CN108147673A - A kind of glass dust, ink and chemically reinforced glass - Google Patents
A kind of glass dust, ink and chemically reinforced glass Download PDFInfo
- Publication number
- CN108147673A CN108147673A CN201810084783.4A CN201810084783A CN108147673A CN 108147673 A CN108147673 A CN 108147673A CN 201810084783 A CN201810084783 A CN 201810084783A CN 108147673 A CN108147673 A CN 108147673A
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- CN
- China
- Prior art keywords
- glass
- ink
- glass dust
- dust
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
Abstract
The present invention relates to glass printing technical field of ink, particularly a kind of glass printing ink glass dust consists of the following components in percentage by weight：0~15% filler, 5~30% ion exchange accelerating agent, surplus are glass base glaze, and the ion exchange accelerating agent is made of the following components for accounting for the weight percent of glass dust：0~5% Li2O, 0.1~18% Na2O, 0.1~5% K2O, 5~11% Al2O3.Advantage is：Ink layer stability is good, can carry out chemical tempering, can play the role of promoting ion exchange.The present invention is also provided simultaneously using ink made of the glass dust and the chemically reinforced glass with ink print side.
Description
Technical field：
The present invention relates to glass printing technical field of ink, particularly a kind of glass printing ink glass dust, using this
Ink made of glass dust and the chemically reinforced glass with ink print side are particularly suitable for the vehicle window interlayer glass of chemical strengthening
Glass.
Background technology：
Vehicle glass is for beautiful, masking or assists cohesive purpose, ink is printed on surface, for general object
Tempered glass is managed, traditional process is that ink is coated to the table of glass baseplate by way of silk-screen printing or ink jet printing
Face, after the drying of (about 150 DEG C) of low temperature, at high temperature (500~700 DEG C) by thermal sintering, be adhered to the surface of glass.It is based on
The ink of this technology mode, in high temperature sintering, the cryogenic glass powder in ink can melt, and occur with glass baseplate viscous
Knot, so as to achieve the purpose that ink layer is combined with glass baseplate.In existing technique, glass baseplate usually requires at high temperature
Be molded, ink is heated to the softening point of glass after printing and drying together with glass baseplate, glass carry out into
While type, ink is sintered to glass substrate surface, while completes physical toughened process by the glass of high temperature.
And to when the glass baseplate of chemical strengthening being needed to carry out ink printing, such as thin glass of the thickness less than 1.1mm or super
Thin glass has the process route of following three kinds of references：1st, glass baseplate first carries out plane ink printing, then carries out hot bending,
Chemical strengthening finally is carried out to the glass for carrying ink；2nd, glass baseplate first passes through chemical strengthening, then carries out plane ink printing,
Finally carry out hot bending；3rd, glass baseplate first carries out hot bending, then carries out chemical strengthening, finally carries out curved surface ink print
Brush.
For route 2, the glass baseplate by chemical strengthening is again heated to glass transition temperature, meeting in forming process
Lead to the stress relaxation of chemical strengthening, so as to seriously weaken the effect for even eliminating chemical strengthening；For route 3, industrial mesh
Preceding equipment and technique there has been no applied to the three-dimensional large curved surface printing of high-volume.Therefore, route 2 and route 3 are in prior art item
It can not be realized under part or cost of implementation is excessively high, route 1 can only be used to carry out ink printing.
However for route 1, the glass powder component in existing ink can cause during chemical strengthening, in fused salt
Ion can not effectively penetrate ink layer and reach glass surface progress ion exchange, within certain chemical strengthening time, ink
The glass baseplate of printing zone can not effectively be strengthened, its base material with non-printing district is caused significant stress difference occur
Away from glass, which can bend, even to be ruptured；Meanwhile the strength of glass of Printing Zone is very low, can not use in practice；It is furthermore existing
The component for having ink can cause in chemical strengthening process, and the pigment of glass dust or auxiliary agent are decomposed in fused salt in ink, pollution
Chemical strengthening equipment and fused salt.
In conclusion existing ink composition can not meet the print request of chemically reinforced glass, therefore, there is an urgent need to one
The novel chemically reinforced glass printing ink glass dust of kind.
Invention content：
The technical problems to be solved by the invention are for above-mentioned technical problem existing for existing glass printing ink, are provided
It is a kind of to promote ion exchange in chemical strengthening process, be not easy the glass printing ink glass dust being decomposed, simultaneously
A kind of chemically reinforced glass that side is printed using ink made of the glass dust and with ink is also provided.
The technical scheme adopted by the invention to solve the technical problem is that：A kind of glass printing ink glass dust, it is special
Sign is, consists of the following components in percentage by weight：0~15% filler, 5.2~30% ion exchange accelerating agent are remaining
It measures as glass base glaze, the ion exchange accelerating agent is made of the following components for accounting for the weight percent of glass dust：0~5%
Li2O, 0.1~18% Na2O, 0.1~5% K2O, 5~11% Al2O3。
Further, the ion exchange accelerating agent is made of the following components for accounting for the weight percent of glass dust：0~
4.3% Li2O, 0.3~16.5% Na2O, 0.3~4.5% K2O, 5.5~10.8% Al2O3。
Further, the Li2O、Na2O and K2The summation that O accounts for the weight percent of glass dust is 0.2~19%.
Further, the glass base glaze is made of the following components for accounting for the weight percent of glass dust：35~60%
Bi2O3, 10~30% SiO2, 0~15% B2O3。
Further, the filler is made of the following components for accounting for the weight percent of glass dust：0~0.02% CaO,
0~0.5% MgO, 0~0.5%BaO, 0~0.5%SrO, 0~5% TiO2, 0~4% ZrO2, 0~8% ZnO.
Further, the summation that described CaO, MgO, BaO and SrO account for the weight percent of glass dust is 0~1%.
The present invention also provides a kind of glass printing ink, which is characterized in that consists of the following components in percentage by weight：15
~25% colorant, 20~35% varnish, surplus are above-described glass dust.
Further, the colorant for carbon black, iron content pigment, containing cobalt pigment, containing cadmium pigment, containing chromium pigment, titaniferous face
Expect, containing at least one of zinc pigment, pigment containing magnesium, pigment containing vanadium and copper chromite black spinel, the varnish includes
Solvent and resin.
The present invention also provides a kind of chemically reinforced glass with ink print side, including glass substrate and are arranged on glass base
Ink print side at least one edge of plate, the glass substrate is the thin glass of chemical strengthening, it is characterised in that：The oil
Ink side is formed using ink printing made of above-described glass dust.
Further, the glass substrate is soda lime glass, alumina silicate glass or aluminium borosilicate glass, thick
It spends for 0.1~2.2mm.
The present invention has the advantages that due to taking above-mentioned technical proposal：
1) ink layer of the present invention has the coefficient of expansion more higher than traditional ink, during chemical strengthening,
Structure can occur loose in fused salt, generate enough ion exchange channels, so as to which the ion in fused salt is effectively allowed to lead to
It crosses, the surface and glass baseplate for reaching glass baseplate carry out ion exchange, can play the role of promoting ion exchange；
2) since the glass baseplate applied is thin or ultra-thin glass, such glass is swollen with higher fusing point and heat in itself
Swollen coefficient, therefore ink of the present invention will not cause to become in temperature because of having higher coefficient of thermal expansion than traditional ink
During change, ink is caused to crack due to coefficient of thermal expansion mismatch between glass baseplate and ink；
3) while after the sintering of the ink of the present invention, ink layer composition is stablized, in addition to ensureing that fused salt ion passes through ink
Layer and outside the partial alkaline-metal ion that swaps, do not have other pigment or auxiliary agent decomposed in fused salt, avoid fused salt by
To pollution.
Description of the drawings：
Fig. 1 is a kind of structure diagram of chemically reinforced glass that side is printed with ink of the present invention；
Attached figure label explanation：1 is glass substrate, and 2 print side for ink.
Specific embodiment：
Present disclosure is described further below in conjunction with attached drawing.
A kind of glass printing ink glass dust of the present invention, which is characterized in that by the group of following weight percent
It is grouped as：0~15% filler, 5.2~30% ion exchange accelerating agent, surplus are glass base glaze, and the ion exchange promotees
It is made of into agent the following components for accounting for the weight percent of glass dust：0~5% Li2O, 0.1~18% Na2O, 0.1~5%
K2O, 5~11% Al2O3, preferably 0~4.3% Li2O, 0.3~16.5% Na2O, 0.3~4.5% K2O, 5.5
~10.8% Al2O3, more preferably 0~3.8% Li2O, 0.45~15.2% Na2O, 0.5~3.8% K2O, 4.8~
8.7% Al2O3。
In the present invention, Al2O3Acceleration can be played in ion exchange process, reason is Al2O3Replace glass
Glass Network former (the SiO in bismuth silicate systems2Or Bi2O3) after, due to Al3+Radius it is big, the volume of system is caused to increase
Greatly, permeability enhances, while is also beneficial to absorb the K of large volume in fused salt+, promote ion exchange.But Al2O3Content it is unsuitable
It is excessively high, the fusing point of glass base glaze system otherwise can be caused to increase, be unfavorable for the sintering of ink.The Li2O、Na2O and K2O etc.
Alkali metal oxide other than as ion exchange accelerating agent, can also reduce the softening point of glass base glaze system, alleviate system
The softening point caused by alumina content is higher increases.
Preferably, the Li2O、Na2O and K2The summation that O accounts for the weight percent of glass dust is 0.2~19%, preferably
0.6~18.6%, more preferably 0.65%~17.5%.
Wherein, the glass base glaze can be the glass for vehicle window printing common ingredient of ink, preferably by accounting for glass dust
The following components composition of weight percent：35~60% Bi2O3, 10~30% SiO2, 0~15% B2O3。
Wherein, the filler is made of the following components for accounting for the weight percent of glass dust：0~0.02% CaO, 0~
0.5% MgO, 0~0.5%BaO, 0~0.5%SrO, 0~5% TiO2, 0~4% ZrO2, 0~8% ZnO.
As a preferred option, alkaline earth oxide is contained in glass dust as filler, it can be with the sintering of regulation system
Temperature and chemical stability.However the presence of alkaline-earth metal ions again can be bad to the generation of the ion exchange process in chemical strengthening
It influences, this is because a small amount of alkaline earth oxide substitution Network former can cause the diffusion of ion exchange to reduce,
The diffusion admittance of alkali metal ion can be blocked simultaneously, ion-exchange speed is caused to decline, efficiency reduces.Therefore, in the present invention,
Need the content of strictly control alkaline earth oxide, it is preferable that described CaO, MgO, BaO, SrO account for the weight percent of glass dust
The summation of ratio is 0~1wt%.
The present invention also provides a kind of glass printing ink, which is characterized in that consists of the following components in percentage by weight：15
~25% colorant, 20~35% varnish, surplus are above-mentioned glass dust.
In the present invention, the colorant for carbon black, iron content pigment, containing cobalt pigment, containing cadmium pigment, containing chromium pigment, titaniferous
Pigment, containing at least one of zinc pigment, pigment containing magnesium, pigment containing vanadium and copper chromite black spinel.It is chosen as CuO-Cr2O3,
CoO-Cr2O3, Fe2O3- MnO, Fe2O3-Cr2O3, CuO-Cr2O3- MnO, Fe2O3-NiO-MnO-Cr2O3And MnO-CuO-Cr2O3-
Fe2O3At least one of-NiO combinations.
In the present invention, the mixture that the varnish is made of organic solvent and resin, for adjusting the glutinous of ink
Degree or dilute thick degree.Wherein, pine tar, α-terpineol, butyl carbitol, acetate of butyl carbitol, third can be selected in organic solvent
Glycol, hexylene glycol, butyl phthalate, kerosene, butanol and other high-boiling point alcohols and high boiling ester.Fiber can be selected in resin
Plain resin, acrylic resin, methacrylic resin, butyral resin, vinyl pyrrolidine ketone resin, ethyl cellulose, phenolic aldehyde tree
Fat, ethyl cellulose and phenolic resin blend, the polymethacrylates of lower alcohol, 2-Butoxyethyl acetate, ethyl fourth
Acetal, butyl formaldehyde, styrene resin, petroleum distillate, wood rosin etc..The varnish is by 30~60wt% organic solvents and 15
~40wt% resins form.Preferably, using propylene glycol-phenolic resin, butyl phthalate-ethyl cellulose and phenolic aldehyde tree
A kind of combination in lipoprotein mixture, α-terpineol-styrene resin, hexylene glycol-butyral resin.
As shown in Figure 1, the present invention also provides a kind of chemically reinforced glass with ink print side simultaneously, including glass substrate
1 prints side 2 with the ink being arranged at least one edge of glass substrate 1, and the glass substrate 1 is the thin glass of chemical strengthening
Or ultra-thin glass, it is characterised in that：The ink print side 2 uses ink printing made of above-mentioned glass dust to form.
In the present invention, the glass substrate be soda lime glass, alumina silicate glass or aluminium borosilicate glass,
Particularly with higher aluminum content sodium-calcium-silicate is thin or ultra-thin glass and containing alkali alumino-silicates are thin or ultra-thin glass.
Wherein, the main component of the soda lime glass is silicon, sodium and calcium, and the thickness of the glass substrate is 0.1~2.2mm,
The ultra-thin soda lime glass or glass containing alkali alumino-silicates of preferably 0.35~1.1mm thickness.
More detailed illustrate is carried out to the present invention below in conjunction with specific embodiment.
Table 1：The weight percent of comparative example and Examples 1 to 4 ink composition
Table 2：Comparative example and the weight percent of Examples 1 to 4 glass dust and coloring agent component
Table 3：Comparative example and Examples 1 to 5 result of the test data
Upper Tables 1 and 2 shows the weight percent of the ink composition of a comparative example and five embodiments, wherein, it is real
The ink composition and embodiment 4 for applying example 5 are identical, no longer list in detail, differ only in the glass substrate used.In table 3
In, Examples 1 to 4 and comparative example use the glass containing alkali alumino-silicates with higher aluminum content that thickness is 0.7mm
Substrate, if aluminum content is 13.5%, the relatively low soda-lime glass substrate of the aluminum content that embodiment 5 uses thickness to be 0.7mm, such as
Aluminum content is 1.8%.
By upper table 3 it is found that in the time, being printed with the glass of the ink of comparative example in identical chemical strengthening (ion exchange)
The bearing stress in region is relatively low, and chemical strengthening effect is undesirable.And in Examples 1 to 4, it is printed with the glass of ink of the present invention
Glass print border region (i.e. the ink print border region of Fig. 1) can reach and should without the close surface pressure of the non-print border region for printing ink
Power shows that ion exchange has effectively penetrated ink layer, and chemical strengthening works well.
In addition, fused salt changes colour after comparative example chemical strengthening, surface colourant is broken down into fused salt, and embodiment 1
~5 fused salt does not change colour, shows that colorant is not melted into fused salt.
In addition, the ink printed glass of comparative example and embodiment is after chemical strengthening, in 80 DEG C, 0.1N sulfuric acid solutions
After impregnating 72h, do not change colour, disclosure satisfy that the acid resistance requirement of glass for vehicle window.
More than content has been described in detail a kind of glass dust of the present invention, ink and chemically reinforced glass, but
It is that the present invention is not limited to by specific embodiments described above content, so what all technical essentials according to the present invention carried out
Any improvement, equivalent modifications and replacement etc., belong to the scope of protection of the invention.
Claims (10)
1. a kind of glass printing ink glass dust, which is characterized in that consist of the following components in percentage by weight：0~15%
Filler, 5.2~30% ion exchange accelerating agent, surplus be glass base glaze, the ion exchange accelerating agent is by accounting for glass dust
Weight percent following components composition：0~5% Li2O, 0.1~18% Na2O, 0.1~5% K2O, 5~11%
Al2O3。
2. glass dust according to claim 1, it is characterised in that：The ion exchange accelerating agent is by accounting for the weight of glass dust
The following components composition of percentage：0~4.3% Li2O, 0.3~16.5% Na2O, 0.3~4.5% K2O, 5.5~
10.8% Al2O3。
3. glass dust according to claim 1, it is characterised in that：The Li2O、Na2O and K2O accounts for the weight hundred of glass dust
The summation for dividing ratio is 0.2~19%.
4. glass dust according to claim 1, it is characterised in that：The glass base glaze is by accounting for the weight percent of glass dust
Following components composition：35~60% Bi2O3, 10~30% SiO2, 0~15% B2O3。
5. glass dust according to claim 1, it is characterised in that：The filler by account for glass dust weight percent with
The following group is grouped as：0~0.02% CaO, 0~0.5% MgO, 0~0.5%BaO, 0~0.5%SrO, 0~5% TiO2,
0~4% ZrO2, 0~8% ZnO.
6. glass dust according to claim 5, it is characterised in that：Described CaO, MgO, BaO and SrO account for the weight of glass dust
The summation of percentage is 0.05~1%.
7. a kind of glass printing ink, which is characterized in that consist of the following components in percentage by weight：15~25% coloring
Agent, 20~35% varnish, surplus are any glass dust of claim 1~6.
8. glass printing ink according to claim 7, it is characterised in that：The colorant is carbon black, iron content pigment, contains
Cobalt pigment, containing cadmium pigment, containing chromium pigment, containing titanium pigment, it is brilliant containing zinc pigment, pigment containing magnesium, pigment containing vanadium and copper chromite black point
At least one of stone, the varnish include organic solvent and resin.
9. a kind of chemically reinforced glass with ink print side, including glass substrate (1) and is arranged on glass substrate (1) at least
Ink print side (2) on one edge, the glass substrate (1) are the thin glass of chemical strengthening, it is characterised in that：The ink
Print side (2) is formed using ink printing made of any glass dust of claim 1~6.
10. chemically reinforced glass according to claim 9, it is characterised in that：The glass substrate is sodium-calcium-silicate glass
Glass, alumina silicate glass or aluminium borosilicate glass, thickness are 0.1~2.2mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810084783.4A CN108147673A (en) | 2018-01-29 | 2018-01-29 | A kind of glass dust, ink and chemically reinforced glass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810084783.4A CN108147673A (en) | 2018-01-29 | 2018-01-29 | A kind of glass dust, ink and chemically reinforced glass |
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ID=62459168
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655329A (en) * | 2019-10-31 | 2020-01-07 | 维达力实业(深圳)有限公司 | Glass printing ink for chemical tempering and preparation method and application thereof |
| CN111592234A (en) * | 2020-04-26 | 2020-08-28 | 维达力实业(深圳)有限公司 | Patterned curved glass and preparation method and application thereof |
| CN112574614A (en) * | 2020-11-18 | 2021-03-30 | 福耀玻璃工业集团股份有限公司 | Printing composition for laser film removal and method for manufacturing laminated glass |
| CN113174151A (en) * | 2021-05-07 | 2021-07-27 | 珠海市力众实业有限公司 | Slurry and preparation method and application thereof |
| CN113512322A (en) * | 2021-06-25 | 2021-10-19 | 吴江南玻玻璃有限公司 | Environment-friendly water-based ink mixing oil for photovoltaic glass glaze and preparation method thereof |
| CN113651529A (en) * | 2021-09-23 | 2021-11-16 | 北京北旭电子材料有限公司 | Glass composition, glass powder, glass ink and application of glass ink |
| US20220024817A1 (en) * | 2018-12-21 | 2022-01-27 | Corning Incorporated | Strengthened 3d printed surface features and methods of making the same |
| CN114605087A (en) * | 2022-03-21 | 2022-06-10 | 杭州杰奇玻璃材料有限公司 | Processing method for manufacturing soft-vision energy-saving glass by adopting glaze printing technology |
| CN115286263A (en) * | 2022-07-08 | 2022-11-04 | 苏州胜利精密制造科技股份有限公司 | Preparation method of curved surface cover plate |
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| US20220024817A1 (en) * | 2018-12-21 | 2022-01-27 | Corning Incorporated | Strengthened 3d printed surface features and methods of making the same |
| CN110655329B (en) * | 2019-10-31 | 2022-07-12 | 维达力实业(深圳)有限公司 | Glass printing ink for chemical tempering and preparation method and application thereof |
| CN110655329A (en) * | 2019-10-31 | 2020-01-07 | 维达力实业(深圳)有限公司 | Glass printing ink for chemical tempering and preparation method and application thereof |
| US11970421B2 (en) * | 2019-12-05 | 2024-04-30 | Corning Incorporated | Strengthened 3D printed surface features and methods of making the same |
| CN111592234B (en) * | 2020-04-26 | 2022-06-21 | 维达力实业(深圳)有限公司 | Patterned curved glass and preparation method and application thereof |
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| CN112574614A (en) * | 2020-11-18 | 2021-03-30 | 福耀玻璃工业集团股份有限公司 | Printing composition for laser film removal and method for manufacturing laminated glass |
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Application publication date: 20180612 |