CN105175027A - Ceramic with three-dimensional decoration effect and preparation method thereof - Google Patents
Ceramic with three-dimensional decoration effect and preparation method thereof Download PDFInfo
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- CN105175027A CN105175027A CN201510577953.9A CN201510577953A CN105175027A CN 105175027 A CN105175027 A CN 105175027A CN 201510577953 A CN201510577953 A CN 201510577953A CN 105175027 A CN105175027 A CN 105175027A
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Abstract
The invention relates to ceramic with a three-dimensional decoration effect and a preparation method thereof. A distributor is firstly utilized to distribute powder into a pattern corresponding to an ink-jetted pattern on the surface; a body is then formed by pressing; the surface of the body is then covered by a layer of overglaze paste with coloring auxiliary after drying, and permeating ink is then jetted after the body is dried again; the body is then fired, and thereby the ceramic is produced; in a ceramic tile, the permeation depth of the permeating ink in the overglaze layer is 0.2mm to 0.5mm; the permeating ink is oil-based ink containing a transitional metal complex, wherein the transitional metal complex comprises nickel carbonyl, iron pentacarbonyl, chromium hexacarbonyl, titanium hexacarbonyl, dicobalt octacarbonyl, titanium(IV)-oxy acetylacetonate, vanadium(IV)-oxy acetylacetonate, chromium acetylacetonate, cobalt acetylacetonate, praseodymium acetylacetonate and iron acetylacetonate. An oil-based system is adopted as the ink, a high-permeability organic solvent with small molecular volume and low surface tension is adopted as a permeation promoter to replace water, and the osmotic gradient of coloring salt is small.
Description
Technical field
The present invention relates to architectural pottery technical field, particularly relate to and a kind of there is pottery of three-dimensional infiltration decorative effect and preparation method thereof.
Background technology
Inkjet technology is a kind of contactless printing technology, changes traditional silk screen or roller contact pressure stamp mode, has the ability of VDP, personal printing, printing on demand.Traditional stamp mode, when changing the line of production different pattern, all will change colored net or roller, changes screen printing glaze, wastes time and energy.And spray ink Printing only need can be completed by simple computation and changes the line of production, can the order of the various different batch of sweetly disposition and kind, be more applicable to ceramic decoration fashion, personalization, diversified development trend.
Current domestic most ink-jet printing ink is only applicable to surface decoration, cannot realize vertical three-dimensional infiltration decorative effect.If open application for a patent for invention numbers 200910311821.6, application number 201110006128.5 etc. are all adopt super-refinement powder pigment as tinting material, surface decoration can only be made, not there is perviousness.Application number 201110187245.6 utilizes soluble inorganic salt to prepare water-base ink, and finally water spray helps and oozes, the problem such as have that pattern diffusion is fuzzy, color penetration deep mixedly causes, color development is not bright-coloured.Therefore, architectural pottery field is in the urgent need to a kind of infiltration ink of excellent performance.
Summary of the invention
The present invention is intended to overcome the defect that present mode does not have excellent penetrating quality, the invention provides a kind ofly to have pottery of three-dimensional infiltration decorative effect and preparation method thereof.
The invention provides a kind of pottery with three-dimensional decorative effect, described pottery utilizes distributor first powder cloth to be gone out the decorative pattern corresponding with ink-jetting pattern on face, compression moulding again, the starch adhesive that one deck has color auxiliary is covered again after drying in billet surface, spray printing infiltration ink again after drying treatment again, then obtained through burning till, described infiltration ink is the oily ink containing transition metal complex, wherein transition metal complex comprises nickel tetracarbonyl, pentacarbonyl iron, Chromium hexacarbonyl, six carbonyl titaniums, cobalt octacarbonyl, methyl ethyl diketone oxygen titanium, vanadyl acetylacetonate, chromium acetylacetonate, acetylacetone cobalt, methyl ethyl diketone praseodymium and/or ferric acetyl acetonade.
Preferably, in described infiltration ink, the content of transition metal complex is 30-65wt%.
Preferably, in described infiltration ink, solvent comprises ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, glycol ether, trolamine, methylene dichloride and/or ethyl acetate.
Preferably, described infiltration ink is blue ink, and described blue ink contains:
20 ~ 50wt% cobalt octacarbonyl, or
10-50wt% acetylacetone cobalt, or
10 ~ 50wt% cobalt octacarbonyl and 5 ~ 30wt% acetylacetone cobalt.
Preferably, described infiltration ink is yellow ink, and described yellow ink contains:
10-50wt% methyl ethyl diketone praseodymium, or
10 ~ 50wt% six carbonyl titanium, or 5 ~ 30wt% vanadyl acetylacetonate, or
5 ~ 50wt% methyl ethyl diketone oxygen titanium, or one or more in 5 ~ 10wt% Chromium hexacarbonyl.
Preferably, described infiltration ink is brown ink, and described brown ink contains:
One or more in 5-20wt% Chromium hexacarbonyl, 5-20wt% six carbonyl titanium, 5-20wt% methyl ethyl diketone, 5-20wt% nickel tetracarbonyl, 5-20wt% pentacarbonyl iron.
Preferably, described solvent is ethylene glycol 15-25v%, dimethyl formamide 30-40v%, methyl ethyl diketone 15-25v%, methylene dichloride 20-30v% prepare in proportion and mix the mixed solvent obtained.
Again, present invention also offers the pottery with three-dimensional infiltration decorative effect prepared by a kind of above-mentioned infiltration ink, described pottery is on the cover coat with color auxiliary, print infiltration ink, then obtained through burning till, in described ceramic tile, described infiltration ink depth of penetration in cover coat is 0.2-0.5mm.
In addition, present invention also offers a kind of preparation method of pottery, comprising:
1) described infiltration ink and penetration-assisting agent is prepared;
2) cover coat slurry is imposed on ceramic body, simultaneously printing step 1) the described infiltration ink prepared and and penetration-assisting agent, form pattern;
3) by step 2) carry out successively after prepare ceramic body 10-15 minute burning till, polishing, thus obtain described pottery.
Preferably, penetration-assisting agent comprises at least one in ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, propyl alcohol, Virahol, ethyl acetate, methylene dichloride.
Preferably, the composition of cover coat comprises: SiO
265 ~ 70wt%, Al
2o
316 ~ 22wt%, CaO0.4 ~ 0.8wt%, MgO0.2 ~ 0.8wt%, K
2o2 ~ 5wt%, Na
2o3 ~ 4wt%;
Solvent in cover coat slurry is water;
In cover coat slurry, the amount ratio of cover coat component and solvent is 1g:(0.35 ~ 0.45) mL.
Preferably, the composition of cover coat also comprises 3 ~ 6wt% color auxiliary, and color auxiliary comprises at least one in Rutile type Titanium Dioxide, sodium fluoroaluminate, Sodium Fluoride, Sodium Silicofluoride, lanthanide rare metal-salt.
Preferably, simultaneously printing step 1) the described infiltration ink prepared and and penetration-assisting agent refer to: penetration-assisting agent uses as a kind of blank colorless ink, and all operations all complete on a machine simultaneously, just prints sequencing different.Colored ink first prints.
Preferably, permeating used ink amount is 12 ~ 30g/cm
2; Described infiltration ink and penetration-assisting agent be that to add penetration-assisting agent gray scale be 80 ~ 100% to ink gray scale with magnitude relation, preferably 100%.
So-called gray color, just refer to pure white, black and a series of intermediate colors from black to white in both, ordinary representation method is per-cent, and scope is from 0% to 100%.Here require that ink and penetration-assisting agent gray scale add up to 100%.Namely the local penetration-assisting agent that ink is many is just few, guarantees that depth of penetration meets production requirement and do not waste again.
Preferably, firing temperature is 1180 ~ 1240 DEG C, and the time is 40-80 minute, and temperature rise rate is 10 ~ 50 DEG C/min.
Preferably, described infiltration ink depth of penetration in cover coat is 0.2-0.5mm.
Beneficial effect of the present invention:
Ink adopts oleaginous system, and penetration-assisting agent adopts molecular volume little, and the hypertonicity organic solvent that surface tension is low replaces water, and color development salt penetration gradient is little.Adopt color auxiliary guarantee ink color development bright-coloured in base substrate or starch adhesive.Ink infilters base substrate, and its decorative pattern formation mechenism, closer to lithotome, more can embody stone material special texture effect through polishing.
Accompanying drawing explanation
Fig. 1 shows in embodiments of the invention 1 photo in kind preparing ceramic surface;
Fig. 2 shows in embodiments of the invention 1 photo in kind preparing ceramic side;
Fig. 3 shows the photo in kind of the pottery of preparation in comparative example 1;
Fig. 4 shows in the embodiment of the present invention 1 cross-section photograph preparing pottery.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
A kind of clear patterns that the present invention aims to provide, color penetration gradient is little, color development is bright-coloured, is applicable to the infiltration ink of ceramic ink jet printing and the using method in ceramic tile thereof.
The present invention adopts following technical scheme to realize above-mentioned purpose:
A kind of pottery with three-dimensional decorative effect and preparation method thereof, first distributor is utilized first powder cloth to be gone out the decorative pattern corresponding with ink-jetting pattern on face, compression moulding again, the starch adhesive that one deck has color auxiliary is covered again after drying in billet surface, spray printing infiltration ink again after drying treatment again, then obtained through burning till.Infiltration ink is with the oily ink of transition metal complex, solvent allotment, infiltration ink is adopted to be printed to and with the addition of on the brick face of color auxiliary by design picture proof by ink-jet printer, print penetration-assisting agent simultaneously, adobe is walked on glaze line, can rapid osmotic be completed in 10 minutes, then enter klining one-tenth, namely polishing obtain desired product.
Described transition metal complex includes but not limited to nickel tetracarbonyl, pentacarbonyl iron, Chromium hexacarbonyl, six carbonyl titaniums, cobalt octacarbonyl, methyl ethyl diketone oxygen titanium, vanadyl acetylacetonate, chromium acetylacetonate, acetylacetone cobalt, methyl ethyl diketone praseodymium, ferric acetyl acetonade etc.
The main color development transition metal complex of blue ink is cobalt octacarbonyl, acetylacetone cobalt etc.
The main color development transition metal complex of yellow ink is methyl ethyl diketone praseodymium, six carbonyl titaniums, vanadyl acetylacetonate, methyl ethyl diketone oxygen titanium etc.
The main color development transition metal complex of brown ink is nickel tetracarbonyl, pentacarbonyl iron, Chromium hexacarbonyl, six carbonyl titaniums, methyl ethyl diketone oxygen titanium, vanadyl acetylacetonate, chromium acetylacetonate etc.
In described infiltration ink, solvent comprises one or more mixing solutionss in ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, glycol ether, trolamine, ethyl acetate.
Described penetration-assisting agent comprises one or more mixing solutionss in ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, propyl alcohol, Virahol, ethyl acetate, methylene dichloride.
One or more comprising in Rutile type Titanium Dioxide, sodium fluoroaluminate, Sodium Fluoride, Sodium Silicofluoride, lanthanide rare metal-salt of described color auxiliary mix.
Formed in the cover coat slurry in brick face, solvent is water;
In cover coat slurry, the amount ratio of cover coat component and solvent is 1g:(0.35 ~ 0.45) mL;
The composition of cover coat comprises SiO
265 ~ 70wt%, Al
2o
316 ~ 22wt%, CaO0.4 ~ 0.8wt%, MgO0.2 ~ 0.8wt%, K
2o2 ~ 5wt%, Na
2o3 ~ 4wt%.
The depth of penetration of described infiltration ink on brick face is 0.2 ~ 0.5mm.
Ink and penetration-assisting agent be that to add penetration-assisting agent gray scale be 100% to ink gray scale with magnitude relation.
Compared with prior art, its beneficial effect is in the present invention:
Ink adopts oleaginous system, and penetration-assisting agent adopts molecular volume little, and the hypertonicity organic solvent that surface tension is low replaces water, and color development salt penetration gradient is little.Adopt color auxiliary guarantee ink color development bright-coloured in base substrate or starch adhesive.Ink infilters base substrate, and its decorative pattern formation mechenism, closer to lithotome, more can embody stone material special texture effect through polishing.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
Blueness, yellow, brown three kinds of oily inks are deployed into respectively with organotransition metal complex, solvent, by ink-jet printer, design picture proof is printed to and with the addition of on the starch adhesive layer of color auxiliary, print penetration-assisting agent, through burning till, namely polishing obtain desired product simultaneously.
Concrete steps are as follows:
1) preparation of solvent:
Ethylene glycol 15 ~ 25%, dimethyl formamide 30 ~ 40%, methyl ethyl diketone 15 ~ 25%, methylene dichloride 20 ~ 30% are prepared in proportion and mix;
2) preparation of blue ink:
10 ~ 50% acetylacetone cobalts are dissolved in above-mentioned solvent;
3) preparation of yellow ink:
10 ~ 50% methyl ethyl diketone praseodymiums are dissolved in above-mentioned solvent;
4) preparation of brown ink:
5 ~ 20% Chromium hexacarbonyls, 5 ~ 20% 6 carbonyl titaniums, 5 ~ 20% ferric acetyl acetonades are dissolved in above-mentioned solvent;
5) preparation of penetration-assisting agent:
Ethylene glycol 15 ~ 20%, dimethyl formamide 30 ~ 40%, methyl ethyl diketone 15 ~ 30%, ethyl acetate 15 ~ 30%, Virahol 15 ~ 30%;
6) preparation of cover coat slurry:
Cover coat consist of SiO
265 ~ 70%, Al
2o
316 ~ 22wt%, CaO0.4 ~ 0.8%, MgO0.2 ~ 0.8%, K
2o2 ~ 5%, Na
2o3 ~ 4%, additional color auxiliary titanium dioxide 0.4 ~ 1.5%, sodium fluoroaluminate 0.5 ~ 3%;
In slurry, solvent is water;
In cover coat slurry, the amount ratio of cover coat component and solvent is 1g:0.4mL;
7) preparation of ceramic body:
Impose on ceramic body by described cover coat slurry, print described infiltration ink and penetration-assisting agent after drying, infiltration used ink amount is 15g/cm
2, ink and penetration-assisting agent be that to add penetration-assisting agent gray scale be 100% to ink gray scale with magnitude relation;
8) burn till:
By executing glaze slip, the base substrate of ink enters klining, and maximum sintering temperature is 1200 DEG C, and firing period is 65 minutes;
9) polishing:
Finished product after burning till is carried out surface finish process, obtains minute surface high abrasion in-glaze decoration ceramic product.
Fig. 1 shows the ceramic surface prepared in the present embodiment photo in kind, as can be seen from this figure, the pattern that ink inside of the present invention is formed, bright in luster, texture is clear;
Fig. 2 shows in embodiments of the invention 1 photo in kind preparing ceramic side, and as can be seen from this figure, evenly, ceramic color prepared by the present invention is penetrating in ink inside infiltration of the present invention;
Fig. 4 shows the cross-section photograph of pottery prepared by the present embodiment, as can be seen from this figure, permeates ink and form the depth of penetration 0.2 ~ 0.5mm of pattern in ceramic cover coat in the present invention.
Comparative example 1
Adopt the water-base ink that Foshan company produces
1) blue ink, it is water-soluble that ink consists of cobalt chloride;
2) yellow ink, ink consists of chromium chloride, titanous oxalate, praseodymium nitrate, water-soluble;
3) brown ink, ink consists of chromium chloride, iron(ic) chloride, nickelous chloride are water-soluble;
4) spray water after spray ink Printing pattern;
5) preparation of cover coat slurry:
Cover coat consist of SiO
265 ~ 70%, Al
2o
316 ~ 22wt%, CaO0.4 ~ 0.8%, MgO0.2 ~ 0.8%, K
2o2 ~ 5%, Na
2o3 ~ 4%, additional color auxiliary titanium dioxide 0.4 ~ 1.5%, sodium fluoroaluminate 0.5 ~ 3%;
In slurry, solvent is water;
In cover coat slurry, the amount ratio of cover coat component and solvent is 1g:0.4mL;
6) preparation of ceramic body:
Described cover coat slurry is imposed on ceramic body, prints described infiltration ink, then water spray helps and oozes;
7) burn till:
By executing glaze slip, the base substrate of ink enters klining, and maximum sintering temperature is 1200 DEG C, and firing period is 65 minutes;
8) polishing:
Finished product after burning till is carried out surface finish process, obtains ceramic product.
From Fig. 1, Fig. 3: the present invention permeates the product (Fig. 1) that ink is produced, and color development is bright-coloured, clean mark.The product (Fig. 3) that contrast aqueous infiltrating ink is produced, color development is dim, because diffusion causes dim pattern.
Fig. 4 is that the present invention permeates ink production product cross section figure, from partial enlarged drawing: depth of penetration penetrates cover coat, can meet need of production.
Claims (14)
1. one kind has the pottery of three-dimensional decorative effect, it is characterized in that, described pottery utilizes distributor first powder cloth to be gone out the decorative pattern corresponding with ink-jetting pattern on face, compression moulding again, the starch adhesive that one deck has color auxiliary is covered again after drying in billet surface, spray printing infiltration ink again after drying treatment again, then obtained through burning till, in described ceramic tile, described infiltration ink depth of penetration in cover coat is 0.2 ~ 0.5mm, described infiltration ink is the oily ink containing transition metal complex, wherein transition metal complex comprises nickel tetracarbonyl, pentacarbonyl iron, Chromium hexacarbonyl, six carbonyl titaniums, cobalt octacarbonyl, methyl ethyl diketone oxygen titanium, vanadyl acetylacetonate, chromium acetylacetonate, acetylacetone cobalt, methyl ethyl diketone praseodymium, ferric acetyl acetonade.
2. pottery according to claim 1, is characterized in that, described drying treatment again makes moisture controlled below 1%.
3. pottery according to claim 1 and 2, is characterized in that, in described infiltration ink, the content of transition metal complex is 30 ~ 65wt%.
4. pottery according to any one of claim 1 to 3, it is characterized in that, in described infiltration ink, solvent comprises ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, glycol ether, trolamine, methylene dichloride and/or ethyl acetate.
5. pottery according to claim 4, is characterized in that, described infiltration ink is blue ink, and described blue ink contains:
20 ~ 50wt% cobalt octacarbonyl, or
10 ~ 50wt% acetylacetone cobalt, or
10 ~ 50wt% cobalt octacarbonyl and 5 ~ 30wt% acetylacetone cobalt.
6. pottery according to claim 4, is characterized in that, described infiltration ink is yellow ink, and described yellow ink contains:
10 ~ 50wt% methyl ethyl diketone praseodymium, or
10 ~ 50wt% six carbonyl titanium, or
5 ~ 30wt% vanadyl acetylacetonate, or
10 ~ 50wt% methyl ethyl diketone oxygen titanium, or
One or more in 5 ~ 10wt% Chromium hexacarbonyl.
7. pottery according to claim 4, is characterized in that, described infiltration ink is brown ink, and described brown ink contains:
One or more in 5 ~ 20wt% Chromium hexacarbonyl, 5 ~ 20wt% six carbonyl titanium, 5 ~ 20wt% methyl ethyl diketone, 5 ~ 20wt% nickel tetracarbonyl, 5 ~ 20wt% pentacarbonyl iron.
8. the pottery according to any one of claim 1-7, it is characterized in that, described solvent is ethylene glycol 15 ~ 25v%, dimethyl formamide 30 ~ 40v%, methyl ethyl diketone 15 ~ 25v%, methylene dichloride 20 ~ 30v% prepare in proportion and mix the mixed solvent obtained.
9. a preparation method for pottery according to any one of claim 1-8, is characterized in that, comprising:
1) described infiltration ink and penetration-assisting agent is prepared;
2) impose on ceramic body by adding the cover coat slurry of color auxiliary, printing step 1 simultaneously) the described infiltration ink prepared and and penetration-assisting agent, form pattern;
3) by step 2) ceramic body prepared carries out after 10 ~ 15 minutes burning till successively, polishing, thus obtain described pottery.
10. preparation method according to claim 9, is characterized in that, described penetration-assisting agent comprises at least one in ethylene glycol, ethylene glycol monomethyl ether, dimethyl formamide, methyl ethyl diketone, quadrol, propyl alcohol, Virahol, ethyl acetate, methylene dichloride.
11. preparation methods according to claim 9 or 10, it is characterized in that, the composition of cover coat comprises: SiO
265 ~ 70wt%, Al
2o
316 ~ 22wt%, CaO0.4 ~ 0.8wt%, MgO0.2 ~ 0.8wt%, K
2o2 ~ 5wt%, Na
2o3 ~ 4wt%; Solvent in cover coat slurry is water; In cover coat slurry, the amount ratio of cover coat component and solvent is 1g:(0.35 ~ 0.45) mL.
12. according to described preparation method arbitrary in claim 9-11, it is characterized in that, the composition of cover coat also comprises 3 ~ 6wt% color auxiliary, and color auxiliary comprises at least one in Rutile type Titanium Dioxide, sodium fluoroaluminate, Sodium Fluoride, Sodium Silicofluoride, lanthanide rare metal-salt.
13. according to described preparation method arbitrary in claim 9-12, and it is characterized in that, infiltration used ink amount is 12 ~ 30g/cm
2; Described infiltration ink and penetration-assisting agent be that to add penetration-assisting agent gray scale be 80 ~ 100% to ink gray scale with magnitude relation, preferably 100%.
14. according to described preparation method arbitrary in claim 9-13, and it is characterized in that, firing temperature is 1180 ~ 1200 DEG C, and the time is 40 ~ 80 minutes, and temperature rise rate is 10 ~ 50 DEG C/min.
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| CN105948823A (en) * | 2016-06-06 | 2016-09-21 | 广东萨米特陶瓷有限公司 | Ceramic tile containing color paste and permeable ink and making method |
| CN105948823B (en) * | 2016-06-06 | 2019-03-01 | 广东萨米特陶瓷有限公司 | A kind of Ceramic Tiles and production method of slurry containing chromatic colour and infiltration ink formation |
| CN106083212A (en) * | 2016-06-06 | 2016-11-09 | 广东格莱斯陶瓷有限公司 | A kind of infiltration ink Novel marble ceramic and preparation method thereof |
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| CN106426517A (en) * | 2016-08-24 | 2017-02-22 | 广东萨米特陶瓷有限公司 | Ceramic tile combining blank patterns with penetration ink patterns and production method of ceramic tile |
| CN106365694A (en) * | 2016-08-31 | 2017-02-01 | 广东萨米特陶瓷有限公司 | Stereo pattern ceramic tile with combined ceramic ink and production method of stereo pattern ceramic tile with combined ceramic ink |
| CN106365694B (en) * | 2016-08-31 | 2019-12-13 | 广东萨米特陶瓷有限公司 | Ceramic tile with three-dimensional pattern and combined ceramic ink and production method thereof |
| CN106746642A (en) * | 2016-11-11 | 2017-05-31 | 广东道氏技术股份有限公司 | A kind of ceramics ooze the supporting glaze of colored ink |
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