CN105062215A - Bismuth-oxide-base red pigment for glass digital inkjet printing and preparation method thereof - Google Patents
Bismuth-oxide-base red pigment for glass digital inkjet printing and preparation method thereof Download PDFInfo
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- CN105062215A CN105062215A CN201510557348.5A CN201510557348A CN105062215A CN 105062215 A CN105062215 A CN 105062215A CN 201510557348 A CN201510557348 A CN 201510557348A CN 105062215 A CN105062215 A CN 105062215A
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Abstract
The invention relates to a bismuth-oxide-base red pigment for glass digital inkjet printing and a preparation method thereof. The invention is characterized in that the bismuth-oxide-base red pigment for glass digital inkjet printing is prepared from bismuth oxide (alpha-Bi2O3), amorphous silicon oxide (SiO2), boron oxide (B2O3), lithium oxide (Li2O), aluminum oxide (Al2O3), zirconium oxide (ZrO2) and iron red. The preparation method comprises the following steps: uniformly mixing the bismuth oxide (alpha-Bi2O3), amorphous silicon oxide (SiO2), boron oxide (B2O3), lithium oxide (Li2O), aluminum oxide (Al2O3) and zirconium oxide (ZrO2), carrying out sufficient machine alloying by high-energy ball milling, mixing the powder obtained by ball milling with the iron red, and carrying out ball milling. The maximum particle size of the bismuth-oxide-base red pigment for glass digital inkjet printing is less than 2 mu m, the sintering temperature on glass is 600-700 DEG C, and the sintered bismuth-oxide-base red pigment for glass digital inkjet printing has high binding force with glass. Thus, the bismuth-oxide-base red pigment for glass digital inkjet printing 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 red colorant of a kind of glass numerial code spray drawing printing oxidation bismuthino 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 red colorant of glass numerial code spray drawing printing oxidation bismuthino 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
A kind of glass numerial code spray drawing printing is the object of the present invention is to provide to be oxidized red colorant of bismuthino and preparation method thereof.
The technical solution used in the present invention is:
A kind of glass numerial code spray drawing prints with the red colorant of oxidation bismuthino, 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 iron oxide red composition, wherein, bismuth oxide (α-type Bi
2o
3) mass percent be 31.27 ~ 41.27%, amorphous silica (SiO
2) mass percent be 12.33 ~ 16.33%, boron oxide (B
2o
3) mass percent be 4.5 ~ 8.5%, Lithium Oxide 98min (Li
2o) mass percent is 3.1 ~ 5.1%, aluminum oxide (Al
2o
3) mass percent be 2.13 ~ 3.13%, zirconium white (ZrO
2) mass percent be 0.97 ~ 1.37%, the mass percent of iron oxide red is 24.3 ~ 45.7%; Each component sum is 100%
Each raw material of described red colorant 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 iron oxide red powder all need to be less than 1 μm;
The preparation method of described red colorant, 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 iron oxide red is mixed, put into high energy ball mill by certain ball milling parameter ball milling mixing certain hour, namely obtain described red colorant.
Step 2 in the preparation method of described red colorant) 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 red colorant, 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 red colorant on glass is 600 ~ 700 DEG C.
The invention has the beneficial effects as follows:
(1) the red colorant of glass numerial code spray drawing printing oxidation bismuthino provided by the invention, even particle size distribution, 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) the red colorant of glass numerial code spray drawing printing oxidation bismuthino provided by the invention, the sintering temperature on glass is low, between 600 ~ 700 DEG C.
(3) the red colorant of glass numerial code spray drawing printing provided by the invention oxidation bismuthino, 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 redness of different colourity, meet the various demands of client to color, market adaptability is strong.
(5) objectionable impuritiess such as the raw material of the red colorant of glass numerial code spray drawing printing provided by the invention oxidation bismuthino is harmless metal oxide powder, not leaded, mercury, environmental friendliness, is easy to be accepted.
(6) preparation method of red colorant provided by the invention is simply efficient, and controllability is good, is applicable to industrialization scale operation.
(7) the invention discloses red colorant of a kind of glass numerial code spray drawing printing oxidation bismuthino 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 the red colorant of glass numerial code spray drawing printing oxidation bismuthino prepared by the embodiment of the present invention 1.
Fig. 2 is the red colorant SEM figure of glass numerial code spray drawing printing oxidation bismuthino prepared by the embodiment of the present invention 1.
Fig. 3 is the XRD figure of the red colorant of glass numerial code spray drawing printing oxidation bismuthino 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 the red colorant of oxidation bismuthino, and its preparation method is:
First, for 500ml ball grinder, be once suitable for grinding the red colorant of 25g, according to bismuth oxide (α-type Bi
2o
3) 36.27%, amorphous silica (SiO
2) 14.33%, boron oxide (B
2o
3) 6.5%, Lithium Oxide 98min (Li
2o) 4.1%, aluminum oxide (Al
2o
3) 2.63%, zirconium white (ZrO
2) 1.17%, the mass percent of iron oxide red 35%, calculate the red each raw materials quality required for colorant of ball milling 25g, bismuth oxide (α-type Bi
2o
3) 9.05 grams, amorphous silica (SiO
2) 3.6 grams, boron oxide (B
2o
3) 1.6 grams, Lithium Oxide 98min (Li
2o) 1.02 grams, aluminum oxide (Al
2o
3) 0.65 gram, zirconium white (ZrO
2) 0.29 gram, iron 8.79 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 188g 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 biography speed of 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, (optionally can be the arbitrary time between 12-60 hour), stop ball milling, take out the powder obtained in ball grinder;
Then, the powder of above-mentioned taking-up is mixed with load weighted iron oxide red, 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 rotating speed between 200-300r/min), after ball milling 1-12h, stop ball milling, obtain the described red colorant of glass numerial code spray drawing printing oxidation bismuthino.
The red colorant that the present embodiment obtains, as shown in Figure 1, finished products-red colorant, uniform color, color is red, Figure 2 shows that the SEM figure of finished products-red colorant, 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 red colorant 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) 31.27%, amorphous silica (SiO
2) 12.33%, boron oxide (B
2o
3) 4.5%, Lithium Oxide 98min (Li
2o) 3.1%, aluminum oxide (Al
2o
3) 2.13%, zirconium white (ZrO
2) 0.97%, the mass percent of iron oxide red 45.7%, calculate the red each raw materials quality required for colorant of ball milling 25g, bismuth oxide (α-type Bi
2o
3) 7.8 grams, amorphous silica (SiO
2) 3.1 grams, boron oxide (B
2o
3) 1.1 grams, Lithium Oxide 98min (Li
2o) 0.77 gram, aluminum oxide (Al
2o
3) 0.53 gram, zirconium white (ZrO
2) 0.24 gram, iron 11.46 grams, then weigh according to calculation result, step below and embodiment 1 completely the same.
The red colorant that the present embodiment obtains, similar with Fig. 1, finished products-red colorant and embodiment one ratio, color and luster is more even, color is scarlet, the SEM figure of finished products-red colorant 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 similar to Fig. 3, can find out the abundant mechanical alloying of each feed composition, and the sintering temperature of red colorant 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) 41.27%, amorphous silica (SiO
2) 16.33%, boron oxide (B
2o
3) 8.5%, Lithium Oxide 98min (Li
2o) 5.1%, aluminum oxide (Al
2o
3) 3.13%, zirconium white (ZrO
2) 1.37%, the mass percent of iron oxide red 24.3%, calculate each raw materials quality required for ball milling 25g red ink powder colorant, bismuth oxide (α-type Bi
2o
3) 10.3 grams, amorphous silica (SiO
2) 4.1 grams, boron oxide (B
2o
3) 2.1 grams, Lithium Oxide 98min (Li
2o) 1.27 grams, aluminum oxide (Al
2o
3) 0.78 gram, zirconium white (ZrO
2) 0.34 gram, iron oxide red 6.11 grams, then weigh according to calculation result, step below and embodiment 1 completely the same.
The red colorant that the present embodiment obtains, similar with Fig. 1, finished products-red colorant and embodiment one ratio, color and luster is more even, color is incarnadine, the SEM figure of finished products-red colorant 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 similar to Fig. 3, can find out the abundant mechanical alloying of each feed composition, and the sintering temperature of red colorant 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 red colorant of glass numerial code spray drawing printing oxidation bismuthino 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 the red colorant of oxidation bismuthino, 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 iron oxide red composition, wherein, bismuth oxide (α-type Bi
2o
3) mass percent be 31.27 ~ 41.27%, amorphous silica (SiO
2) mass percent be 12.33 ~ 16.33%, boron oxide (B
2o
3) mass percent be 4.5 ~ 8.5%, Lithium Oxide 98min (Li
2o) mass percent is 3.1 ~ 5.1%, aluminum oxide (Al
2o
3) mass percent be 2.13 ~ 3.13%, zirconium white (ZrO
2) mass percent be 0.97 ~ 1.37%, the mass percent of iron oxide red is 24.3 ~ 45.7%; The mass percent sum of each component is 100%, and the maximum particle diameter of above-mentioned each raw material all needs to be less than 1 μm.
2. the preparation method of the red colorant of glass numerial code spray drawing printing according to claim 1 oxidation bismuthino, 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 iron oxide red of the first step, put into high energy ball mill ball milling mixing certain hour, namely obtain described red colorant.
3. according to the preparation method of the red colorant of glass numerial code spray drawing printing oxidation bismuthino according to claim 2, it is characterized in that step 2) in the rotating speed of attritor mill be 250 ~ 400r/min, ratio of grinding media to material setting 6-15:1, Ball-milling Time is 12 ~ 60h, and after ball milling, the maximum particle diameter of colorant powder is no more than 2 μm.
4. the glass numerial code spray drawing according to Claims 2 or 3 prints the preparation method with the red colorant of oxidation bismuthino, it 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. the red colorant of glass numerial code spray drawing printing according to claim 1 oxidation bismuthino, is characterized in that its sintering temperature on glass is 600 ~ 700 DEG C.
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| CN201510557348.5A CN105062215A (en) | 2015-09-02 | 2015-09-02 | Bismuth-oxide-base red pigment for glass digital inkjet printing and preparation method thereof |
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| CN105062215A true CN105062215A (en) | 2015-11-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107352806A (en) * | 2017-08-14 | 2017-11-17 | 广东工业大学 | Print glass ink coloured glass powder and its preparation method and application |
| 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107352806A (en) * | 2017-08-14 | 2017-11-17 | 广东工业大学 | Print glass ink coloured glass powder and its preparation method and application |
| CN107352806B (en) * | 2017-08-14 | 2020-12-15 | 广东工业大学 | Colored glass powder for printing glass ink and preparation method and application thereof |
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Application publication date: 20151118 |