Ink suitable for glass hot bending forming and application of ink in mobile phone
Technical Field
The invention relates to the field of ink, in particular to ink suitable for glass hot bending forming. In addition, the invention also relates to application of the ink suitable for glass hot bending forming in a mobile phone.
Background
With the development of smart phones and the approach of the 5G era, the 3D glass suitable for the front and rear covers of the mobile phone will become mainstream in the industry. In order to solve the coating problem of the 3D glass frame decoration ink, two processes which are suitable for manufacturers at present are as follows: 1. the common PET printing ink is printed on a softer PET material with UV glue, after the PET printing ink is cured, the PET is transferred to 3D glass through a special tool, and then the PET is cured through UV. 2. The required pattern is carved by spraying full plate ink and then adopting a laser carving process. The process 1 can only be used for making two parallel concave edges, can not meet the requirement of glass with four concave edges, and the PET film can only be used once, so that the cost is high, the efficiency is low, and the waste is serious. The process 2 has low efficiency for large area and high requirement on equipment, and laser etching generates a lot of toxic gas to influence the health of staff, and the laser etching is easy to damage glass to cause scrapping.
Disclosure of Invention
The invention provides application of ink suitable for glass hot bending forming in a mobile phone, and aims to solve the technical problem that an existing 3D glass frame device is complex in process.
The technical scheme adopted by the invention is as follows:
the invention discloses an ink suitable for glass hot bending forming, which comprises, by weight, 3-10 parts of polyvinyl alcohol with the molecular weight of 25000-250000, 3-10 parts of polyvinyl butyral with the molecular weight of 30000-45000, 8-17 parts of water-based organic silicon resin, 10-25 parts of water, 10-25 parts of silicon dioxide, 15-30 parts of zirconium oxide, 1-4.5 parts of cosolvent and 0.01-0.5 part of auxiliary agent.
The ink further comprises 5-10 parts of polyvinyl alcohol with the molecular weight of 30000-150000, 5-10 parts of polyvinyl butyral with the molecular weight of 30000-40000, 10-17 parts of water-based organic silicon resin, 15-25 parts of water, 19-25 parts of silicon dioxide, 20-30 parts of zirconium oxide, 2.5-4.5 parts of cosolvent and 0.2-0.5 part of auxiliary agent.
Further, the ink comprises 10 parts of polyvinyl alcohol with the molecular weight of 30000-150000, 5-10 parts of polyvinyl butyral with the molecular weight of 30000-40000, 10-17 parts of water-based organic silicon resin, 15-18 parts of water, 19-22 parts of silicon dioxide, 24-28 parts of zirconium oxide, 4-4.5 parts of cosolvent and 0.4-0.5 part of auxiliary agent.
Further, the silica is nano silica, and the zirconia is nano zirconia.
Further, the water-based silicone resin comprises water-based silicone epoxy resin, water-based silicone polyester resin, water-based silicone alkyd resin or water-based silicone acrylic resin.
Further, the cosolvent is methanol, ethanol, propanol, ethylene glycol, glycerol or diacetone alcohol, preferably, the cosolvent is ethanol, glycerol or diacetone alcohol.
Further, the auxiliary agent comprises a leveling agent and an antifoaming agent.
Further, the ink also comprises inorganic pigment, and the inorganic pigment comprises one or more of iron oxide red, iron oxide black, titanium dioxide, cobalt blue and vanadium yellow.
The invention also discloses application of the ink suitable for glass hot bending forming in a mobile phone.
The invention has the following beneficial effects: the ink suitable for glass hot bending molding is characterized in that a high polymer with a lower molecular weight is mostly used in the ink, so that the ink has good printability and good water solubility, and a proper printing effect is obtained. And the water-based organic silicon resin can also provide a proper medium for silica and zirconia, so that the silica and the zirconia can be well sintered on glass. Silica, zirconia and water-based silicone resin are used as final film forming substances, so that the ink can resist high temperature. Therefore, the ink can be printed on the plane glass in advance, and the heat energy in the glass bending process is utilized to sinter and form the plane glass together with the glass. The adhesive force of the ink on the glass is 5B, and the hardness of the ink is equivalent to that of the glass, so that the ink does not need to be printed and cured for molding subsequently. The 3D glass frame decorated by the ink can reduce the complexity of the process of decorating the ink and reduce the energy consumption of the whole process.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention is described in further detail below.
Detailed Description
The embodiments of the invention are described in detail below, but the invention can be implemented in many different ways, which are defined and covered by the claims.
The preferred embodiment of the invention provides an ink suitable for glass hot bending forming, which comprises 3-10 parts by weight of polyvinyl alcohol with the molecular weight of 25000-250000, 3-10 parts by weight of polyvinyl butyral with the molecular weight of 30000-45000, 8-17 parts by weight of water-based organic silicon resin, 10-25 parts by weight of water, 10-25 parts by weight of silicon dioxide, 15-30 parts by weight of zirconium oxide, 1-4.5 parts by weight of cosolvent and 0.01-0.5 part by weight of assistant.
The polyvinyl alcohol is PVA resin, and the polyvinyl butyral is PVB resin. During the high-temperature forming process, polyvinyl alcohol and polyvinyl butyral are decomposed and volatilized. When the molecular weight of the polyvinyl alcohol and the polyvinyl butyral is too large, the decomposition temperature of the polyvinyl alcohol and the polyvinyl butyral is high during high-temperature molding, so that incomplete volatilization is caused, and part of the polyvinyl alcohol and the polyvinyl butyral remains in the ink, so that abnormal color spots appear on the ink, and the appearance of the ink after molding is influenced. When the molecular weight of the polyvinyl alcohol and the polyvinyl butyral is too small, the polyvinyl alcohol and the polyvinyl butyral are not good in wrapping of powder materials in the ink, the prepared ink is poor in oiliness, flowability and printability, is difficult to level after being printed, is easy to generate surface defects such as pinholes and orange peels, is easy to generate light transmission points after being sintered at high temperature, influences the OD value of the ink, and even is scrapped. Therefore, polyvinyl alcohol having a molecular weight of 25000 to 250000 and polyvinyl butyral having a molecular weight of 30000 to 45000 are selected as the ink.
The main resin of the ink is water-based organic silicon resin, so that the ink not only provides proper printability, but also provides proper media for nano silicon dioxide and nano zirconium oxide in the high-temperature bending process of glass, and the silicon dioxide and the zirconium oxide are well sintered on the glass. When the aqueous organic silicon resin is formed at high temperature, a film is formed, and the film is similar to a ceramic structure. Silica and zirconia provide suitable color and glaze effects during sintering. The nano silicon dioxide, the nano zirconia and the water-based organic silicon resin are taken as film forming substances, so that the ink can resist the high temperature of over 1000 ℃.
The ink provided by the invention comprises 3-10 parts by weight of polyvinyl alcohol with molecular weight of 25000-250000, 3-8 parts by weight of polyvinyl butyral with molecular weight of 30000-45000 and 8-15 parts by weight of water-based organic silicon resin, and provides good printability by taking the water-based organic silicon resin as a film forming substance during surface drying. The proportion can find that the printing ink of the invention mostly uses high polymers with lower molecular weight, and the materials have the common characteristics of good printability, good water solubility, easy decomposition and volatilization at high temperature and obtaining proper printing effect. If the content of the polyvinyl alcohol or polyvinyl butyral in the aqueous silicone resin is too high, the resin is not decomposed and volatilized completely in the glass press-bending molding time, and the resin remains in the finally molded ink, thereby causing abnormal color unevenness. If the content of the vinyl alcohol and the polyvinyl butyral is too low, the powder is not sufficiently wrapped in the production process of the ink, the prepared ink is poor in oiliness, poor in flowability and poor in printability, is difficult to level after being printed, is easy to generate surface defects such as pinholes and orange peels, is easy to generate light transmission points after being sintered at high temperature, influences the OD value of the ink and even is scrapped. The content of silicon dioxide and zirconium oxide is too small, the fullness of the ink after sintering and molding is not enough, the printing ink is easy to transmit light, and the OD value is not enough. The content of silicon dioxide and zirconium oxide is too high, the prepared ink has poor oiliness, flowability and printability, is difficult to level after printing, is easy to generate surface defects such as pinholes and orange peel, is easy to generate light transmission points after high-temperature sintering, influences the OD value of the ink and even is scrapped. The temperature of glass hot bending molding reaches 700-900 ℃, and common ink cannot be printed on glass due to low high temperature resistance and is calcined and molded together with the glass. The ink has high temperature resistance, the adhesive force of the ink on glass is 5B, and the hardness of the ink is equivalent to that of the glass, so that the ink can be printed on plane glass in advance, and the heat energy in glass bending is utilized to be sintered and molded together with the glass in the process of bending the glass into a 3D shape.
The invention has the following beneficial effects: the ink suitable for glass hot bending molding is characterized in that a high polymer with a lower molecular weight is mostly used in the ink, so that the ink has good printability and good water solubility, and a proper printing effect is obtained. And the water-based organic silicon resin can also provide a proper medium for silica and zirconia, so that the silica and the zirconia can be well sintered on glass. Silica, zirconia and water-based silicone resin are used as final film forming substances, so that the ink can resist high temperature. Therefore, the ink can be printed on the plane glass in advance, and the heat energy in the glass bending process is utilized to sinter and form the plane glass together with the glass. The adhesive force of the ink on the glass is 5B, and the hardness of the ink is equivalent to that of the glass, so that the ink does not need to be printed and cured for molding subsequently. The 3D glass frame decorated by the ink can reduce the complexity of the process of decorating the ink and reduce the energy consumption of the whole process.
Optionally, the ink comprises 5-10 parts of polyvinyl alcohol with the molecular weight of 30000-150000, 5-10 parts of polyvinyl butyral with the molecular weight of 30000-40000, 10-17 parts of water-based organic silicon resin, 15-25 parts of water, 19-25 parts of silicon dioxide, 20-30 parts of zirconium oxide, 2.5-4.5 parts of cosolvent and 0.2-0.5 part of auxiliary agent.
Optionally, the ink comprises 10 parts of polyvinyl alcohol with the molecular weight of 30000-150000, 5-10 parts of polyvinyl butyral with the molecular weight of 30000-40000, 10-17 parts of water-based organic silicon resin, 15-15.6 parts of water, 19-22 parts of silicon dioxide, 24-28 parts of zirconium oxide, 4-4.5 parts of cosolvent and 0.4-0.5 part of auxiliary agent.
Alternatively, the silica is nanosilica and the zirconia is nanosilica. The ink is more exquisite and has better hue by selecting the nano silicon dioxide and the nano zirconia.
Alternatively, the aqueous silicone resin comprises an aqueous silicone epoxy resin, an aqueous silicone polyester resin, an aqueous silicone alkyd resin, or an aqueous silicone acrylic resin.
Optionally, the cosolvent is methanol, ethanol, propanol, ethylene glycol, glycerol or diacetone alcohol, preferably, the cosolvent is ethanol, glycerol or diacetone alcohol.
Optionally, the auxiliary agent includes a leveling agent and an antifoaming agent. The proportion of the leveling agent and the defoaming agent can be generally 1: 1-2.
Optionally, the ink further comprises an inorganic pigment, and the inorganic pigment comprises one or more of iron oxide red, iron oxide black, titanium dioxide, cobalt blue and vanadium yellow. The addition of pigments can give inks different colors. The amount of the pigment to be added may be appropriately selected depending on the desired color shade.
The invention also discloses application of the ink suitable for glass hot bending forming in a mobile phone.
Example 1
The parts by weight of the components of the ink of example 1 are shown in Table 1.
TABLE 1
Printing ink
|
Parts by weight
|
Pure water
|
25
|
Ethanol
|
2.7
|
PVA resin
|
10
|
PVB resin
|
5
|
Aqueous silicone alkyd resins
|
14
|
Aqueous leveling agent
|
0.2
|
Aqueous defoaming agent
|
0.1
|
Nano silicon dioxide
|
13
|
Nano zirconium oxide
|
30 |
The rotating speed is 500-1000 rpm, the materials in the table 1 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 15-30 minutes at the rotating speed of 2000-3000 rpm.
And uniformly printing the ink on the treated plate glass by using a 200-400-mesh screen and a 65-80-degree frictioning, baking for 10-15 minutes at 80 ℃, and calcining and molding together with the glass in a glass hot bending furnace at 700-900 ℃.
Example 2
The parts by weight of the components of the ink of example 2 are shown in Table 2.
TABLE 2
The rotating speed is 500-1000 rpm, the materials in the table 2 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 15-30 minutes at the rotating speed of 2000-3000 rpm.
And uniformly printing the ink on the treated plate glass by using a 200-400-mesh screen and a 65-80-degree frictioning, baking for 10-15 minutes at 80 ℃, and calcining and molding together with the glass in a glass hot bending furnace at 700-900 ℃.
Example 3
The parts by weight of the components of the ink in example 3 are listed in table 3.
TABLE 3
Printing ink
|
Parts by weight
|
Pure water
|
20.6
|
Ethanol
|
4
|
PVA resin
|
10
|
PVB resin
|
5
|
Water-based organic silicon acrylic resin
|
17
|
Aqueous leveling agent
|
0.2
|
Aqueous defoaming agent
|
0.2
|
Nano silicon dioxide
|
15
|
Nano zirconium oxide
|
28 |
The rotating speed is 500-1000 rpm, the materials in the table 3 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 15-30 minutes at the rotating speed of 2000-3000 rpm.
And uniformly printing the ink on the treated plate glass by using a 200-400-mesh screen and a 65-80-degree frictioning, baking for 10-15 minutes at 80 ℃, and calcining and molding together with the glass in a glass hot bending furnace at 700-900 ℃.
Example 4
The parts by weight of the components of the ink in example 4 are shown in Table 4.
TABLE 4
The rotating speed is 500-1000 rpm, the materials in the table 4 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 15-30 minutes at the rotating speed of 2000-3000 rpm.
And uniformly printing the ink on the treated plate glass by using a 200-400-mesh screen and a 65-80-degree frictioning, baking for 10-15 minutes at 80 ℃, and calcining and molding together with the glass in a glass hot bending furnace at 700-900 ℃.
Comparative example 1
The parts by weight of the respective components of the inks in the comparative examples are shown in tables 5 and 6.
TABLE 5
Ink main agent component
|
Parts by weight
|
Bisphenol A epoxy resin
|
20
|
Novolac epoxy resin
|
15
|
Isofluorone
|
15
|
Dispersing agent
|
1.5
|
Leveling agent
|
0.3
|
Defoaming agent
|
0.2
|
Fumed silica
|
3
|
Titanium white powder
|
35 |
The rotating speed is 800-1500 rpm, the materials in the table 5 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 25-35 minutes at the rotating speed of 2500-3500 rpm. And then grinding the mixture on a three-roller machine until the fineness is less than 5 microns.
TABLE 6
Curing agent
|
Parts by weight
|
2-methylimidazole
|
8
|
Isofluorone
|
2 |
The dispersion and dissolution are complete.
The main agent and the curing agent are evenly mixed according to the proportion of 9/1, and 3 percent of isophorone is added to adjust the viscosity. 3D glass pretreatment which is subjected to hot bending: spraying ink, curing at 180 ℃ for 30-40 minutes, cooling, repeatedly spraying ink once, curing, cooling, and performing laser etching.
Comparative example 2
The parts by weight of the respective components of the inks in the comparative examples are shown in tables 7 and 8.
TABLE 7
Ink main agent component
|
Parts by weight
|
Hydroxy acrylic resin
|
30
|
Polyester resin
|
25
|
Isofluorone
|
17
|
Dispersing agent
|
1.5
|
Leveling agent
|
0.3
|
Defoaming agent
|
0.2
|
Fumed silica
|
1
|
Carbon black
|
15 |
The rotating speed is 800-1500 rpm, the materials in the table 5 are sequentially added while stirring, and after uniform mixing, the materials are dispersed for 25-35 minutes at the rotating speed of 2500-3500 rpm. And then grinding the mixture on a three-roller machine until the fineness is less than 5 microns.
TABLE 8
Curing agent
|
Parts by weight
|
Toluene diisocyanate
|
10 |
The main agent and the curing agent are evenly mixed according to the proportion of 9/1, and 3 percent of isophorone is added to adjust the viscosity. Pre-treating the bent 3D glass with two concave sides: printing the printing ink on a specially-made PET film, curing for 30-40 minutes at 120 ℃, cooling, and then hot-pressing the PET film on glass through a specially-made roller for curing.
The results of the performance tests of the inks prepared in examples 1 to 4 and comparative examples 1 to 2 are shown in Table 9.
The comparative examples are the basic formulation and ink usage of the conventional 3D glass ink on the market, and the results obtained by testing according to the national standard are shown in table 9.
TABLE 9 test results of ink Performance for examples 1-4 and comparative examples 1-2
As can be seen from Table 9, the inks prepared in examples 3 and 4 are the most excellent in all properties, and the inks prepared in the present invention are superior to those obtained in the comparative examples in all properties.
Pencil hardness test standard reference GB/T6739-2006
Adhesion test standard refers to GB/T6739-2006
Standard reference for boiling test GB/T1733 (second method)
QUV test Standard reference GB/T23987-2009
Reference GB/T1766 for cosmetic-resistant test standard
High-temperature high-humidity test standard reference GB/1740
Reference for acid resistance test standard GB1785-79
Standard reference for solvent resistance test GB/T1733 (first method)
Alkali-resistant test standard reference GB1763-79
Salt spray resistance test standard reference GB1771-79
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.