CN101555163A - Noble metal preparation or luster preparation for direct or indirect silk screen printing - Google Patents
Noble metal preparation or luster preparation for direct or indirect silk screen printing Download PDFInfo
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- CN101555163A CN101555163A CNA2009101073013A CN200910107301A CN101555163A CN 101555163 A CN101555163 A CN 101555163A CN A2009101073013 A CNA2009101073013 A CN A2009101073013A CN 200910107301 A CN200910107301 A CN 200910107301A CN 101555163 A CN101555163 A CN 101555163A
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Abstract
The invention discloses a noble metal preparation or a luster preparation used for direct or indirect silk screen printing, which is characterized by comprising one or more types of noble metal compounds of Au, Ag, Pt, Pd, Rh, Au/Pt, Au/Ag, Au/Pd or Au/Rh, or metal resinate, a bonding agent system and one or more types of thixotropic agents. The thixotropic agent is at least one type of polyurea. The noble metal preparation or the luster preparation for direct or indirect silk screen printing is beautiful in color after baking and good in adhesion property and has long quality guarantee period, cracking resistance property and good rheological property.
Description
Technical field
The invention belongs to the noble metal preparation or the gloss preparation that are used for the direct or indirect silk screen printing in silicate base material surface, especially relate to a kind of precious metal or gloss preparation that is used for directly or indirectly carrying out the precious metal decoration at pottery, glass or porcelain substrate surface.
Background technology
Usually by being dissolved in organic support material (especially resinate, sulfo-resinate, mercaptan resin hydrochlorate, terpenes mercaptan resin hydrochlorate and other sulfhydryl compounds) organic gold compound, organic palladium compound and platinic compound and guaranteeing to adhere to specific organometallic compound fusing assistant on the related solid support material, special metal comprises rhodium, chromium, vanadium, copper, silicon etc. to the noble metal preparation on silicate such as ambetti, pottery base material surface.In roasting process, described organic compound is being decomposed into corresponding oxide compound or metal, thereby obtains having on the base material metallic membrane of adhesivity and optical property.Further, this noble metal preparation also contains one or more synthetic or natural resin solution that has thermoplasticity and can merge each other usually.On silicate base materials such as glass, pottery, after the high temperature more than 450 ℃ baked, the result formed gold (or palladium or platinum) ornament layer of light with this noble metal preparation coating.
German patent DE 3616547C1 puts down in writing a kind of indirect screen printing technology, with a kind of special paper of mould printing, scribbles dextrin or water soluble adhesive on the paper, in order to cover resulting decoration, needs one deck varnish mask.
Although organic binder bond system contained in the noble metal preparation can be burnt when roasting, they still have remarkable influence to the quality of decorations sample.Have been found that the decorations sample of bonder system, usually can produce color dimness, speck and bonding problem such as bad final formation.Moreover the solubility precious metal chemical complex can discharge from the varnish mask layer, thereby causes adoring the luminance brightness reduction of sample and producing pink shade.Moreover, in decoration process because high-temperature roasting, can stretching transition appear also and after, defectives such as cracking may appear in the precious metal ornament layer.
In order to overcome and to improve the problems referred to above, German patent DE-AS1232168 discloses the sealing coat that employing does not make coated substance see through between ornament layer and mask layer, though this sealing coat has reduced defectives such as ghost image, has increased printing and material cost.
German patent DE-PS3616547 discloses a kind of bright noble metal preparation, and it contains the thermoplastic resin of 8-30 weight fraction, and the resin that is used as thermoplastic resin comprises bituminous resins, polyamide resin, maleic acid resin, resol and Resins, epoxy etc.Only use one type resin can make the precious metal ornament layer in a certain respect or many aspects poor effect (as aberration, cracking etc.).
German patent DE-AS1421865 discloses and adopted more than one bonder systems in noble metal preparation, and as the mixture of Gum Rosin and bituminous resins, yet this mixture can make defectives such as the precious metal ornament layer cracks.In this patent documentation, the technical scheme of public use rheological agent also useless.
German patent DE 19831141A1 and DE19831141C2 disclose a kind of noble metal preparation, this noble metal preparation adopts direct or indirect printing technology at glass, forming precious metal on the silicate base materials such as pottery decorates, the bonder system of this noble metal preparation contains polyamide resin, Gum Rosin and resol, or form by the reaction product that the mixture of described resin forms under 50-150 ℃ of condition, described noble metal preparation can obtain bigger improvement on printing quality, but the quality guaranteed period of this noble metal preparation is very limited, can in the relative short period even under the room temperature, wear out, the very thickness that becomes, cracking also can appear because of the fragility of precious metal ornament layer in the marble paper of long-term storage.
Summary of the invention
The object of the present invention is to provide a kind of long quality-guarantee period, it is beautiful in colour to bake the back, adhesion property is good, and has the ability of cracking resistance and good rheological performance, the precious metal or the gloss preparation that are used for direct or indirect silk screen printing solve the defective that prior art exists.
For achieving the above object, the present invention adopts following technical scheme:
A kind of being used for directly or/and the noble metal preparation of indirect screen printing or gloss preparation, it is characterized in that: described being used for directly and the noble metal preparation of indirect screen printing and precious metal chemical complex or the metal-resin hydrochlorate that the gloss preparation comprises one or more Au, Ag, Pt, Pd, Rh, Au/Pt, Au/Ag, Au/Pd or Au/Rh, a kind of bonder system and one or more thixotropic agent, described bonder system comprises:
(a) 15-20wt (weight percent) polyamide resin;
(b) one or more sulfuration resins of 5-35wt%;
(c) one or more Gum Rosins of 5-35wt%;
(c) one or more alkyl phenolic resins of 0-25wt%;
(d) other resins of 0-50wt%.
Bonder system can be used for directly or/and the 1-50wt% of the noble metal preparation of indirect screen printing or gloss preparation for whole.
Preferred scheme is: described thixotropic agent is at least a polyureas, the content of this polyureas is described being used for directly and the noble metal preparation of indirect screen printing and the 0.5-10wt% of gloss preparation, in the whole thixotropic agent system, also can contain operable wetting and dispersed color and stop settled reagent: comprise aliphatic polyvalent carboxylic acid, the amine salt of high molecular weight polyesters, the polyether ester anion surfactant, the long-chain amine salt of high molecular poly carboxylic acid, the salt of long-chain polyaminoamide and high molecular weight polyesters acid, the salt of long-chain polyaminoamide and phosphoric acid, specific modified polyamide, phosphate ester surfactants, the amide group amine salt of high molecular weight polyesters acid.
More preferred scheme is: described noble metal preparation or the gloss preparation that is used for direct and indirect screen printing also comprises one or more natural or synthetic resins, organic pigment and filler, solvent and defoamers.
Another object of the present invention is to provide a kind of is used for directly and the noble metal preparation of indirect screen printing or the purposes of gloss preparation, for realizing this purpose, the present invention is used for directly or indirectly silk screen printings of silicate base materials surface such as pottery, glass or porcelain with described noble metal preparation or the gloss preparation that is used for direct and indirect screen printing.
Another object of the present invention is to provide a kind of decalcomania, for realizing this purpose, decalcomania of the present invention adopts the noble metal preparation of aforementioned goal of the invention or gloss preparation to make.
We find that the precious metal or the gloss preparation that contain a certain amount of polyureas in the medium polar solvent system can keep stable for a long time and have good rheological.
Polyureas is that the natural or synthetic resins reaction that comprises one or more isocyanate functional group's components and at least a amine functional group component mixes a kind of elastomerics that forms, described isocyanate functional group's component can be aromatic series or aliphatics, can be monomeric form, polymer form, semi prepolymer or be the prepolymer form.Structural formula is:
[-NH-CO-NH-R-NH-CO-NH-R`]
n
Wherein R and R` can be the same or different, and represent the aromatic group or the aliphatic group of divalence, as CH
2OH etc.
The validity of rheology is to form three-dimensional system by the medium polar solvent mixed system to realize, in storage process, being substituted by this three-dimensional system of resin part of the thick trend that becomes sticky is arranged.The hydrogen bond of the intermolecular formation of urea can make the solvent of middle polarity and interlaminar resin form network or crystalline network.The solvent that is fit to comprises hexalin, butanols, ethylhexanol, Pyranton, propylene glycol monomethyl ether, butyl glycol ether or butyl glycol ether, suitable nonpolar aromatic hydrocarbons or the aliphatic hydrocarbon of comprising.Noble metal preparation of the present invention or gloss preparation are by adding polyurea elastomer, form three-dimensional network, not only reduce the usage quantity of resin, make them weaken by the crosslinked trend of sulphur bridge, this three-dimensional network also can effectively stop the crosslinked of interlaminar resin simultaneously, therefore can deposit for a long time, and good rheological property is arranged, can satisfy the various requirements that are used for direct or indirect silk screen printing.
Noble metal preparation of the present invention or gloss preparation comprise the solubility organic compound of one or more precious metals, and described metal is Au, Ag, Pt, Pd, Rh, Au/Pt, Au/Ag, Au/Pd or Au/Rh or the array configuration between them etc.Among the present invention, precious metal in the solubility organic compound of described precious metal can be incorporated on the organic backbone by sulphur bridge or oxo bridge, be generally the resinate of precious metal and/or the sulfo-resinate of precious metal, as the form existence of cyclic terpene mercaptan hydrochlorate, sulphur resinate or analogue.The content of precious metal chemical complex or metal-resin hydrochlorate can be 1-50wt% in the preparation, is preferably 1-30wt%.
Described precious metal or gloss preparation are printed in the layer of precious metal that forms behind the paper carrier that is used for indirect screen printing, good springiness is arranged, the full characteristics such as gorgeous of color simultaneously, can not cause other problem after adherent precious metal or the roasting of gloss preparation yet after the roasting.
Among the present invention, with 6-15wt%, especially 9-14wt% is good as the precious metal chemical complex of the gloss preparation that is used for direct or indirect silk screen printing or metal-resin phosphate content.
Suitable gelifying agent comprises sulphur, polysulphide, organic disulfide and low polysulphide, sulphenamide, dithiocar-bamate (being preferably dithio-4 especially, 4 '-dimorpholine); Described gelifying agent content is generally between the 0.5-2wt.Usually in the gelation process, precious metal can occur bonding, so just can reach the rheological property of expection but also can improve its roasting effect.
Described noble metal preparation or gloss preparation also have one or more organic solvents of 15-45wt% usually, and its viscosity is subjected to the influence of the process factors such as (time, temperature, sulfide contents) of the weight of resinous type, molecular weight, solvent and polarity and formation gel.When preparation is used in the ointment preparation of silk screen printing, gel reaction takes place in bonder system under the effect of precious metal organic solution and gelifying agent, finally between resin, solvent, gel and polyureas, form a three-dimensional network, described bonder system has very high snappiness, thereby makes use noble metal preparation of the present invention or gloss preparation be used for phenomenons such as ftractureing, aberration is bigger can not appear in direct or indirect silk screen printing.At preparation system of the present invention, especially contain precious metal or the gloss preparation of Au/Ag, can obtain very bright gorgeous precious metal ornament layer.
The softening temperature of polyamide thermoplastic is generally decided according to the situation of dimer fatty acid between 90-120 ℃, and the softening temperature of Gum Rosin is between 60-160 ℃, and 90-150 ℃ is optimum temperature range.Contain one or more organic solvents of 15-45wt%, be generally pitch, cycloaliphatic, aromatic hydrocarbon, ketone, ethers or ethanol, its boiling spread is usually between 140-230 ℃.
The preparation between 30-120 ℃ usually of precious metal of the present invention or gloss preparation, bonder systems such as sulfuration Gum Rosin, polyamide resin and pitch can soften in this temperature range and uniform mixing.When the described reagent of preparation, polyureas at room temperature is dissolved in the N-Methyl pyrrolidone.After bonder system, precious metal solubility organometallic compound, solvent and the gelation of gelifying agent hybrid reaction, during thing cool to room temperature to be mixed, add the polyureas that is dissolved in the N-Methyl pyrrolidone again, and whole mixture is mixed.
Noble metal preparation of the present invention or gloss preparation can be used for the production of ceramic marble paper, this marble paper is made of three parts, water-soluble carrier or softening thermofin, ornament layer (using noble metal preparation of the present invention or gloss preparation) and mask layer (main component is methacrylic resin).In addition, between solubleness carrier or softening thermofin and the ornament layer or between ornament layer and the mask layer sealing coat can be arranged, sealing coat is that oxide compound or glass powder are formed, and can effectively improve adhesion property and cause matt effect.
Noble metal preparation of the present invention or gloss preparation also can be used for ceramic decalcomania, marble paper contains noble metal preparation of the present invention or gloss preparation, this marble paper can be by direct or indirect being printed on glass, pottery or the porcelain base material of existing screen printing technique, roasting in the maturing temperature scope of suitable base material separately.
By noble metal preparation of the present invention or gloss preparation directly or indirect screen printing on glass, pottery or porcelain base material, can obtain dazzling, the no any rimose precious metal ornament layer of decorative effect light.
Embodiment
Embodiment 1: the preparation of clear gel
Hexalin (Cyclohexanol) 84wt (weight fraction) %
Herba Lysimachiae foenumgraeci quintessence oil Lavandine Oil 10wt%
N-Methyl pyrrolidone polyureas solution (Polyurea in N-Methylpyrrolidone) 4wt%
Form clear gel after mixing about 30min under the room temperature.
Embodiment 2: the noble metal preparation wt% that is used for porcelain
| Gold-tert-dodecyl mercaptan resinate is dissolved in Flos Rosae Rugosae quintessence oil (Gold-tert-Dodecylmercaptide in Rosemary) | 33% gold medal (33%Au) | 30.3％ |
| The rhodium resinate is dissolved in Flos Rosae Rugosae quintessence oil | 5% rhodium | 2％ |
| The silicone resin hydrochlorate is dissolved in pine tar (Siliconresinate in Pine Oil) | 10% silicon | 0.1％ |
| The bismuth resinate is dissolved in pine tar | 5% bismuth | 2％ |
| The chromium resinate is dissolved in pine tar | 0.2％ | |
| Bituminous resins is dissolved in spearmint oil (Asphaltresin in Spike Oil) | 6％ | |
| Pimelinketone | 6％ | |
| The phenol red urea formaldehyde is dissolved in tetraline (Sulfurized Phenolic Resin in Tetraline) | 10％ | |
| Polymeric amide is dissolved in Flos Rosae Rugosae quintessence oil | 20％ | |
| Hexalin | 18％ | |
| Spearmint oil | 2.7％ | |
| Sulphur | 1.7％ | |
| The prefabricated clear gel that embodiment 1 is prepared | 1％ |
Embodiment 3: the noble metal preparation wt% that is used for glass
| Gold-tert-dodecyl mercaptan resinate is dissolved in Flos Rosae Rugosae quintessence oil (Gold-tert-Dodecylmercaptide in Rosemary) | 33% gold medal (33%Au) | 30.3％ |
| Silver sulfurized alcohol resinate (Silver-Mercaptide) | 35% silver medal | 5％ |
| The rhodium resinate is dissolved in Flos Rosae Rugosae quintessence oil | 5% rhodium | 2％ |
| The sulfuration Gum Rosin | 14％ | |
| The silicone resin hydrochlorate is dissolved in pine tar (Siliconresinate in Pine Oil) | 10% silicon | 1.7％ |
| The bismuth resinate is dissolved in pine tar | 5% bismuth | 4.4％ |
| The chromium resinate is dissolved in pine tar | 0.1％ | |
| The vanadium solvent | 4% vanadium | 1.7％ |
| Polymeric amide is dissolved in Flos Rosae Rugosae quintessence oil | 19％ | |
| Spearmint oil | 18.8％ | |
| Sulphur | 2％ | |
| The prefabricated clear gel that embodiment 1 is prepared | 1％ |
Embodiment 4 is used for the noble metal preparation of porcelain or glass
The system of present embodiment is the 60wt% (embodiment 1 prepared prefabricated clear gel except) of each component among the embodiment 2, adds the prepared prefabricated clear gel 40wt% of embodiment 1 then; Room temperature vibration shakes up, as noble metal preparation or gloss preparation directly or indirect screen printing on glass, pottery or porcelain base material, can obtain dazzling, the no any rimose precious metal ornament layer of decorative effect light, and the cost of saving precious metal.
The precious metal or the gloss preparation that make by the specific embodiment of the invention have good stability in storage, after the storage several months, still possess good result of use.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to the protection domain of inventing type.
Claims (7)
1, a kind of noble metal preparation or gloss preparation that is used for direct or indirect silk screen printing is characterized in that: described noble metal preparation and the gloss preparation that is used for direct and indirect screen printing comprises:
(a) precious metal chemical complex of one or more Au, Ag, Pt, Pd, Rh, Au/Pt, Au/Ag, Au/Pd or Au/Rh or metal-resin hydrochlorate;
A kind of bonder system;
One or more thixotropic agent, described thixotropic agent are at least a polyureas, and the content of this polyureas is described being used for directly and the noble metal preparation of indirect screen printing and the 0.5-10wt% of gloss preparation.
2, be used for the noble metal preparation or the gloss preparation of direct or indirect silk screen printing according to claim 1, it is characterized in that: described bonder system comprises:
(a) one or more polyamide resins of 15-20wt%;
(b) one or more sulfuration resins of 5-35wt%;
(c) one or more Gum Rosins of 5-35wt%;
(c) one or more alkyl phenolic resins of 0-25wt%;
(d) other resins of 0-50wt%.
3, noble metal preparation or the gloss preparation that is used for direct or indirect silk screen printing as claimed in claim 2 is characterized in that: described noble metal preparation and the gloss preparation that is used for direct or indirect silk screen printing also comprises one or more natural or synthetic resins, organic pigment and filler, solvent and defoamers.
4, noble metal preparation or the gloss preparation that is used for direct or indirect silk screen printing as claimed in claim 3 is characterized in that: described natural or synthetic resins is the middle polarity resin.
5, as the arbitrary described purposes that is used for the noble metal preparation or the gloss preparation of direct or indirect silk screen printing of claim 1-4, it is characterized in that: described noble metal preparation or the gloss preparation that is used for direct and indirect screen printing is used for the directly or indirectly silk screen printing of silicate base material surface.
6, the purposes that is used for the noble metal preparation or the gloss preparation of direct or indirect silk screen printing as claimed in claim 5 is characterized in that: described silicate base material is pottery, glass or porcelain.
7, a kind of ceramic decalcomania is characterized in that: contain just like arbitrary described noble metal preparation of claim 1-4 or gloss preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101073013A CN101555163A (en) | 2009-05-13 | 2009-05-13 | Noble metal preparation or luster preparation for direct or indirect silk screen printing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101073013A CN101555163A (en) | 2009-05-13 | 2009-05-13 | Noble metal preparation or luster preparation for direct or indirect silk screen printing |
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| CN101555163A true CN101555163A (en) | 2009-10-14 |
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| CNA2009101073013A Pending CN101555163A (en) | 2009-05-13 | 2009-05-13 | Noble metal preparation or luster preparation for direct or indirect silk screen printing |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973711A (en) * | 2010-09-17 | 2011-02-16 | 深圳市永丰源瓷业有限公司 | Glazing preparation and preparation method thereof |
| CN102690131A (en) * | 2012-03-02 | 2012-09-26 | 佛山市章氏兄弟建材有限公司 | Manufacturing method of underglaze flashing K gold glazed brick |
| CN101781093B (en) * | 2010-01-19 | 2013-06-05 | 深圳市永丰源实业有限公司 | Noble metal preparation with stable microwave resistant function and manufacturing process and application thereof |
| CN104861871A (en) * | 2014-05-16 | 2015-08-26 | 深圳国瓷永丰源股份有限公司 | Preparation method for silver sulphoresinate |
| CN106280702A (en) * | 2016-08-15 | 2017-01-04 | 汕头市金株新材料有限公司 | A kind of noble metal preparation of silk screen printing |
| CN106830999A (en) * | 2017-01-10 | 2017-06-13 | 深圳市瑞琼科技材料有限公司 | A kind of noble metal preparation of resistance to dish-washing machine |
-
2009
- 2009-05-13 CN CNA2009101073013A patent/CN101555163A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781093B (en) * | 2010-01-19 | 2013-06-05 | 深圳市永丰源实业有限公司 | Noble metal preparation with stable microwave resistant function and manufacturing process and application thereof |
| CN101973711A (en) * | 2010-09-17 | 2011-02-16 | 深圳市永丰源瓷业有限公司 | Glazing preparation and preparation method thereof |
| CN102690131A (en) * | 2012-03-02 | 2012-09-26 | 佛山市章氏兄弟建材有限公司 | Manufacturing method of underglaze flashing K gold glazed brick |
| CN102690131B (en) * | 2012-03-02 | 2013-10-30 | 佛山市章氏兄弟建材有限公司 | Manufacturing method of underglaze flashing K gold glazed brick |
| CN104861871A (en) * | 2014-05-16 | 2015-08-26 | 深圳国瓷永丰源股份有限公司 | Preparation method for silver sulphoresinate |
| CN106280702A (en) * | 2016-08-15 | 2017-01-04 | 汕头市金株新材料有限公司 | A kind of noble metal preparation of silk screen printing |
| CN106830999A (en) * | 2017-01-10 | 2017-06-13 | 深圳市瑞琼科技材料有限公司 | A kind of noble metal preparation of resistance to dish-washing machine |
| CN106830999B (en) * | 2017-01-10 | 2022-09-30 | 深圳市瑞琼科技材料有限公司 | Precious metal preparation resistant to dish washing machine |
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Application publication date: 20091014 |