CN105062198A - Bismuth-oxide-based black pigment used for glass digital inkjet printing and preparation method of bismuth-oxide-based black pigment - Google Patents
Bismuth-oxide-based black pigment used for glass digital inkjet printing and preparation method of bismuth-oxide-based black pigment Download PDFInfo
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- CN105062198A CN105062198A CN201510553661.1A CN201510553661A CN105062198A CN 105062198 A CN105062198 A CN 105062198A CN 201510553661 A CN201510553661 A CN 201510553661A CN 105062198 A CN105062198 A CN 105062198A
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- bismuth
- based black
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Abstract
The invention provides bismuth-oxide-based black pigment used for glass digital inkjet printing and a preparation method of the bismuth-oxide-based black pigment. The bismuth-oxide-based black pigment is characterized in that preparation raw materials of the bismuth-oxide-based black pigment include bismuth oxide (alpha type Bi2O3), amorphous state silicon oxide (SiO2), boron oxide (B2O3), lithium oxide (LiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2) and copper chromite black (common industrial coloring materials); the preparation method includes the steps of evenly mixing bismuth oxide (alpha type Bi2O3), amorphous state silicon oxide (SiO2), boron oxide (B2O3), lithium oxide (LiO2), aluminum oxide (Al2O3) and zirconium oxide (ZrO2), conducting high energy ball milling to make the mixture sufficiently and mechanically alloyed, and mixing the powder obtained through ball milling with copper chromite black in a ball milling mode. The maximum particle size of the bismuth-oxide-based black pigment is smaller than 2 micrometers, the sintering temperature on glass is between 600 DEG C and 700 DEG C, the bonding strength between the bismuth-oxide-based black pigment and the glass is high, and the bismuth-oxide-based black pigment has wide application prospects in the field of digital inkjet printing.
Description
Technical field
The invention belongs to glass numerial code spray drawing printing technique field, particularly a kind of glass numerial code spray drawing printing bismuth oxide based black colorant and preparation method thereof.
Background technology
Glass numerial code spray drawing printing technique as a kind of newly contactless, without pressure, printing technology without forme, pushed current glass fashion, personalization, art up, short run, multi-color, low-carbon environment-friendly development trend to a new height.Since China in 2009 introduces First glass ink jet unit, the development of glass numerial code spray drawing printing technique is advanced by leaps and bounds, and is widely applied.Compared with traditional glass surface printing technology, glass numerial code spray drawing printing technique have product pattern exquisiteness true to nature clear, the advantages such as personalized designs and manufacture, level of automation are high can be realized fast, receive showing great attention to of glass industry, through development in a few years, the share of market of glass numerial code spray drawing product is more and more higher.
The technological process of glass numerial code spray drawing printing technique mainly comprises inkjet printing ink and high temperature sintering two operations.Glass numerial code spray drawing printing technique has two core technologies, and one is the preparation of numerial code spray drawing printing glass ink, and two is manufactures of numerial code spray drawing printing head.Wherein, numerial code spray drawing printing glass ink is generally made up of inorganic powder colorant, tensio-active agent, organic solvent, dispersion agent etc.Inorganic powder colorant is the core substance of numerial code spray drawing printing glass ink.Glass numerial code spray drawing printing technique has very high requirement to inorganic powder colorant, especially requires high to aspects such as its granularity, sintering temperature and glass bonding forces.Its granularity general requirement is not more than 2 μm, otherwise can affect the fine and smooth sharpness of printed product, even blocks ink gun; Its sintering temperature general requirement lower than 700 DEG C, otherwise can cause glass to be out of shape in sintering process; The requirement of itself and glass bonding force aspect is also very high, otherwise printable layer can be made to come off in use procedure after sintering.
Current glass ink is on the market of poor quality, cannot meet the growing demand of human consumer far away.Bismuth oxide as a kind of emerging multi-purpose material, with the glass ink that it is prepared have that sintering temperature is low, processing performance good, with the feature such as glass bonding force is strong.But, up to the present, China does not still have a kind of glass numerial code spray drawing printing bismuth oxide based black colorant having independent intellectual property right and preparation method thereof available, and this constrains the development of China's glass numerial code spray drawing printing technique and products thereof to a certain extent.
Summary of the invention
The object of the present invention is to provide a kind of glass numerial code spray drawing printing bismuth oxide based black colorant and preparation method thereof.
The technical solution used in the present invention is:
A kind of glass numerial code spray drawing prints with bismuth oxide based black colorant, it is characterized in that its raw materials is bismuth oxide (α-type Bi
2o
3), amorphous silica (SiO
2), boron oxide (B
2o
3), Lithium Oxide 98min (Li
2o), aluminum oxide (Al
2o
3), zirconium white (ZrO
2) and copper-chrome black (common industrial colorant), wherein, bismuth oxide (α-type Bi
2o
3) mass percent be 32.95 ~ 42.95%, amorphous silica (SiO
2) mass percent be 13 ~ 17%, boron oxide (B
2o
3) mass percent be 4.8 ~ 8.8%, Lithium Oxide 98min (Li
2o) mass percent is 3.3 ~ 5.3%, aluminum oxide (Al
2o
3) mass percent be 2.25 ~ 3.25%, zirconium white (ZrO
2) mass percent be 1 ~ 1.4%, the mass percent of copper-chrome black (common industrial colorant) is 21.3 ~ 42.7%, and each component sum is 100%.
Each raw material of described black pigment and bismuth oxide (α-type Bi
2o
3), amorphous silica (SiO
2), boron oxide (B
2o
3), Lithium Oxide 98min (Li
2o), aluminum oxide (Al
2o
3), zirconium white (ZrO
2) and the maximum particle diameter of copper-chrome black (common industrial colorant) powder all need to be less than 1 μm;
The preparation method of described black pigment, comprises the following steps:
1) each raw material of colorant is weighed by proportioning, first by bismuth oxide (α-type Bi
2o
3), amorphous silica (SiO
2), boron oxide (B
2o
3), Lithium Oxide 98min (Li
2o), aluminum oxide (Al
2o
3), zirconium white (ZrO
2) be uniformly mixed;
2) above-mentioned raw materials prepared is placed in high energy ball mill and carries out high-energy ball milling, make abundant mechanical alloying between each material component, for dissimilar ball mill, the corresponding change of ball milling parameter.
3) load weighted to powder obtained above and the first step copper-chrome black is mixed, put into high energy ball mill by certain ball milling parameter ball milling mixing certain hour, namely obtain described black pigment.
Step 2 in the preparation method of described black pigment) established standards of described ball milling parameter be Ball-milling Time is 12 ~ 60h, the maximum particle diameter of finished product colorant powder is less than 2 μm, the ball milling parameter of attritor mill is generally set as: rotating speed 250 ~ 400r/min, ratio of grinding media to material setting 6-15:1.
In the preparation method of described black pigment, the established standards of ball milling parameter described in step 3) is Ball-milling Time is 1 ~ 12h, the maximum particle diameter of finished product colorant powder is less than 2 μm, the ball milling parameter of attritor mill is generally set as: rotating speed 200 ~ 300r/min, ratio of grinding media to material setting 6-15:1.
The sintering temperature of described black pigment on glass is 600 ~ 700 DEG C.
The invention has the beneficial effects as follows:
(1) glass numerial code spray drawing printing bismuth oxide based black colorant provided by the invention, its maximum particle diameter is less than 2 μm, greatly reduces the phenomenon that ink gun blocked by ink, has good Ink Jet Printing Performance.
(2) glass numerial code spray drawing printing bismuth oxide based black colorant provided by the invention, the sintering temperature on glass is low, between 600 ~ 700 DEG C.
(3) glass numerial code spray drawing printing bismuth oxide based black colorant provided by the invention, after sintering, and bonding force between glass is strong, and scraping does not come off, do not ftracture.
(4) the present invention obtains desirable colorant component prescription scope and colorant preparation method by a large amount of tests, especially invent the colorant carried out in order and prepared three-step approach, can easily obtain satisfactory colorant by colorant component prescription scope of the present invention and colorant process of preparing.In addition, by changing the mass ratio formula of High Energy Ball Milling Time and raw material, can produce the black of different colourity, meet the various demands of client to color, market adaptability is strong.
(5) raw material of glass numerial code spray drawing printing bismuth oxide based black colorant provided by the invention is harmless metal oxide powder, and the objectionable impurities such as not leaded, mercury, environmental friendliness, is easy to be accepted.
(6) preparation method of black pigment provided by the invention is simply efficient, and controllability is good, is applicable to industrialization scale operation.
(7)the invention discloses a kind of glass numerial code spray drawing printing bismuth oxide based black colorant and preparation method thereof, promote China's glass industry to a certain extent to more personalized, more art up future development.
Accompanying drawing explanation
Fig. 1 is glass numerial code spray drawing printing bismuth oxide based black colorant prepared by the embodiment of the present invention 1.
Fig. 2 is that glass numerial code spray drawing printing bismuth oxide based black colorant SEM prepared by the embodiment of the present invention 1 schemes.
Fig. 3 is the XRD figure of glass numerial code spray drawing printing bismuth oxide based black colorant prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Embodiment one.
A kind of glass numerial code spray drawing prints with bismuth oxide based black colorant, and its preparation method is:
First, for 500ml ball grinder, be once suitable for grinding 25g black pigment, according to according to bismuth oxide (α-type Bi
2o
3) 37.95%, amorphous silica (SiO
2) 15%, boron oxide (B
2o
3) 6.8%, Lithium Oxide 98min (Li
2o) 4.3%, aluminum oxide (Al
2o
3) 2.75%, zirconium white (ZrO
2) 1.2%, the mass percent of copper-chrome black 32%, calculate each raw materials quality required for ball milling 25g black pigment, bismuth oxide (α-type Bi
2o
3) 9.49 grams, amorphous silica (SiO
2) 3.75 grams, boron oxide (B
2o
3) 1.7 grams, Lithium Oxide 98min (Li
2o) 1.08 grams, aluminum oxide (Al
2o
3) 0.68 gram, zirconium white (ZrO
2) 0.3 gram, copper-chrome black 8 grams, then weigh according to calculation result;
Secondly, load weighted each raw material is placed in beaker, stirs, more also can be 6:1 or 15:1 according to 10:1() ratio of grinding media to material weigh 196g agate ball;
Then, above-mentioned raw materials and agate ball are poured in ball grinder together, start ball milling, in mechanical milling process, rotating speed 300r/min(also can be the arbitrary numerical value between 250-400r/min), every 12h shuts down once, open ball grinder the powder of caking is pulverized, ensure the uniform mechanical alloying of powder in mechanical milling process, after ball milling 60h, stop ball milling, take out the powder obtained in ball grinder;
Then, the powder of above-mentioned taking-up is mixed with load weighted copper-chrome black, changes clean ball grinder, more also can be any ratio of grinding media to material between 6:1 or 15:1 according to 10:1() ratio of grinding media to material weigh 250g agate ball;
Finally, above-mentioned raw materials and agate ball are poured in ball grinder together, start ball milling, in mechanical milling process, rotating speed 200r/min (also can be the arbitrary numerical value between 200-300r/min), after ball milling 1-12h, stop ball milling, obtain described glass numerial code spray drawing printing bismuth oxide based black colorant.
The black pigment that the present embodiment obtains, as shown in Figure 1, finished product black pigment, uniform color, color is black, Figure 2 shows that the SEM figure of finished product black pigment, and the particle diameter major part of particle is less than 1 μm, the particle that minority particle diameter is greater than 2 μm, can filter out in later stage Printing ink producing process, Figure 3 shows that the XRD figure of colorant, can find out the abundant mechanical alloying of each feed composition, the sintering temperature of black pigment on glass that the present embodiment obtains is 670 DEG C.
Embodiment two.
Roughly the same, difference is that the mass percent shared by raw material is different for the present embodiment and embodiment one experimental technique.According to bismuth oxide (α-type Bi
2o
3) 32.95%, amorphous silica (SiO
2) 13%, boron oxide (B
2o
3) 4.8%, Lithium Oxide 98min (Li
2o) 3.3%, aluminum oxide (Al
2o
3) 2.25%, zirconium white (ZrO
2) 1%, the mass percent of copper-chrome black 42.7%, calculate each raw materials quality required for ball milling 25g black ink powder colorant, bismuth oxide (α-type Bi
2o
3) 8.2 grams, amorphous silica (SiO
2) 3.25 grams, boron oxide (B
2o
3) 1.2 grams, Lithium Oxide 98min (Li
2o) 0.83 gram, aluminum oxide (Al
2o
3) 0.56 gram, zirconium white (ZrO
2) 0.25 gram, copper-chrome black 10.71 grams, then weigh according to calculation result, step below and embodiment 1 completely the same.
The black pigment that the present embodiment obtains, similar with Fig. 1, finished product black pigment compares with embodiment one, uniform color, blackness is higher, color presents aterrimus, the SEM figure of finished product black pigment is similar to Fig. 2, and the particle diameter major part of particle is less than 1 μm, the particle that minority particle diameter is greater than 2 μm, can filter out in later stage Printing ink producing process, the XRD figure of colorant is also similar to Fig. 3, can find out the abundant mechanical alloying of each feed composition, the sintering temperature of black pigment on glass that the present embodiment obtains is 700 DEG C.
Embodiment three.
Roughly the same, difference is that the mass percent shared by raw material is different for the present embodiment and embodiment one experimental technique.According to bismuth oxide (α-type Bi
2o
3) 42.95%, amorphous silica (SiO
2) 17%, boron oxide (B
2o
3) 8.8%, Lithium Oxide 98min (Li
2o) 5.3%, aluminum oxide (Al
2o
3) 3.25%, zirconium white (ZrO
2) 1.4%, the mass percent of copper-chrome black 21.3%, calculate each raw materials quality required for ball milling 25g black ink powder colorant, bismuth oxide (α-type Bi
2o
3) 10.7 grams, amorphous silica (SiO
2) 4.25 grams, boron oxide (B
2o
3) 2.2 grams, Lithium Oxide 98min (Li
2o) 1.33 grams, aluminum oxide (Al
2o
3) 0.81 gram, zirconium white (ZrO
2) 0.35 gram, copper-chrome black 5.36 grams, then weigh according to calculation result, step below and embodiment 1 completely the same.
The black pigment that the present embodiment obtains, similar with Fig. 1, finished product black pigment compares with embodiment one, uniform color, blackness is lower than embodiment one and two, color presents grey black, the SEM figure of finished product black pigment is similar to Fig. 2, and the particle diameter major part of particle is less than 1 μm, the particle that minority particle diameter is greater than 2 μm, can filter out in later stage Printing ink producing process, the XRD figure of colorant is also similar to Fig. 3, can find out the abundant mechanical alloying of each feed composition, the sintering temperature of black pigment on glass that the present embodiment obtains is 600 DEG C.
Below be only enumerated part formulation, in actual applications, the mass percent of each raw material of filling a prescription can change within the specific limits, coordinates the variation of Ball-milling Time, can produce the glass numerial code spray drawing printing bismuth oxide based black colorant of different colourity.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (5)
1. glass numerial code spray drawing prints with a bismuth oxide based black colorant, it is characterized in that its raw material is by bismuth oxide (α-type Bi
2o
3), amorphous silica (SiO
2), boron oxide (B
2o
3), Lithium Oxide 98min (Li
2o), aluminum oxide (Al
2o
3), zirconium white (ZrO
2) and copper-chrome black (common industrial colorant) composition, wherein, bismuth oxide (α-type Bi
2o
3) mass percent be 32.95-42.95%, amorphous silica (SiO
2) mass percent be 13-17%, boron oxide (B
2o
3) mass percent be 4.8-8.8%, Lithium Oxide 98min (Li
2o) mass percent is 3.3-5.3%, aluminum oxide (Al
2o
3) mass percent be 2.25-3.25%, zirconium white (ZrO
2) mass percent be 1-1.4%, the mass percent of copper-chrome black (common industrial colorant) is 21.3-42.7%; Each component sum is 100%, and the particle diameter of above-mentioned each raw material is all no more than 1 μm.
2. the preparation method of glass numerial code spray drawing printing bismuth oxide based black colorant according to claim 1, is characterized in that three steps that this preparation method mainly comprises next coming in order sequence and carries out:
1) each raw material of colorant is weighed by proportioning, first by bismuth oxide (α-type Bi
2o
3), amorphous silica (SiO
2), boron oxide (B
2o
3), Lithium Oxide 98min (Li
2o), aluminum oxide (Al
2o
3), zirconium white (ZrO
2) mix;
2) the above-mentioned raw material mixed is placed in high energy ball mill and carries out high-energy ball milling, make abundant mechanical alloying between above-mentioned raw materials component, take out after ball milling certain hour, obtain mechanical alloying powder;
3) mechanical alloying powder obtained above is mixed with the load weighted copper-chrome black of the first step, put into high energy ball mill ball milling mixing certain hour, namely obtain described black pigment.
3. the preparation method of glass numerial code spray drawing printing bismuth oxide based black colorant according to claim 2, it is characterized in that step 2) in the ball milling parameter of attritor mill be: rotating speed 250-400r/min, ratio of grinding media to material setting 6-15:1 Ball-milling Time 12-60h, after ball milling, the maximum particle diameter of colorant powder is no more than 2 μm.
4. the preparation method of bismuth oxide based black colorant of the glass numerial code spray drawing printing according to Claims 2 or 3, is characterized in that the rotating speed of attritor mill in step 3) is 200-300r/min, and ratio of grinding media to material setting 6-15:1, Ball-milling Time is 1-12h.
5. glass numerial code spray drawing printing bismuth oxide based black colorant according to claim 1, is characterized in that its sintering temperature on glass is 600-700 DEG C.
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|---|---|---|---|
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|---|---|---|---|
| CN201510553661.1A CN105062198A (en) | 2015-09-02 | 2015-09-02 | Bismuth-oxide-based black pigment used for glass digital inkjet printing and preparation method of bismuth-oxide-based black pigment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085006A (en) * | 2016-06-16 | 2016-11-09 | 江苏大学 | Glass surface inkjet printing bismuth silicon boron system low melting point ink and preparation method thereof |
| WO2017215099A1 (en) * | 2016-06-16 | 2017-12-21 | 江苏大学 | Bismuth-silicon-boron-based low-melting-point nano glass powder suspension for glass jet drawing and preparation method |
| CN109651883A (en) * | 2018-12-25 | 2019-04-19 | 桂林理工大学 | A kind of black ceramic ink and preparation method thereof |
| CN109748514A (en) * | 2019-03-08 | 2019-05-14 | 淄博宝晶新材料股份有限公司 | A kind of environmental protection impact resistance glass pigment |
-
2015
- 2015-09-02 CN CN201510553661.1A patent/CN105062198A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085006A (en) * | 2016-06-16 | 2016-11-09 | 江苏大学 | Glass surface inkjet printing bismuth silicon boron system low melting point ink and preparation method thereof |
| WO2017215111A1 (en) * | 2016-06-16 | 2017-12-21 | 江苏大学 | Bismuth-silicon-boron type low-melting-point ink for glass surface spray painting and printing and preparation method therefor |
| WO2017215099A1 (en) * | 2016-06-16 | 2017-12-21 | 江苏大学 | Bismuth-silicon-boron-based low-melting-point nano glass powder suspension for glass jet drawing and preparation method |
| CN109651883A (en) * | 2018-12-25 | 2019-04-19 | 桂林理工大学 | A kind of black ceramic ink and preparation method thereof |
| CN109651883B (en) * | 2018-12-25 | 2021-11-26 | 桂林理工大学 | Black ceramic ink and preparation method thereof |
| CN109748514A (en) * | 2019-03-08 | 2019-05-14 | 淄博宝晶新材料股份有限公司 | A kind of environmental protection impact resistance glass pigment |
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Application publication date: 20151118 |
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