CN109306202A

CN109306202A - The application method of flux

Info

Publication number: CN109306202A
Application number: CN201710626909.1A
Authority: CN
Inventors: 汪国军
Original assignee: Qiaodi (shanghai) Industrial Co Ltd
Current assignee: Qiaodi (shanghai) Industrial Co Ltd
Priority date: 2017-07-27
Filing date: 2017-07-27
Publication date: 2019-02-05

Abstract

The present invention relates to the application methods of flux, the more particularly, to application method of glass or the glass earth flux in the high temperature number ink of ceramics printing, technical solution is: the application method of flux, including using the flux as the component for the high temperature number ink for being used for glass or ceramics printing, the ink includes liquid phase and the solid phase that is suspended in liquid phase；By weight, the weight ratio of liquid phase and solid phase is 1.5~2.8, and the solid phase refers to that solid inorganic oxide pigment, the pigment include pigment and the flux；The liquid phase includes that solvent and the ink being dissolved in solvent are subjected to auxiliary agent；The flux meets following chemical formula: SiZn_aB_bX_cL_dZ_eO_x, wherein Si, Zn, B and O indicate elemental silicon, zinc, boron and oxygen；X is selected from least one of alkali or alkaline earth metal element；L indicates at least one of titanium, aluminium and zirconium element；Z indicates at least one of IIIB metal element.

Description

The application method of flux

Technical field

The present invention relates to the production of the secondary industrial processing decoration pattern of glass, and in particular to the application method of flux, especially It is related to the application method of the glass earth flux in the high temperature number ink printed for glass.

Background technique

As artificial intelligence technology develops, industrial glass secondary operation production decorative pattern uses digital printing skill in recent years Art gradually increases, mainly since compared with traditional silk-screen, roller coating, bat printing, digital printing makes glass decoration pattern color Bright-coloured, pattern is full.Being able to produce and sell in the world at present high temp glass marking ink is mainly external two companies, but he Product generally do ink solvent, such as US201500386616A1 using linear paraffin, aromatic hydrocarbons, ether monomer, US007803221B2, CN101163761A, not only solvent odor is big in these technologies, and harm to the human body is serious, influences product and answers With, and aldehyde, ketone solvent are generally used when cleaning speckles with the equipment of these inks, it is bigger to the harm of human body and environment.

The current glass digital printing of Chinese market generally uses UV marking ink, such as CN103042834A, UV marking ink Pigment used is organic matter, and binder is various aliphatic polyurethanes organic matters, and the pattern after printing is roasted without high temperature Burn, by above-mentioned ester-based organic compound under ultraviolet light irradiation crosslinking curing, thus by organic pigment sealing in glass or ceramic tile table Face forms decorative pattern.Therefore, the pattern of UV printing technique glass and ceramic surface not there is only it is easy scratch, not acid and alkali-resistance, The drawbacks such as easy peeling fades in case of wet, pattern is easy to fall off, and ultraviolet light generates a large amount of ozone during resin crosslinking curing, Threaten the health of operator；UV ink in contact with equipment need to use the high carcinogenic solvent such as aldehydes or ketone to clean；Because even Splicing and pigment are organic matter, and high-temperature process is unable to after printing, and pattern has the hidden danger of the easily safety and environmental protection such as kindling.

Also there are a small number of research and development for carrying out high temperature digital printing ink: CN104403419A and CN104861779A in the country in recent years All disclose a kind of inkjet printing glass ink, but the solvent used is identical with offshore company product, mainly alcohol ethers are acyclic Border friendly solvent, in addition the maximum disadvantage of the patent is to need infrared lamps glass to 90-100 DEG C before printing, and begin This temperature to printing is kept to terminate eventually, it is not only inconvenient for use in this way, and also energy consumption is very big when production, therefore limits the patent Technology and product promotion application.CN105153809A announces a kind of glass ink-jet printing ink, inorganic oxygen when in order to solve printing Compound ink is easy blocking spray head problem, needs inorganic pigment to be first made into frit, while frit stabilizer is added, therefore limit The hair color effect of colorant can reduce pattern color saturation degree after printing.CN104861780A discloses a kind of for glass baseplate Dispersion resin liquid and ink, modified acrylic resin, the non-environmental protection materials such as thiol molecule regulator, Er Qiese is not used only Element is organic pigment, can not high-temperature process and UV ink belong to same type low temperature marking ink.CN102675967A is disclosed A kind of aqueous ceramic space pattern marking ink and preparation method thereof, the ink also contain acrylic compounds and poly- as UV ink Urethane resinoid, while also being used to adjust the pH value of ink containing odorous big organic amine, therefore the patented product is in addition to having Outside all disadvantages of UV marking ink, and ink also will affect user's health.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the shortcomings of existing high temperature digital printing ink, a kind of glass is provided The application method of flux, this method are used to have good hair color effect, printing smoothness, imaging exquisite when high temperature marking ink, storage The characteristics of time length, good weatherability.

In order to solve the above technical problems, The technical solution adopted by the invention is as follows:

The application method of flux, including using the flux as the group for the high temperature number ink for being used for glass or ceramics printing Point, the ink includes liquid phase and the solid phase that is suspended in liquid phase；By weight, the weight ratio of liquid phase and solid phase be 1.5~ 2.8, the solid phase refers to that solid inorganic oxide pigment, the pigment include pigment and the flux；The liquid phase includes molten Agent and the ink being dissolved in solvent are subjected to auxiliary agent；The flux meets following chemical formula:

SiZn_aB_bX_cL_dZ_eO_x

Wherein Si, Zn, B and O indicate elemental silicon, zinc, boron and oxygen；

X is selected from least one of alkali or alkaline earth metal element；

L indicates at least one of titanium, aluminium and zirconium element；

Z indicates at least one of IIIB metal element；

A, b, c, d and e indicate that the relative atom ratio of each element, x meet needed for the total chemical valence of other elements The number of oxygen atom, the atomic ratio based on Si element are 1.

In above-mentioned technical proposal, the application method preferably includes following steps:

By ink printed to glass or ceramic surface；

Heat treatment.

After disclosing using the ink composition of flux of the present invention, those skilled in the art can reasonably select this ink and exist For high temp glass printing concrete technology condition and need not make the creative labor.

In above-mentioned technical proposal, when printing to glass surface, heat treatment temperature can be 680~720 DEG C, non-limiting It enumerates and can be 690 DEG C, 700 DEG C, 750 DEG C, 710 DEG C, 715 DEG C etc..

In above-mentioned technical proposal, when printing to glass surface, heat treatment time be can be 1~10 minute.In this heat It handles in time range, can be 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 points as more specific non limiting example Clock, 4.5 minutes, 4.9 minutes, 5 minutes, 5.1 minutes, 5.5 minutes, 6 minutes, 6.5 minutes, 7 minutes etc., at most preferred heat Managing the time is 4.9~5.12 minutes.

Concrete technology condition when only just printing to glass surface above has carried out for example, those skilled in the art's root According to ceramics and the nature difference of glass, for example, while printing to ceramic surface the temperature that needs it is higher etc., can rationally determine tool Body printing process conditions and creative labor need not be paid.

In above-mentioned technical proposal, the value range of a is preferably 0.3~1.2.

In above-mentioned technical proposal, the value range of b is preferably 0.1~0.6.

In above-mentioned technical proposal, the value range of c is preferably 0.2~1.0.

In above-mentioned technical proposal, the value range of d is preferably 0.2~0.8.

In above-mentioned technical proposal, the value range of e is preferably 0.01~0.5.

The addition of IIIB metal improves suspension stability of the solid phase in ink system.

In above-mentioned technical proposal, IIIB metal preferably includes at least one of Y, La, Ce and Pr.

In above-mentioned technical proposal, IIIB metal more preferably includes Y and La, perhaps preferably includes Y and Ce or preferably includes Ce and La.Y and La, Y and Ce and Ce have in terms of improving suspension stability of the solid phase in ink system with La cooperates with work With.

In above-mentioned technical proposal, most preferred flux is the IIIB metal while including Y, Ce and La, and three elements exist Also there is triple combination effect in terms of improving suspension stability of the solid phase in ink system.

In above-mentioned technical proposal, the specific ratio of Y and La, Y and Ce and Ce and La are not particularly limited, such as but not The atomic ratio for being limited to Y and La, Y and Ce and Ce and La is independently selected from 0.1~10, within the scope of this atomic ratio, as more specific Atomic ratio can stand alone as but be not limited to 0.2,0.4,0.6,0.8,1.0,1.2,1.4,1.6,2.0,2.5,3.0,4.0, 5.0,6.0,7.0,8.0,9.0 etc..

Flux described in above-mentioned technical proposal is using the preparation method preparation included the following steps:

(1) stock dispersion containing element needed for flux is obtained into slurry in water；

(2) dry slurry obtains solid precursors；

(3) it roasts.

In above-mentioned technical proposal, about step (1), slurry how to be made as known to those skilled in the art, and need not pay Creative work.

In above-mentioned technical proposal, about step (2), dry mode is not particularly limited, but spray drying obtains Solid precursors particle is thinner, it is possible to reduce to the Grin-ding energ7 of solid phase when preparing ink.Do not have to dry temperature and time Especially limitation.

In above-mentioned technical proposal, temperature those skilled in the art of step (3) roasting can be reasonably selected, and need not pay Creative work.The temperature such as, but not limited to roasted is 450-800 DEG C, within this range, unrestricted to enumerate for example But it is not limited to 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C etc..

In above-mentioned technical proposal, time those skilled in the art of step (3) roasting can be reasonably selected, and need not pay Creative work.Such as, but not limited to calcining time is 20 minutes to 2 hours, within this range, unrestricted to enumerate example Such as, but not limited to, 0.5 hour, 0.7 hour, 0.9 hour, 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours, 1.9 hours etc. Deng.

In above-mentioned technical proposal, the step of preroast, prebake can also be increased between step (3) after step (2) The purpose of burning is to make the raw material salt component portion of element in flux or all decompose, and makes the roasting process of step (3) so more It is mild easily controllable.The temperature of preroast is preferably 200~300 DEG C；The time of preroast is preferably 0.5~2 hour.

In above-mentioned technical proposal, the atmosphere of roasting and/or preroast is not particularly limited, but independent preferably oxygenous Atmosphere, such as air atmosphere the most economic.

In above-mentioned technical proposal, the weight ratio of flux and pigment is preferably 0.1~10.In this numberical range, non-limit Property processed be exemplified as 0.5,0.8,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5, 8.0,8.5,9.0 etc., but more preferable 1.5~5.0, still more preferably 2~4.To count on year-on-year basis, the specific embodiment of the invention In to generally use the weight ratio of flux and pigment be 3.

In above-mentioned technical proposal, the solid phase is preferably nano particle.Such as the nano-particle diameter is to receive greater than 0 Rice to 1000 nanometers hereinafter, within this range, it is non-limiting enumerate can be but not limited to 900 nanometers, 800 nanometers, 700 receive Rice, 600 nanometers, 500 nanometers, 400 nanometers, 300 nanometers, 200 nanometers, 150 nanometers, 100 nanometers, 90 nanometers, 80 nanometers, 70 receive Rice, 60 nanometers, 50 nanometers etc..One skilled in the art will appreciate that the smaller suspension stability of particle diameter more tends to improve, therefore The diameter that those skilled in the art have motivation to reduce particle using existing technology.

In above-mentioned technical proposal, the preferred inorganic compound of the pigment, more preferable inorganic oxide, such as, but not limited to At least one of titanium white pigment, chrome green pigment, zaffer, iron oxide red pigment, titanium yellow pigment and copper-chrome black pigment.According to three The primary colors complementation mixture of colours and the principle for offsetting relationship, those skilled in the art can carry out color according to coloration according to actual needs With the allotment of coloration.Only meter, the specific embodiment of the invention are all made of zaffer on year-on-year basis.

In above-mentioned technical proposal, it is preferably 0.03~0.20 that ink, which is subjected to auxiliary agent and the weight ratio of liquid phase,.In this model In enclosing, it is non-limiting enumerate such as, but not limited to 0.04,0.05,0.06,0.07,0.08,0.09,0.11,0.13,0.15, 0.17,0.19 etc..

In above-mentioned technical proposal, solvent preferably includes the alcohol selected from C2~C5.Such as, but not limited to ethylene glycol, propylene glycol, At least one of glycerine, isobutanol and pentanediol, more preferably more than one.The characteristics of these solvents be miscible with water or There is biggish solubility in water, have the characteristics that environmental protection.

In above-mentioned technology, the preferably described solvent includes main solvent and secondary solvent, the main solvent be essentially ethylene glycol and/ Or propylene glycol, the secondary solvent include being selected from least one of glycerine and isobutanol, secondary solvent depositing in a solvent The suspension stability of solid phase in the liquid phase is being increased, to increase the storage stability of ink.Secondary solvent and solvent Weight ratio is preferably greater than 0 and 0.02 hereinafter, after this ratio is beyond 0.02, and the stability of ink is obviously opposite to be deteriorated. Within the scope of this weight ratio unrestricted specific value can for example be but not limited to 0.0001,0.0002,0.0004, 0.0005,0.0006,0.0007,0.0008,0.0009,0.010,0.012,0.014,0.015,0.018,0.019 etc..

In above-mentioned technical proposal, the connotation of " main solvent is essentially ethylene glycol and/or propylene glycol " is ethylene glycol in main solvent And/or component based on propylene glycol.It is preferred that ethylene glycol and/or propylene glycol are main solvent 95% or more until all by weight For ethylene glycol and/or propylene glycol.Propylene glycol is similar as solvent solubility with ethylene glycol, but propylene glycol is more environmentally-friendly, from environmental protection Angle is set out, and more preferable main solvent is essentially propylene glycol；But ethylene glycol has more price advantage than propylene glycol, and economic factor considers It is preferred that ethylene glycol.

In propylene glycol, 1,2-PD and/or 1,3-PD can achieve the object of the invention and obtain comparable Technical effect, but be meter on year-on-year basis, propylene glycol is all made of 1,3-PD in specific embodiment.

In above-mentioned technical proposal, more preferable secondary solvent includes glycerine and isobutanol simultaneously, and the two exists in raising solid phase There is synergistic effect in terms of suspension stability in liquid phase.The specific ratio of glycerine and isobutanol between the two does not limit especially System, the such as, but not limited to weight ratio of glycerine and isobutanol are 0.01~100, more specifically non-in this numberical range Restricted citing, 0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0,3.5, 4.0,4.5,5.0,5.5,6.0,7.0,8.0,9.0,10,15,20,30,40,50,60 etc. but more preferable 0.1~10.Only It counts on year-on-year basis, the numerical value of same size has been generallyd use in the specific embodiment of the invention.

In above-mentioned technical proposal, ink is subjected to auxiliary agent and can be selected from those of commonly used in the art, and need not pay creativeness Labour.Such as, but not limited to these inks, which are subjected to auxiliary agent, can be selected from wetting agent, dispersing agent, levelling agent, tension controller, anti-settling One of depressant prescription and antistatic agent or more than one.

In above-mentioned technical proposal, as non limiting example, the cellulose that dispersing agent can be soluble in the solvent spreads out Biology, such as hydroxyethyl cellulose, hydroxypropyl cellulose, sodium hydroxyethyl cellulose and hydroxypropyl cellulose sodium, cellulose acetate At least one of with ethyl cellulose.It is known that the dissolubility of the cellulose derivative is by substituent group and replaces degree It influences, as universal law, substitution degree height is then conducive to be dissolved in solvent of the present invention, and such cellulose derivative is suitable 's.And degree is replaced often to be indicated with the content of substituent group.Those skilled in the art can specified solvent according to the present invention, close It manages the type for selecting substituent group and substituent group content and need not make the creative labor.Such as, but not limited to, when using hydroxypropyl When cellulose, hydroxypropyl weight content optional 7~16%, specific content point value can be but not limited to 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, 15% etc..It is merely convenient of on year-on-year basis, fiber in the specific embodiment of the invention Plain derivative is all made of representative of the hydroxypropyl cellulose that hydroxypropyl weight content is 11% as cellulose derivative.

Commercially available BYKJET-9170 and DISPERBYK-180 can also serve as wetting agent and dispersing agent, and commercially available BYK-345 can be with As levelling agent etc..

In above-mentioned technical proposal, the ink can be using the method preparation included the following steps:

Above-mentioned various raw materials are mixed in the desired amount；

Wet grinding.

The particle diameter of degree solid phase into ink of preferred wet-milling is less than 1000 nanometers in above-mentioned technical proposal, can also be with Make the particle diameter of solid phase in ink less than 1000 nanometers by overanxious operation after grinding.About the equipment of wet-milling, ability Field technique personnel can reasonably select, and need not make the creative labor.The wet milling device such as, but not limited to used is sand milling Machine.Process conditions those skilled in the art of wet grinding can be reasonably selected and need not be made the creative labor, such as when When using sand mill, in order to reach degree of the particle diameter less than 1000 nanometers of solid phase in ink, it can be, but not limited to be sanded Revolving speed of the machine in 3000rpm is ground 4-10 hours.Simultaneously one skilled in the art will appreciate that in order to reduce the volatilization loss of solvent, Preferably wet grinding at a lower temperature, such as 0~90 DEG C, it is such as, but not limited to 1 DEG C, 5 DEG C, 10 in this temperature range DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C etc..

It only particulate abrasive to D99 is 1000 nanometers in the specific embodiment of the invention, then using aperture to count on year-on-year basis It is filtered for 1000 nanometers of filters.

Suspension stability of the present invention evaluation method is as follows: by 20ml ink be packed into 50ml tool screw socket transparent glass sample In bottle, lid is tightened, in 25 DEG C of thermostatic chambers, each week observation is primary, and record generates the time of precipitating.Generate the time of precipitating Shorter explanation is more unstable, and the longer the time for generating precipitating the more stable, and what is do not precipitated within observing time is most stable.

The stablizing effect not precipitated in 1 year can achieve under evaluation condition using the ink of flux of the present invention, from And spray head smoothness out of ink when ensuring printing, pattern are exquisite, full color.

Below by embodiment, the present invention is further elaborated, these examples are intended merely to understand purport of the invention The further explanation done, and the whole of non-present invention, for those skilled in the art, without prejudice to before general principles Done any change is put, should be all considered within the claims in the present invention protection scope.

Specific embodiment

Embodiment 1

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O mixing, adds 1000 grams of water and dissolves by heating, obtain material (A)；It will be suitable In 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in 200 grams of hot water, obtains Material (C)；Weigh 1500 grams of SiO₂The silica solution that content is 40%, obtains material (D).Material is sequentially added under 200rpm stirring (A), (B), (C) are arrived in material (D), obtain mixed slurry, manufactured slurry is carried out microballoon in 15000rpm spray dryer Grain molding is finally 89 millimeters in internal diameter, and length is in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 590 DEG C 1.5h is roasted, composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03O_xHigh temperature digital printing ink flux.

2, prepared by ink

3340 grams of solvents (solvent is propylene glycol) is taken, 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 grams are added DISPERBYK-180,54 grams of BYK-345, stirring obtain 3600 grams of liquid phase of the present invention to being uniformly mixed.Weigh 350 grams of cobalts Cyanine and 1050 grams of flux, are added in liquid phase, are dispersed 1 hour with dispersion machine 2000rpm, are then ground to sand mill solid Phase particle D99 is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

20ml ink is fitted into the tool screw socket transparent glass sample bottle of 50ml, lid is tightened, in 25 DEG C of thermostatic chambers, often Observation in one week is primary, and record generates the time of precipitating.The time shorter explanation for generating precipitating is more unstable, generates the time of precipitating More longer, more stable, what is do not precipitated within observing time is most stable.

For convenient for comparing, test result is listed in table 1, and the number of flux and solvent is shown in Table 2 and table 3 in table 1.

Embodiment 2

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 1 mole of Y (NO₃)₃Mixing, adds 1000 grams of water and dissolves by heating, obtain Material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in In 200 grams of hot water, material (C) is obtained；Weigh 1500 grams of SiO₂The silica solution that content is 40%, obtains material (D).It is stirred in 200rpm Under sequentially add material (A), (B), (C) in material (D), obtain mixed slurry, manufactured slurry done by spraying in 15000rpm Framboid molding is carried out in dry device, is finally 89 millimeters in internal diameter, length is the rotation of 1700 millimeters (89 × 1700 millimeters of φ) In 590 DEG C of roasting 1.5h in roaster, composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.1O_xHigh temperature number Code marking ink flux.

2, prepared by ink

3340 grams of solvents (solvent is with embodiment 1) are taken, 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 are added Gram DISPERBYK-180,54 grams of BYK-345, stirring obtain 3600 grams of liquid phase of the present invention to being uniformly mixed.Weigh 350 grams Zaffer and 1050 grams of flux, are added in liquid phase, are dispersed 1 hour with dispersion machine 2000rpm, are then ground to sand mill Solid phase particles D99 is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 3

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 1 mole of La (NO₃)₃Mixing, adds 1000 grams of water and dissolves by heating, obtain Material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in In 200 grams of hot water, material (C) is obtained；The silica solution that 1500 grams of Si02 contents are 40% is weighed, material (D) is obtained.It is stirred in 200rpm Under sequentially add material (A), (B), (C) in material (D), obtain mixed slurry, manufactured slurry done by spraying in 15000rpm Framboid molding is carried out in dry device, is finally 89 millimeters in internal diameter, length is the rotation of 1700 millimeters (89 × 1700 millimeters of φ) In 590 DEG C of roasting 1.5h in roaster, composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03La_0.1O_xHigh temperature number Code marking ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 4

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 1 mole of Ce (NO₃)₃Mixing, adds 1000 grams of water and dissolves by heating, obtain Material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in In 200 grams of hot water, material (C) is obtained；Weigh 1500 grams of SiO₂The silica solution that content is 40%, obtains material (D).It is stirred in 200rpm Under sequentially add material (A), (B), (C) in material (D), obtain mixed slurry, manufactured slurry done by spraying in 15000rpm Framboid molding is carried out in dry device, is finally 89 millimeters in internal diameter, length is the rotation of 1700 millimeters (89 × 1700 millimeters of φ) In 590 DEG C of roasting 1.5h in roaster, composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Ce_0.1O_xHigh temperature number Code marking ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 5

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 1 mole of Pr (NO₃)₃Mixing, adds 1000 grams of water and dissolves by heating, obtain Material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in In 200 grams of hot water, material (C) is obtained；Weigh 1500 grams of SiO₂The silica solution that content is 40%, obtains material (D).It is stirred in 200rpm Under sequentially add material (A), (B), (C) in material (D), obtain mixed slurry, manufactured slurry done by spraying in 15000rpm Framboid molding is carried out in dry device, is finally 89 millimeters in internal diameter, length is the rotation of 1700 millimeters (89 × 1700 millimeters of φ) In 590 DEG C of roasting 1.5h in roaster, composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Pr_0.1O_xHigh temperature number Code marking ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 6

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 0.5 mole of Y (NO₃)₃, 0.5 mole of La (NO₃)₃Mixing, adds water It 1000 grams and dissolves by heating, obtains material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will It is equivalent to 1 mole of TiCl₄It is dissolved in 200 grams of hot water, obtains material (C)；Weigh 1500 grams of SiO₂The silica solution that content is 40%, It obtains material (D).Material (A), (B), (C) are sequentially added under 200rpm stirring in material (D), are obtained mixed slurry, will be made Slurry framboid molding is carried out in 15000rpm spray dryer, finally internal diameter be 89 millimeters, length be 1700 millimeters In 590 DEG C of roasting 1.5h in the rotary roasting furnace of (89 × 1700 millimeters of φ), composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.05La_0.05O_xHigh temperature digital printing ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 7

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 0.5 mole of Y (NO₃)₃, 0.5 mole of Ce (NO₃)₃Mixing, adds water It 1000 grams and dissolves by heating, obtains material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will It is equivalent to 1 mole of TiCl₄It is dissolved in 200 grams of hot water, obtains material (C)；Weigh 1500 grams of SiO₂The silica solution that content is 40%, It obtains material (D).Material (A), (B), (C) are sequentially added under 200rpm stirring in material (D), are obtained mixed slurry, will be made Slurry framboid molding is carried out in 15000rpm spray dryer, finally internal diameter be 89 millimeters, length be 1700 millimeters In 590 DEG C of roasting 1.5h in the rotary roasting furnace of (89 × 1700 millimeters of φ), composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.05Ce_0.05O_xHigh temperature digital printing ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 8

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 0.5 mole of Ce (NO₃)₃, 0.5 mole of La (NO₃)₃Mixing, adds water It 1000 grams and dissolves by heating, obtains material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water, obtains material (B)；It will It is equivalent to 1 mole of TiCl₄It is dissolved in 200 grams of hot water, obtains material (C)；Weigh 1500 grams of SiO₂The silica solution that content is 40%, It obtains material (D).Material (A), (B), (C) are sequentially added under 200rpm stirring in material (D), are obtained mixed slurry, will be made Slurry framboid molding is carried out in 15000rpm spray dryer, finally internal diameter be 89 millimeters, length be 1700 millimeters In 590 DEG C of roasting 1.5h in the rotary roasting furnace of (89 × 1700 millimeters of φ), composition is made are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Ce_0.05La_0.05O_xHigh temperature digital printing ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 9

1, the preparation of flux

It will be equivalent to 6 moles of Zn (NO₃)₂.6H₂O, 3 moles of Mg (NO₃)₂, 1.5 moles of LiNO₃, 1 mole of Al (NO₃)₃.9H₂O, 0.3 mole of Zr (NO₃)₄.5H₂O, 0.2 mole of Y (NO₃)₃, 0.4 mole of Ce (NO₃)₃, 0.4 mole La(NO₃)₃Mixing, adds 1000 grams of water and dissolves by heating, obtain material (A)；It will be equivalent to 4 moles of HBO₃It is dissolved in 300 grams of hot water In, obtain material (B)；It will be equivalent to 1 mole of TiCl₄It is dissolved in 200 grams of hot water, obtains material (C)；Weigh 1500 grams of SiO₂Content For 40% silica solution, material (D) is obtained.Material (A), (B), (C) are sequentially added under 200rpm stirring in material (D), are obtained Manufactured slurry is carried out framboid molding by mixed slurry in 15000rpm spray dryer, is finally 89 millimeters in internal diameter, Length is that composition is made in 590 DEG C of roasting 1.5h in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) are as follows: SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.02Ce_0.04La_0.04O_xHigh temperature digital printing ink flux.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 10

1, the preparation of flux

It is same as Example 1.

2, prepared by ink

Take 3340 grams of solvents (solvent be propylene glycol 99.0w%+1.0w% glycerine), be added 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring obtain of the present invention to being uniformly mixed 3600 grams of liquid phase.350 grams of zaffers and 1050 grams of flux are weighed, are added in liquid phase, it is small with dispersion machine 2000rpm dispersion 1 When, being then ground to solid phase particles D99 with sand mill is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 11

1, the preparation of flux

It is same as Example 2.

2, prepared by ink

3340 grams of solvents (solvent is with embodiment 10) are taken, 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 are added Gram DISPERBYK-180,54 grams of BYK-345, stirring obtain 3600 grams of liquid phase of the present invention to being uniformly mixed.Weigh 350 grams Zaffer and 1050 grams of flux, are added in liquid phase, are dispersed 1 hour with dispersion machine 2000rpm, are then ground to sand mill Solid phase particles D99 is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 12

1, the preparation of flux

It is same as Example 3.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 13

1, the preparation of flux

It is same as Example 4.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 14

1, the preparation of flux

It is same as Example 5.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 15

1, the preparation of flux

It is same as Example 6.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 16

1, the preparation of flux

It is same as Example 7.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 17

1, the preparation of flux

It is same as Example 8.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 18

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 19

1, the preparation of flux

It is same as Example 1.

2, prepared by ink

Take 3340 grams of solvents (solvent be propylene glycol 99.0w%+1.0w% isobutanol), be added 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring obtain of the present invention to being uniformly mixed 3600 grams of liquid phase.350 grams of zaffers and 1050 grams of flux are weighed, are added in liquid phase, it is small with dispersion machine 2000rpm dispersion 1 When, being then ground to solid phase particles D99 with sand mill is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 20

1, the preparation of flux

It is same as Example 2.

2, prepared by ink

3340 grams of solvents (solvent is with embodiment 19) are taken, 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 are added Gram DISPERBYK-180,54 grams of BYK-345, stirring obtain 3600 grams of liquid phase of the present invention to being uniformly mixed.Weigh 350 grams Zaffer and 1050 grams of flux, are added in liquid phase, are dispersed 1 hour with dispersion machine 2000rpm, are then ground to sand mill Solid phase particles D99 is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 21

1, the preparation of flux

It is same as Example 3.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 22

1, the preparation of flux

It is same as Example 4.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 23

1, the preparation of flux

It is same as Example 5.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 24

1, the preparation of flux

It is same as Example 6.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 25

1, the preparation of flux

It is same as Example 7.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 26

1, the preparation of flux

It is same as Example 8.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 27

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 28

1, the preparation of flux

It is same as Example 1.

2, prepared by ink

3340 grams of solvents (solvent is propylene glycol 99.0w%+ glycerine 0.50w%+ isobutanol 0.50w%) is taken, is added 78 Gram cellulose derivative, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring to being uniformly mixed, Obtain 3600 grams of liquid phase of the present invention.350 grams of zaffers and 1050 grams of flux are weighed, is added in liquid phase, uses dispersion machine 2000rpm disperses 1 hour, and being then ground to solid phase particles D99 with sand mill is 1000 nanometers, filters through 1000 nanofiltration membranes To ink products.

3, suspension stability is evaluated

Embodiment 29

1, the preparation of flux

It is same as Example 2.

2, prepared by ink

3340 grams of solvents (solvent is with embodiment 28) are taken, 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 are added Gram DISPERBYK-180,54 grams of BYK-345, stirring obtain 3600 grams of liquid phase of the present invention to being uniformly mixed.Weigh 350 grams Zaffer and 1050 grams of flux, are added in liquid phase, are dispersed 1 hour with dispersion machine 2000rpm, are then ground to sand mill Solid phase particles D99 is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 30

1, the preparation of flux

It is same as Example 3.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 31

1, the preparation of flux

It is same as Example 4.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 32

1, the preparation of flux

It is same as Example 5.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 33

1, the preparation of flux

It is same as Example 6.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 34

1, the preparation of flux

It is same as Example 7.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 35

1, the preparation of flux

It is same as Example 8.

2, prepared by ink

3, suspension stability is evaluated

Embodiment 36

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

3, suspension stability is evaluated

Ink after being placed above 1 year is attached in the ink-cases of printers of computer control of 6 spray heads, is printed on glass Then various multicolour patterns are heat-treated 5 minutes for 680-720 DEG C, produce that color is full, the extremely strong various decoration figures of three-dimensional sense Case.

Embodiment 37

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

Take 3340 grams of solvents (solvent be propylene glycol 97.0w%+ glycerine 3.0w%), be added 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring obtain of the present invention to being uniformly mixed 3600 grams of liquid phase.350 grams of zaffers and 1050 grams of flux are weighed, are added in liquid phase, it is small with dispersion machine 2000rpm dispersion 1 When, being then ground to solid phase particles D99 with sand mill is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 38

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

Take 3340 grams of solvents (solvent be propylene glycol 97.0w%+ isobutanol 3.0w%), be added 78 grams of cellulose derivatives, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring obtain of the present invention to being uniformly mixed 3600 grams of liquid phase.350 grams of zaffers and 1050 grams of flux are weighed, are added in liquid phase, it is small with dispersion machine 2000rpm dispersion 1 When, being then ground to solid phase particles D99 with sand mill is 1000 nanometers, and ink products is obtained by filtration through 1000 nanofiltration membranes.

3, suspension stability is evaluated

Embodiment 39

1, the preparation of flux

It is same as Example 9.

2, prepared by ink

3340 grams of solvents (solvent is propylene glycol 97.0w%+ glycerine 1.5w%+ isobutanol 1.5w%) is taken, is added 78 grams Cellulose derivative, 108 grams of BYKJET-9170,20 grams of DISPERBYK-180,54 grams of BYK-345, stirring are obtained to being uniformly mixed To 3600 grams of liquid phase of the present invention.350 grams of zaffers and 1050 grams of flux are weighed, is added in liquid phase, uses dispersion machine 2000rpm disperses 1 hour, and being then ground to solid phase particles D99 with sand mill is 1000 nanometers, filters through 1000 nanofiltration membranes To ink products.

3, suspension stability is evaluated

The composition and evaluation result of 1 ink of table

	Flux number	Solvent composition	Sedimentation time, all numbers
				Embodiment 1	Molten 1	Molten I	2
Embodiment 2	Molten 2	Molten I	4
				Embodiment 3	Molten 3	Molten I	4
Embodiment 4	Molten 4	Molten I	5
				Embodiment 5	Molten 5	Molten I	5
Embodiment 6	Molten 6	Molten I	7
				Embodiment 7	Molten 7	Molten I	8
Embodiment 8	Molten 8	Molten I	7
				Embodiment 9	Molten 9	Molten I	18
Embodiment 10	Molten 1	Molten II	3
				Embodiment 11	Molten 2	Molten II	5
Embodiment 12	Molten 3	Molten II	6
				Embodiment 13	Molten 4	Molten II	6
Embodiment 14	Molten 5	Molten II	7
				Embodiment 15	Molten 6	Molten II	10
Embodiment 16	Molten 7	Molten II	11
				Embodiment 17	Molten 8	Molten II	10
Embodiment 18	Molten 9	Molten II	28
				Embodiment 19	Molten 1	Molten III	4
Embodiment 20	Molten 2	Molten III	6
				Embodiment 21	Molten 3	Molten III	8
Embodiment 22	Molten 4	Molten III	6
				Embodiment 23	Molten 5	Molten III	10
Embodiment 24	Molten 6	Molten III	12
				Embodiment 25	Molten 7	Molten III	13
Embodiment 26	Molten 8	Molten III	12
				Embodiment 27	Molten 9	Molten III	31
Embodiment 28	Molten 1	Molten IV	22
				Embodiment 29	Molten 2	Molten IV	27
Embodiment 30	Molten 3	Molten IV	32
				Embodiment 31	Molten 4	Molten IV	27
Embodiment 32	Molten 5	Molten IV	37
				Embodiment 33	Molten 6	Molten IV	45
Embodiment 34	Molten 7	Molten IV	48
				Embodiment 35	Molten 8	Molten IV	45
Embodiment 36	Molten 9	Molten IV	52 have no precipitating
				Embodiment 37	Molten 9	The molten II of ※	24
Embodiment 38	Molten 9	The molten III of ※	27
				Embodiment 39	Molten 9	The molten IV of ※	34

Note: ※ indicates that cosolvent accounts for solvent strength 3w% in table.

Table 2

Flux	Flux number
		SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03O_x	Molten 1
SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.1O_x	Molten 2
		SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03La_0.1O_x	Molten 3
SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Ce_0.1O_x	Molten 4
		SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Pr_0.1O_x	Molten 5
SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.05La_0.05O_x	Molten 6
		SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.05Ce_0.05O_x	Molten 7
SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Ce_0.05La_0.05O_x	Molten 8
		SiZn_0.6B_0.4Mg_0.3Li_0.15Al_0.1Ti_0.1Zr_0.03Y_0.02Ce_0.04La_0.04O_x	Molten 9

Table 3

Solvent	Solvent number
		Propylene glycol	Molten I
Propylene glycol+glycerine	Molten II
		Propylene glycol+isobutanol	Molten III
Propylene glycol+glycerine+isobutanol	Molten IV

Claims

1. the application method of flux, including using the flux as the group for the high temperature number ink for being used for glass or ceramics printing Point, the ink includes liquid phase and the solid phase that is suspended in liquid phase；By weight, the weight ratio of liquid phase and solid phase be 1.5~ 2.8, the solid phase refers to that solid inorganic oxide pigment, the pigment include pigment and the flux；The liquid phase includes molten Agent and the ink being dissolved in solvent are subjected to auxiliary agent；The flux meets following chemical formula:

SiZn_aB_bX_cL_dZ_eO_x

Wherein Si, Zn, B and O indicate elemental silicon, zinc, boron and oxygen；

X is selected from least one of alkali or alkaline earth metal element；

L indicates at least one of titanium, aluminium and zirconium element；

Z indicates at least one of IIIB metal element；

A, b, c, d and e indicate that the relative atom ratio of each element, x are the originals of oxygen needed for meeting the total chemical valence of other elements The number of son, the atomic ratio based on Si element are 1.

2. application method according to claim 1, it is characterized in that including the following steps:

By ink printed to glass or ceramic surface；

Heat treatment.

3. application method according to claim 2, it is characterized in that heat treatment temperature is 680~720 DEG C.

4. application method according to claim 2, it is characterized in that heat treatment time is 1~10 minute.

5. application method according to claim 1, it is characterized in that the value range of a is 0.3~1.2.

6. application method according to claim 1, it is characterized in that the value range of b is 0.1~0.6.

7. application method according to claim 1, it is characterized in that the value range of c is 0.2~1.0.

8. application method according to claim 1, it is characterized in that the value range of d is 0.2~0.8.

9. application method according to claim 1, it is characterized in that the value range of e is 0.01~0.5.

10. application method according to any one of claims 1 to 9, it is characterized in that flux use included the following steps Preparation method preparation:

(2) dry slurry obtains solid precursors；

(3) it roasts.