-4 μm, and the thickness of the indium or tin plating layer is 200-600 nm.

According to some embodiments of the present application, the 3D decorative glass includes a flat plate region and a curved region, and a ratio of respective line spacings formed in the same pattern on the curved region and the flat plate region is 1±0.003. In this case, the 3D decorative glass can exhibit a more beautiful three-dimensional pattern, and the stereoscopic pattern exhibited is more precise.

In the present application, the above "corresponding line distance in the same pattern" means a linear distance between two corresponding points in the same pattern. For example, if the same pattern is a square, you can select two opposite diagonal points (points) in the square as corresponding points, and calculate the linear distance between the two; when the opposite angles are set in the square on the curved area ( The distance between the points is A, and when the distance between the two opposite diagonal points (points) in the square on the flat plate area is B, the same pattern is formed on the curved area and the flat area The ratio of the corresponding line spacing in the middle is A/B.

Meanwhile, in the present application, there is also provided a method for preparing a 3D decorative glass, the method comprising the steps of: S1, spraying a light-absorbing ink on one side surface of a 3D glass substrate (or preparing a light-absorbing ink, and spraying in 3D) a side surface of the glass substrate), and dried and solidified to form a light absorbing ink layer; S2, a laser is injected from the other side of the 3D glass substrate, and the light absorbing ink layer is etched to form a partially hollow decorative ink layer; S3, in 3D a hollow surface filled with the decorative ink layer forms a metal mirror filling layer on the one surface of the glass substrate; S4, forming a surface on a side of the decorative ink layer and the metal mirror filling layer away from the 3D glass substrate Black shading ink layer.

The above method provided by the present application is simple in steps, easy to reproduce, and etches the light-absorbing ink layer attached to the other side of the 3D glass substrate by means of a laser to transmit the glass, thereby facilitating the edge in the formed decorative ink layer. The burr extends toward one side away from the 3D glass substrate, and when the decorative ink layer is formed through the 3D glass substrate, the edge of the decorative ink layer is even and smooth, almost no burrs after etching are observed, and a layer or The multi-layer background ink can mask the side (surface burr) of the decorative ink layer away from the 3D glass substrate, so that the edge of the decorative ink layer is smooth and smooth under the 100-times and 200-fold electronic magnifying glasses, and has no pointed protrusions. Compared with the screen printing method and the film thermal transfer method, the scheme adopts laser etching to absorb the ink layer to form a partial hollow (with a specific pattern) decorative ink layer, and the formed pattern has higher precision, so that the prepared The decorative effect of 3D decorative glass is better and more beautiful.

A method according to some embodiments of the present application, wherein the step of formulating the light absorbing ink in S1 comprises: mixing the light absorbing ink composition with an organic solvent. In view of the fact that the method according to the present application corresponds to the formation of the aforementioned 3D decorative glass of the present application, the composition and components of the light absorbing ink, and the light absorbing ink composition employed, and the raw material descriptions in the method according to the present application are the same as the aforementioned 3D. The requirements in the decorative glass are the same. For details, please refer to the related description in the 3D decorative glass. Moreover, the requirements for the transmittance and maximum bending of the 3D glass substrate are also the same as those in the aforementioned 3D decorative glass. For details, please refer to Related descriptions in the aforementioned 3D decorative glass.

According to the method of some embodiments of the present application, the S1 includes: S11, formulating the light absorbing ink, and adjusting the viscosity of the light absorbing ink in the Iwata 2# cup at 25 ° C to 12-14 s; S12, S11 The viscosity-adjusting light-absorbing ink is sprayed on one side surface of the 3D glass substrate, and dried at 140-150 ° C for 20-40 min to obtain a light-absorbing ink layer.

According to the method of some embodiments of the present application, in order to better reflect the three-dimensional pattern on the 3D decorative glass, the thickness of the light absorbing ink layer is 5-7 μm.

According to the method of some embodiments of the present application, in order to optimize the etching effect of the light absorbing ink layer, the edge of the formed decorative ink layer is more clear, and the irradiation intensity of the laser in the S2 is 0.01-200 W, and some implementations of the present application are implemented. In an embodiment, the intensity of the laser light in S2 is 10-200 W. In some embodiments of the present application, the spot diameter of the laser formed on the light-absorbing ink layer is less than 0.05 mm. In some embodiments of the present application, the laser is absorbing light. The spot diameter formed on the ink layer is 0.03-0.05 mm. By controlling the diameter of the spot formed on the light absorbing ink layer by the laser, it is advantageous to better improve the etching precision, so that the edge of the formed decorative ink layer is more clear.

According to the method of the present application, the purpose of forming a metal mirror fill layer in S3 is to form a visual difference with the formed decorative ink layer to form a three-dimensional pattern. There may be no special requirements for the method of forming the metal mirror fill layer in the present application, and reference may be made to conventional methods in the art. In one embodiment, the step of forming a metal mirror fill layer in the S3 comprises: spraying the mirror silver ink in the hollow region of the decorative ink layer on the one side surface of the 3D glass substrate, and drying and curing ( The metal mirror filling layer (that is, the mirror silver ink filling layer) is formed according to the nature of the primer or the ultraviolet curing; the mirror silver ink which can be used may be any commercially available product as long as the adhesion and color satisfy the use requirements. . For example, GM-911 mirror silver commercially available from Shenzhen Guxingda Ink, JMY-9200 mirror silver ink commercially available from Shenzhen Sunflower Electronic Materials Co., Ltd., or SP-8580 mirror silver ink commercially available from Seiko Ink.

According to the method of some embodiments of the present application, in order to form a more steric pattern, the thickness of the metal mirror filling layer is smaller than the thickness of the light absorbing ink layer, for example, the thickness of the metal mirror filling layer is smaller than the thickness of the light absorbing ink layer. In some embodiments of the present application, the thickness of the metal mirror filling layer is 2.5-6 μm. In some embodiments of the present application, the thickness of the metal mirror filling layer is 4-6 μm. In order to control the film thickness of the metal mirror-filled layer in the range of 4-6 μm, in some embodiments of the present application, in the step of forming the metal mirror fill layer by the S3, the mirror silver ink is in Iwata 2# The cup was sprayed in the hollowed out region of the decorative ink layer after adjusting the viscosity to 10-12 s at 25 °C.

According to a method of some embodiments of the present application, in another embodiment, the metal mirror fill layer includes a transparent ink fill layer formed on a surface of the 3D glass and an indium or tin plating layer formed on the transparent ink fill layer. The step of forming the metal mirror filling layer in the S3 includes: S31, spraying a transparent vacuum coating primer on the hollow surface of the decorative ink layer on the one side surface of the 3D glass substrate, and drying and curing ( Forming a transparent ink filling layer according to the nature of the primer or ultraviolet curing; S32, plating indium or tin on the exposed surface of the transparent ink filling layer to form an indium or tin plating layer. The transparent vacuum coating primer used therein is excellent in adhesion, high in surface light, and is suitable for electroplating indium or tin, for example, CP-9600 primer commercially available from Korea KCC coating, or commercially available from Guangdong Shenzhan Industry Co., Ltd. Ltd. SZ-6301 primer. In some embodiments of the present application, in order to optimize the leveling effect of the vacuum coating primer, the transparent vacuum coating primer is adjusted in the S31 in the Iwasaki 2# cup, and the viscosity is adjusted to 8-10 s after spraying at 25 ° C. In the hollowed out region of the decorative ink layer, in some embodiments of the present application, the transparent ink filled layer has a thickness of 2-4 μm. The indium or tin plating may be performed by vacuum evaporation or ion sputtering, and the plating material may be selected from the group consisting of metal tin, metal indium, TiN or TiO. In some embodiments of the present application, the thickness of the indium or tin plating layer formed is Between 200nm and 600nm.

According to the method of some embodiments of the present application, the black shading ink is sprayed on the side surface of the hollow ink decorative layer away from the 3D glass substrate in the S4 to form a black shading ink layer. In some embodiments of the present application, The black shading ink layer has a thickness of 5-7 μm. The purpose of forming the black light-shielding ink layer in the S4 is to protect the decorative ink layer and the metal mirror-filled layer on the one hand, and to eliminate trapping in order to better reflect the formed 3D decorative glass in the formed 3D decorative glass. Three-dimensional pattern. In order to spray control the film thickness, in some embodiments of the present application, the black shading ink (after adjusting the viscosity to 12-14 s in the Iwata 2# cup under the condition of 25 ° C) is sprayed on the hollow ink decorative layer in the S4. A black light-shielding ink layer is formed on a side surface away from the 3D glass substrate. In some embodiments of the present application, the black light-shielding ink layer has a thickness of 5-7 μm.

According to the method of some embodiments of the present application, in order to increase the insulation of the prepared 3D decorative glass, the insulation resistance of the black light-shielding ink layer is greater than 10 GΩ (GΩ). In some embodiments of the present application, the black shading The insulation resistance of the ink layer is 10-50 GΩ. In order to achieve the above object, black shading inks which can be used in the present application are commercially available, for example, from Imperial Ink MRX-912 (black), EG-911C (dense black), Seiko ink 1000-710 (black), 1000-710C (concentrated). black).

Further, a 3D decorative glass formed by the method of preparing a 3D decorative glass according to the above is also provided in the present application. The 3D decorative glass comprises: a 3D glass substrate, a partially hollow decorative ink layer, a metal mirror filling layer, and a black shading ink layer, wherein the decorative ink layer is attached to one side surface of the 3D glass substrate, the metal a mirror-filled layer attached to the one side surface of the 3D glass substrate and filled in a hollowed-out region of the decorative ink layer, the black light-shielding ink layer covering the decorative ink layer and the metal mirror-filled layer Exposed on the face. The 3D decorative glass has the same combination and composition as the 3D decorative glass described in the foregoing application. For a detailed description of the 3D decorative glass, refer to the foregoing description of the 3D decorative glass of the present application.

The 3D decorative glass provided by the present application can exhibit a more beautiful three-dimensional pattern, and the precision of the three-dimensional pattern exhibited is high, and the boundary between the decorative ink layer and the metal mirror filling layer is clear and substantially non-serrated; The surface coating of the 3D decorative glass has good adhesion and meets the requirements for use.

The beneficial effects of the 3D decorative glass of the present application and the preparation method thereof will be further described below in conjunction with specific examples and comparative examples.

Examples 1 to 4 and Comparative Example 1

(1) Ink composition for forming a light-absorbing ink layer: The manufacturer, model, and related physical properties of the raw materials used are as follows, and the raw material distribution is as shown in Table 1:

Saturated polyester resin: SIPKYD 8208 resin of Xipu Chemical Co., Ltd., Tg is 67 ° C;

Amino resin: MR-625 of Lixinxin Company, methyl etherified melamine formaldehyde resin;

Carbon black: Evonik's FW-200, blackness value My is 296, particle size distribution is 5-15nm;

Precipitated silica: OK607 of Degussa Company, oil absorption is 220g/100g, particle size D90 is 6μm;

Dispersant: BYK-2000 of BYK, Germany;

Silane coupling agent: Z-6040 of Dow Corning Company, epoxy silane coupling agent;

Leveling agent: Digo 600 of Germany Digo Company;

Defoamer: Digo 900 of Germany Digo Company;

Table 1.

	Example 1	Example 2	Example 3	Example 4	Comparative example 1
Saturated polyester resin (wt%)	55	50	65	70	64
Amino resin (wt%)	twenty four	26	18	15	twenty four
Carbon black (wt%)	5	6	3	4	2
Precipitated silica (wt%)	10	12	8	6	4
Dispersant (wt%)	4	4	4	3	4
Silane coupling agent (wt%)	0.8	0.1	0.5	0.8	0.8
Leveling agent (wt%)	0.6	0.5	0.7	0.6	0.6
Defoamer (wt%)	0.6	0.5	0.8	0.6	0.6

(2) Method for preparing 3D decorative glass:

S1, weighed and mixed the above ink composition in propylene glycol ether acetate (commercially available from Jianghaitian Chemical Co., Ltd.), and formulated into a light absorption ink having a viscosity of 12.5 s at 25 ° C in Iwata 2# cup, and The light absorbing ink is sprayed on a 3D glass substrate (commercially available from Dow Corning's Gorilla Glass, having a light transmittance of 99%, and the structure is as shown in FIG. 1, including a flat plate region 11 and a curved region 12, wherein the curved region 12 is opposed to the flat plate region 11 on the side of the maximum curvature of 45 ° C), and dry curing (150 ° C drying for 30 min) to form a light-absorbing ink layer (thickness of 6 μm);

S2, laser light is injected from the other side of the 3D glass substrate (intensity is 10 W, the spot diameter is 0.05 mm), and the light-absorbing ink layer is etched to form a partially hollow decorative ink layer; FIG. 2 and FIG. 3 are respectively Embodiment 1 The scanning electron micrograph of the 3D glass substrate forming the partially hollow decorative ink layer obtained in the step S2 after magnifying 100 times and 200 times, as can be seen from FIG. 2 and FIG. 3, the method for preparing the 3D decorative glass according to the present application The edge of the decorative ink layer formed by the laser etching of the light absorbing ink layer is still smooth and smooth under the 100-times and 200-fold electronic magnifying glasses, and has no pointed protrusions;

S3, take the JMY-9200 mirror silver from Shenzhen Sunflower Electronic Materials Co., Ltd. as the metal mirror silver ink, and adjust the viscosity to 12s in the Iwata 2# cup at 25 °C; then on the 3D glass substrate On the one side surface, the mirror silver ink is sprayed in the hollow region of the decorative ink layer, and then dried and solidified (baked at 150 ° C for 30 min) to form a metal mirror filling layer filled in the hollow region of the decorative ink layer. (thickness is 4 μm);

S4, commercially available from Imperial Ink MRX-912 (black) as a black shading ink, and the ink is adjusted in the Iwata 2# cup at 25 ° C for 12 s and then sprayed on the hollow ink decorative layer away from the 3D glass. A black light-shielding ink layer (thickness: 6 μm) was formed on one surface of the substrate to obtain a 3D decorative glass, and the obtained 3D decorative glass was designated as G1-G4 and DG1, respectively.

The formed 3D decorative glass comprises: a 3D glass substrate, a partially hollow decorative ink layer (thickness of 6 μm), a metal mirror-filled layer (4 μm), and a black light-shielding ink layer (6 μm), the decorative ink layer being attached to the On one side surface of the 3D glass substrate, the metal mirror filling layer is adhered to the one side surface of the 3D glass substrate and filled in a hollow region of the decorative ink layer, and the black light-shielding ink layer covers On the exposed surface of the decorative ink layer and the metal mirror fill layer.

4 is a schematic view of the image of the 3D decorative glass G1 prepared as described above, wherein 21 is a decorative ink layer and 22 is a metal mirror-filled layer. It can be seen from FIG. 4 that the 3D decorative glass prepared by the method for preparing 3D decorative glass according to the present application has a beautiful three-dimensional structure, high graphic precision, no deformation, clear boundary, and no serration.

Fig. 5 is a schematic view showing the image of the 3D decorative glass DG1 prepared as described above. As can be seen from Fig. 5, when the ink composition of Comparative Example 1 is used, since the ink composition is not within the scope of the present application, particularly the amount of carbon black and precipitated silica does not meet the requirements, The ink layer formed by the ink composition has insufficient light absorption and diffuse reflection effects, which in turn leads to poor etching effect of the formed ink layer during laser etching, and remains in the area that should be hollowed out. Residual ink components destroy the aesthetics of the prepared 3D decorative glass pattern and are difficult to obtain commercial applications.

Example 5

(1) an ink composition for forming a light absorbing ink layer: the same as in the first embodiment;

(2) Preparation method of 3D decorative glass: Refer to Example 1, the difference is:

S3, taken from Guangdong Shenzhan Industrial Co., Ltd. SZ-6301 primer as a transparent vacuum coating primer, and the primer in the Iwata 2 # cup, 25 ° C conditions to adjust the viscosity to 8.5s; then in 3D glass On the one side surface of the substrate, the mirror silver ink is sprayed in the hollow region of the decorative ink layer, and then dried and cured (ultraviolet intensity is 1200 mj/cm ² ) to form a transparent layer filled in the hollow region of the decorative ink layer. An ink filling layer (thickness: 3 μm), and then the 3D glass subjected to the foregoing treatment is placed in a vacuum coating machine such that one side of the 3D glass in which the transparent ink filling layer is formed is exposed, and metal indium is used as a plating material in a vacuum degree. The indium plating layer (thickness: 200 nm) was formed by evaporation plating at 0.98 MPa for 30 min. The obtained 3D decorative glass was designated as G5.

The formed 3D decorative glass comprises: a 3D glass substrate, a partially hollow decorative ink layer (thickness of 6 μm), a metal mirror filling layer, and a black light-shielding ink layer (6 μm), the decorative ink layer being attached to the 3D glass substrate On one side surface, the metal mirror fill layer is attached on the one side surface of the 3D glass substrate and filled in the hollow region of the decorative ink layer, and the metal mirror fill layer is formed in 3D a clear ink filling layer (3 μm) on the surface of the glass and an indium plating layer (200 nm) formed on the transparent ink filling layer, the black light-shielding ink layer covering the exposed surface of the decorative ink layer and the metal mirror filling layer .

Example 6

(1) Ink composition for forming a light-absorbing ink layer: Refer to Example 1, except that a saturated polyester resin having a Tg of 10 ° C (SIPKYD 8214 resin commercially available from Xipu Chemical Co., Ltd.) was used instead of Example 1. Saturated polyester resin.

(2) Preparation method of 3D decorative glass: Refer to Example 1, except that the ink composition for forming a light-absorbing ink layer in the above (1) was used, and the obtained 3D decorative glass was designated as G6.

Example 7

(1) Ink composition for forming a light-absorbing ink layer: Refer to Example 1, except that melamine formaldehyde resin (BR-20SE resin commercially available from Lixinxin Co., Ltd.) was used instead of methyl etherified melamine formaldehyde in Example 1. Resin.

(2) Preparation method of 3D decorative glass: Refer to Example 1, except that the ink composition for forming a light-absorbing ink layer in the above (1) was used, and the obtained 3D decorative glass was designated as G7.

Comparative example 2

(1) Ink composition for forming a light-absorbing ink layer: Refer to Example 1, except that carbon black having a blackness value My of 200 is substituted for carbon black in Example 1, and a precipitate having a oil absorption of 280 g/100 g is used. Silica was used in place of the precipitated silica in Example 1.

(2) Method for preparing 3D decorative glass: Refer to Example 1, except that the ink composition for forming a light-absorbing ink layer in the above (1) was used, and the obtained 3D decorative glass was designated as DG2.

Since the ink composition used in this comparative example is not within the scope of the present application, in particular, the blackness value My of the carbon black and the oil absorption amount of the precipitated silica are simultaneously unsatisfactory, which makes it possible to The ink layer formed by the ink composition has insufficient light absorption and diffuse reflection effects, which in turn causes the formed ink layer to have poor etching effect during laser etching, and remains in the area that should be hollowed out. The ink composition destroys the aesthetics of the prepared 3D decorative glass pattern (see Fig. 5), making it difficult to obtain commercial applications.

Comparative example 3

(1) Ink composition for forming a light-absorbing ink layer: the same as in Example 1.

(2) Preparation method of 3D decorative glass: refer to Example 1, except that in step S2, the laser light does not penetrate the 3D glass substrate, and the light-absorbing ink layer is directly etched to form a partially hollow decorative ink layer, and the obtained 3D is obtained. Decorative glass is recorded as DG3;

6 and FIG. 7 are scanning electron micrographs of the 3D glass substrate forming the partially hollow decorative ink layer obtained in step S2 of Comparative Example 3 after magnifying 100 times and 200 times, respectively, as can be seen from FIG. 6 and FIG. When the light-absorbing ink layer is directly etched by the laser without the glass, although the partially hollow decorative ink layer can be formed, the edge of the formed decorative ink layer forms a continuous pointed protrusion, so that This results in a pattern that is not smooth at the edges.

test:

1) Adhesion test: Refer to standard ISO 2409 (color paint and varnish - cross-cut test)

Test method: use the back of the surgical knife (the back angle of the knife is 20 ° ~ 30 °) to scratch 12 scratches on the coating, at least two scratches at an angle of 90 ° with other scratches to form a grid on the surface The grid has a side length of 1 mm. Make sure that each scratch is cut to the base material. Brush each brush 5 times in both directions along the scratch. Stick the 3M tape (Dongguan Omico, tape type 3M600) to the surface, and wipe the tape with your fingertips to ensure good contact with the coating. 60° from the free end of the tape in 5 minutes. The angle is peeled off the tape regularly in 0.5-1 seconds.

classification:

5B: The edge of the slit is completely smooth, and the square of the lattice is not peeled off;

4B: the area of the peeling portion is not more than 5% of the area of the tape in contact with the surface;

3B: the area of the peeling portion is greater than 5% of the area of the tape in contact with the surface, and not more than 15%;

2B: the area of the peeling portion is greater than 15% of the area of the tape in contact with the surface, and not more than 35%;

1B: The area of the peeling portion is larger than 35% of the area of the tape in contact with the surface, and does not exceed 65%.

0B: The area of the peeling part is larger than 1B

This test requires adhesion performance ≥ 3B. The results are shown in Table 2.

2) Water resistance (also known as water resistance):

The 3D decorative glass was added to 100 ° C hot water for 1 h, and the adhesion of the surface coating was tested after taking out. For the measurement method of the adhesion of the surface coating, refer to the adhesion test in 1). The results are shown in Table 2.

3) Appearance observation:

The edge of the decorative ink layer was observed under a 200-fold electron microscope. The results are shown in Table 2.

4) Degree of deformation

The ratio of the respective line spacings formed in the same pattern on the curved region and the flat plate region in the 3D decorative glass is tested by SEM microscopy (see the foregoing description of the ratio), and the degree of deformation is calculated, the degree of deformation being equal to the same The ratio of the linear distance between the corresponding points when the pattern is formed on the curved area to the linear distance between the corresponding points on the flat area. The results are shown in Table 2.

Table 2.

	Adhesion	Water resistance	Appearance observation	Degree of deformation
G1	5B	5B	Clear edge structure, no abnormal protrusion	1
G2	5B	5B	Clear edge structure, no abnormal protrusion	1.002
G3	5B	5B	Clear edge structure, no abnormal protrusion	1.003
G4	4B	4B	Clear edge structure, no abnormal protrusion	1.002
G5	5B	5B	Clear edge structure, no abnormal protrusion	1.002
G6	3B	3B	Clear edge structure, no abnormal protrusion	1.002
G7	5B	3B	Clear edge structure, no abnormal protrusion	1.003
DG3	5B	5B	The edge structure is not clear, there are continuous abnormal bulges	1.002

As can be seen from Table 2, the 3D decorative glass prepared by using Examples 1 to 7 of the method for producing 3D decorative glass according to the present application, while maintaining the adhesion of the 3D glass surface coating, was compared with Comparative Example 3. The formed pattern boundaries are clearer and have no abnormal protrusions.

Meanwhile, in the 3D decorative glass prepared by the first to seventh embodiments of the method for producing 3D decorative glass according to the present application, the ratio of the unit line pitch (ie, the degree of deformation) of the same pattern located on the curved region and the flat plate region approaches 1. It can be seen that the pattern precision of the 3D decorative glass prepared by the method for preparing 3D decorative glass according to the present application is high, which is advantageous for optimizing the decorative effect of the prepared 3D decorative glass to make it more beautiful.

Moreover, in the present application, the surface decoration of the 3D glass can be realized by the spraying process combined with the laser etching process and the optional coating process, which can avoid the development of high-precision abrasive tools required for various printing and coating, and is beneficial to save equipment costs. And because there is no need to develop the molds required for the transfer of the printing press, the new products are greatly reduced, the new pattern development cycle is shortened, and the production efficiency is improved.

The preferred embodiments of the present application have been described in detail above, but the application is not limited thereto. Within the scope of the technical idea of the present application, various simple modifications can be made to the technical solutions of the present application, including the various technical features combined in any other suitable manner, and these simple variations and combinations should also be regarded as the contents disclosed in the present application. All belong to the scope of protection of this application.

Claims (73)

1. A 3D decorative glass comprising: a 3D glass substrate, a partially hollow decorative ink layer, a metal mirror filling layer, and a black shading ink layer, the decorative ink layer being attached to one side surface of the 3D glass substrate, a metal mirror fill layer attached to the one side surface of the 3D glass substrate and filled in a hollow region of the decorative ink layer, the black light-shielding ink layer covering the decorative ink layer and the metal mirror surface a bare surface of the filling layer; wherein the partially hollow decorative ink layer is formed by spraying a light absorbing ink on the one side surface of the 3D glass substrate, and drying and curing to form a light absorbing ink layer, and then from the 3D glass The other side of the substrate is formed by laser etching the light absorbing ink layer.
2. The 3D decorative glass according to claim 1, wherein the light absorbing ink comprises carbon black and precipitated silica, and the content of the carbon black is 3 based on the dry basis weight of the oil absorbing ink. 6 wt%, the precipitated silica is contained in an amount of 6 to 12% by weight.
3. The 3D decorative glass according to claim 2, wherein the carbon black has a blackness value My of more than 250.
4. The 3D decorative glass according to claim 3, wherein the carbon black has a blackness value My of 250 to 350.
5. The 3D decorative glass according to any one of claims 2 to 4, wherein the amount of oil absorbed by the precipitated silica in the light absorbing ink is less than 250 g/100 g.
6. The 3D decorative glass according to any one of claims 2 to 5, wherein the oil absorption amount of the precipitated silica in the light absorbing ink is (100 - 240) g / 100 g.
7. The 3D decorative glass according to any one of claims 2 to 6, wherein the carbon black has a feed particle diameter of less than 20 nm.
8. The 3D decorative glass according to any one of claims 2 to 7, wherein the carbon black has a feed particle size distribution in the range of 4 to 16 nm.
9. The 3D decorative glass according to any one of claims 2 to 8, wherein the precipitated silica has a feed particle diameter D90 of more than 5 μm.
10. The 3D decorative glass according to any one of claims 2 to 9, wherein the precipitated silica has a feed particle diameter D90 of 5 to 10 μm.
11. The 3D decorative glass according to any one of claims 1 to 10, wherein the light absorbing ink is prepared by mixing a light absorbing ink composition with an organic solvent, wherein the light absorbing ink composition has a total weight of The benchmarks include: 45-72% by weight of saturated polyester resin, 15-30% by weight of amino resin, 3% by weight of carbon black, 6% by weight of precipitated silica, and 0.1-2% by weight of silane. Coupling agent, 0.1-10% by weight of functional auxiliary.
12. The 3D decorative glass according to claim 11, wherein the saturated polyester resin is a saturated polyester resin having a glass transition temperature Tg of from 20 to 70 °C.
13. The 3D decorative glass according to claim 11 or 12, wherein the amino resin is a methyl etherified melamine formaldehyde resin or a butylated etherified melamine formaldehyde resin.
14. The 3D decorative glass according to any one of claims 11 to 13, wherein the silane coupling agent is an amino group or an epoxy silane coupling agent.
15. The 3D decorative glass according to any one of claims 11 to 14, wherein the light absorbing ink composition comprises, based on the total weight thereof, 50 to 65 wt% of the saturated polyester resin, 18 to 26 parts by weight. % of the amino resin, 3 to 6% by weight of the carbon black, 8 to 12% by weight of the precipitated silica, 0.5 to 1% by weight of the silane coupling agent, 0.1 to 8% by weight The functional auxiliary.
16. The 3D decorative glass according to any one of claims 11 to 15, wherein the functional auxiliary agent is one or more selected from the group consisting of a dispersing agent, a leveling agent, an antifoaming agent, and a thixotropic agent.
17. The 3D decorative glass according to claim 16, wherein the functional auxiliary comprises, based on the total weight of the light-absorbing ink composition, 3 to 6% by weight of the organic dispersant, 0.5 to 1% by weight. The leveling agent, 0.5-1% by weight of the antifoaming agent, and 0-1% by weight of the thixotropic agent.
18. The 3D decorative glass according to any one of claims 11 to 17, wherein the organic solvent is an environmentally friendly dibasic acid ester.
19. The 3D decorative glass according to any one of claims 11 to 18, wherein the organic solvent is selected from the group consisting of propylene glycol methyl ether acetate, dibutyl carbonate, dimethyl carbonate, dimethyl glutarate, and hexane. One or more of dimethyl esters.
20. The 3D decorative glass according to any one of claims 1 to 19, wherein the 3D glass substrate has a light transmittance of more than 90%.
21. The 3D decorative glass according to any one of claims 1 to 20, wherein the 3D glass substrate has a light transmittance of more than 95%.
22. The 3D decorative glass according to any one of claims 1 to 21, wherein the 3D glass substrate has a light transmittance of more than 98%.
23. The 3D decorative glass according to any one of claims 1 to 2, wherein the 3D glass substrate comprises a flat plate region and a curved region, and a maximum curvature of the curved region relative to the flat plate region is not more than 90° .
24. The 3D decorative glass according to any one of claims 1 to 23, wherein the decorative ink layer has a thickness of 5 to 7 μm.
25. The 3D decorative glass according to any one of claims 1 to 24, wherein the metal mirror-filled layer has a thickness of 2.5 to 6 μm.
26. The 3D decorative glass according to any one of claims 1 to 25, wherein the metal mirror-filled layer has a thickness smaller than a thickness of the decorative ink layer.
27. The 3D decorative glass according to any one of claims 1 to 26, wherein the thickness of the metal mirror-filled layer is 1-3 μm smaller than the thickness of the decorative ink layer.
28. The 3D decorative glass according to any one of claims 1 to 27, wherein the black light-shielding ink layer has a thickness of 5 to 7 μm.
29. A 3D decorative glass according to any one of claims 1 to 28, wherein the metal mirror fill layer is a mirror silver ink filled layer.
30. The 3D decorative glass according to claim 29, wherein the mirror silver ink filled layer has a thickness of 2.5 to 6 μm.
31. The 3D decorative glass according to any one of claims 1 to 28, wherein the metal mirror filling layer comprises a transparent ink filling layer formed on a surface of the 3D glass and indium or formed on the transparent ink filling layer Tin plating.
32. The 3D decorative glass according to claim 31, wherein the transparent ink-filled layer has a thickness of 2-4 μm.
33. The 3D decorative glass according to claim 31 or 32, wherein the indium or tin plating layer has a thickness of 200 to 600 nm.
34. The 3D decorative glass according to any one of claims 1 to 3, wherein the 3D decorative glass includes a flat plate region and a curved region, and is formed in a corresponding line in the same pattern on the curved region and the flat plate region The ratio of the pitch is 1 ± 0.003.
35. A method of preparing a 3D decorative glass, comprising the steps of:

    S1, spraying the light-absorbing ink on one side surface of the 3D glass substrate, and drying and solidifying to form a light-absorbing ink layer;

    S2, injecting a laser from the other side of the 3D glass substrate, and etching the light absorbing ink layer to form a partially hollow decorative ink layer;

    S3, on the one side surface of the 3D glass substrate, filling a hollow area of the decorative ink layer to form a metal mirror surface filling layer;

    S4, forming a black light-shielding ink layer on a surface of the decorative ink layer and the metal mirror filling layer away from the 3D glass substrate.
36. The method according to claim 35, wherein said light absorbing ink comprises carbon black and precipitated silica, and the content of carbon black is from 3 to 6% by weight based on the dry basis weight of said light absorbing ink, and precipitation The content of silica is 6-12% by weight.
37. The method according to claim 36, wherein the carbon black has a blackness value My of more than 250.
38. The method according to claim 36 or 37, wherein the carbon black has a blackness value My of from 250 to 350.
39. The method according to any one of claims 36 to 38, wherein the oil absorption of the precipitated silica in the light absorbing ink is less than 250 g/100 g.
40. The method according to any one of claims 36 to 39, wherein the oil absorption of the precipitated silica in the light absorbing ink is (100 - 240) g / 100 g.
41. The method according to any one of claims 36 to 40, wherein the carbon black has a feed particle size of less than 20 nm.
42. The method according to any one of claims 36 to 41, wherein the carbon black has a feed particle size distribution in the range of 4 to 16 nm.
43. The method according to any one of claims 36 to 42, wherein the precipitated silica has a feed particle diameter D90 of more than 5 μm.
44. The method according to any one of claims 36 to 43, wherein the precipitated silica has a feed particle diameter D90 of 5 to 10 μm.
45. The method of any of claims 35-44, wherein the 3D glass has a light transmission greater than 90%.
46. The method of any of claims 35-45, wherein the 3D glass has a light transmission greater than 95%.
47. The method of any of claims 35-46, wherein the 3D glass has a light transmission greater than 98%.
48. The method according to any one of claims 35-47, wherein the 3D glass substrate comprises a flat plate region and a curved region, and the maximum curvature of the curved region relative to the flat plate region is no more than 90°.
49. The method according to any one of claims 35 to 48, wherein the step of formulating the light absorbing ink in S1 comprises: mixing the light absorbing ink composition with an organic solvent; wherein the light absorbing ink composition is based on its total weight The benchmarks include: 45-72% by weight of saturated polyester resin, 15-30% by weight of amino resin, 3% by weight of carbon black, 6% by weight of precipitated silica, and 0.1-2% by weight of silane. Coupling agent, 0.1-10% by weight of functional auxiliary.
50. The method according to claim 49, wherein the saturated polyester resin is a saturated polyester resin having a glass transition temperature Tg of from 20 to 70 °C.
51. The method according to claim 49 or 50, wherein the amino resin is a methyl etherified melamine formaldehyde resin or a butylated etherified melamine formaldehyde resin.
52. The method according to any one of claims 49 to 51, wherein the silane coupling agent is an amino group or an epoxy silane coupling agent.
53. The method according to any one of claims 49 to 52, wherein the light absorbing ink composition comprises, based on the total weight thereof, 50 to 65 wt% of the saturated polyester resin, 18 to 26 wt% The amino resin, 3-6 wt% of the carbon black, 8-12 wt% of the precipitated silica, 0.5-1 wt% of the silane coupling agent, 0.1-8 wt% of the stated Functional additives.
54. The method according to any one of claims 49 to 53, wherein the functional auxiliary agent is one or more selected from the group consisting of a dispersing agent, a leveling agent, an antifoaming agent, and a thixotropic agent.
55. The method according to any one of claims 49 to 54, wherein the functional auxiliary comprises: 3 to 6% by weight of an organic dispersant, 0.5-1, based on the total weight of the light-absorbing ink composition A wt% leveling agent, 0.5-1% by weight of an antifoaming agent, and 0-1% by weight of a thixotropic agent.
56. The method according to claim 55, wherein the organic solvent is an environmentally friendly dibasic acid ester.
57. The method according to claim 55 or 56, wherein the organic solvent is selected from the group consisting of propylene glycol methyl ether acetate, dibutyl carbonate, dimethyl carbonate, dimethyl glutarate and dimethyl adipate. One or several.
58. The method of any of claims 35-57, wherein said S1 comprises:

    S11, preparing the light-absorbing ink, and adjusting the viscosity of the light-absorbing ink in Iwata 2# cup at 25 ° C to 12-14 s;

    S12, spraying the light-adjusting ink after adjusting the viscosity in S11 on the one side surface of the 3D glass substrate, and drying at 140-150 ° C for 20-40 min to obtain the light-absorbing ink layer.
59. The method according to any one of claims 35 to 58, wherein the light absorbing ink layer has a thickness of 5 to 7 μm.
60. The method according to any one of claims 35 to 59, wherein the intensity of the laser light in the S2 is from 0.01 to 200 W.
61. The method according to any one of claims 35-60, wherein the intensity of the laser light in the S2 is 10-200 W.
62. The method according to any one of claims 35-61, wherein the spot diameter of the laser formed on the light absorbing ink layer in S2 is less than 0.05 mm.
63. The method according to any one of claims 35-62, wherein the spot diameter of the laser formed on the light absorbing ink layer in S2 is 0.03-0.05 mm.
64. The method according to any one of claims 35 to 63, wherein the step of forming a metal mirror fill layer in the S3 comprises: hollowing out the decorative ink layer on the one side surface of the 3D glass substrate A mirror silver ink is sprayed and dried to form the metal mirror fill layer.
65. The method according to any one of claims 35 to 64, wherein the metal mirror-filled layer has a thickness of 2.5 to 6 μm.
66. The method of any of claims 35-65, wherein the thickness of the metal mirror fill layer is less than the thickness of the light absorbing ink layer.
67. The method according to any one of claims 35 to 66, wherein the thickness of the metal mirror fill layer is 1-3 μm smaller than the thickness of the light absorbing ink layer.
68. The method according to any one of claims 35-63, 65-67, wherein the metal mirror fill layer comprises a transparent ink fill layer formed on the surface of the 3D glass and a transparent ink fill layer formed on the surface The indium or tin plating layer; the step of forming the metal mirror filling layer in the S3 comprises:

    S31, on the one side surface of the 3D glass substrate, spraying a transparent vacuum coating primer in the hollow region of the decorative ink layer to form the transparent ink filling layer;

    S32, indium or tin is plated on the exposed surface of the transparent ink filling layer to form an indium or tin plating layer.
69. The method according to claim 68, wherein said transparent ink-filled layer has a thickness of from 2 to 4 μm.
70. The method according to claim 68 or 69, wherein the indium or tin plating layer has a thickness of 200 to 600 nm.
71. The method according to any one of claims 35 to 70, wherein a black shading ink is sprayed on the side surface of the hollow ink decorative layer and the metal mirror filling layer away from the 3D glass substrate in the S4 A black shading ink layer is formed thereon.
72. The method according to any one of claims 35 to 71, wherein the black light-shielding ink layer has a thickness of 5 to 7 μm.
73. A 3D decorative glass formed by the production method according to any one of claims 35 to 72.

Images