CN102433059A - Metal protective layer composition and preparation method and use thereof - Google Patents
Metal protective layer composition and preparation method and use thereof Download PDFInfo
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- CN102433059A CN102433059A CN2011102957023A CN201110295702A CN102433059A CN 102433059 A CN102433059 A CN 102433059A CN 2011102957023 A CN2011102957023 A CN 2011102957023A CN 201110295702 A CN201110295702 A CN 201110295702A CN 102433059 A CN102433059 A CN 102433059A
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Abstract
The invention provides a metal protective layer composition and a preparation method and use thereof. The composition, based on the total weight, comprises the following components: (1) 10 to 30 weight percent of polyester, wherein the polyester is a branched hydroxyl polyester of which the hydroxyl value is more than 120; (2) 5 to 25 weight percent of nitrocellulose resin, wherein the nitrocellulose resin is low-nitrogen nitrocellulose resin of which the nitrogen content is less than 12.4; (3) 5 to 30 weight percent of coupling agent which is aliphatic isocyanate; (4) 5 to 25 weight percent of pigment; and (5) 10 to 60 weight percent of organic solvent. The metal protective layer composition provided by the invention has high adhesion force with a metal layer, can effectively prevent the corrosion of an etching solution to the metal layer, and has high re-coating performance and film-forming property.
Description
Technical field
The present invention relates to a kind of coat of metal composition and method of making the same and application.
Background technology
Along with expanding economy, people's material life is greatly improved.But, when people when enjoying life to the full, also puzzled by a large amount of counterfeit and shoddy goods.In order to protect consumers in general's rights and interests, various false proof modes and anti-fake product arise at the historic moment.
At present, high-end product is generally all used anti-counterfeiting line, anti-counterfeiting label or false proof the purpose that reaches the identification counterfeit and shoddy goods that has the optical anti-counterfeiting element.But since anti-counterfeiting line, anti-counterfeiting label or false proof itself is less, structure is comparatively simple; Be easy to copy; Therefore, it but is the problem of the unusual worries that false proof staff faced that anti-counterfeiting line, anti-counterfeiting label or false proof who how to let these public be prone to identification itself can be difficult to forge.Go metal fretwork technology anti-counterfeiting technology anti-counterfeiting technology comparatively complicated as concentrated multiple technologies, processing and the high performance anti-fake material of need use to rise just gradually.
Summary of the invention
The purpose of this invention is to provide a kind of and metal level binding property good, can effectively prevent the corrosion of corrosive fluid to metal level, and have the coat of metal composition and method of making the same and the application of above-mentioned compsn in going metal hollow out anti-counterfeiting technology of good recoatability and film-forming properties.
The invention provides a kind of metal protection layer composition, wherein, is benchmark with the gross weight of said compsn, and said compsn contains following component:
(1) polyester of 10-30 weight %, said polyester are hydroxyl value greater than 120 collateralization hydroxyl polyester;
(2) Nitrocellulose of 5-25 weight %, said Nitrocellulose are the low nitrogen Nitrocellulose of nitrogen content＜12.4 weight %;
(3) linking agent of 5-30 weight %, said linking agent are aliphatic isocyanates;
(4) pigment of 5-25 weight %; And
(5) organic solvent of 10-60 weight %.
Said polyester, Nitrocellulose, pigment, linking agent and organic solvent can play synergy; Make the compsn that contains said components can stick on the metal level preferably, effectively prevent the corrosion of corrosive fluid, and have good recoatability and film-forming properties metal level; Wherein, said recoatability is meant the ability of other coatings of coating on the film that said metal protection layer composition forms.Contriver of the present invention finds; When the hydroxyl value of the polyester in the said metal protection layer composition greater than 120 and the nitrogen content of Nitrocellulose when being lower than 12.4 weight %; Not only can give the higher hardness and the film-forming properties of said compsn, can guarantee that also said Nitrocellulose and polyester can be dissolved in the said organic solvent well.In addition; When said organic solvent is the mixed solvent of fatty ester series solvent and ketone series solvent; Can make said polyester, Nitrocellulose, pigment and linking agent mix more evenly; Thereby improve the adhesivity and the film-forming properties of said metal protection layer composition, the over-all properties of the metal protection layer composition that obtains is more excellent.
The present invention also provides a kind of coat of metal preparation of compositions method; This method comprises mixes polyester, Nitrocellulose, linking agent, pigment and organic solvent, and said polyester, Nitrocellulose, linking agent and pigment are dispersed in the said organic solvent, wherein; Gross weight with said compsn is a benchmark; The content of said polyester is 10-30 weight %, and the content of said Nitrocellulose is 5-25 weight %, and the content of said linking agent is 5-30 weight %; The content of said pigment is 5-25 weight %, and the content of said organic solvent is 10-60 weight %; And said polyester is a hydroxyl value greater than 120 collateralization hydroxyl polyester, and said Nitrocellulose is the low nitrogen Nitrocellulose of nitrogen content＜12.4 weight %, and said linking agent is an aliphatic isocyanates.
In addition, the present invention also provides the application of above-mentioned metal protection layer composition in going metal hollow out anti-counterfeiting technology.
Other features and advantages of the present invention will partly specify in embodiment subsequently.
Embodiment
Following specific embodiments of the invention is elaborated.Should be understood that embodiment described herein only is used for explanation and explains the present invention, is not limited to the present invention.
According to metal protection layer composition of the present invention, wherein, be benchmark with the gross weight of said compsn, said compsn contains following component:
(1) polyester of 10-30 weight %, said polyester are hydroxyl value greater than 120 collateralization hydroxyl polyester;
(2) Nitrocellulose of 5-25 weight %, said Nitrocellulose are the low nitrogen Nitrocellulose of nitrogen content＜12.4 weight %;
(3) linking agent of 5-30 weight %, said linking agent are aliphatic isocyanates;
(4) pigment of 5-25 weight %; And
(5) organic solvent of 10-60 weight %.
According to the present invention, although as long as have good anti-corrosion, recoatability and film-forming properties just contain the metal protection layer composition of polyester, Nitrocellulose, linking agent, pigment and the organic solvent of said components and content, and good with the binding property of metal level; But can mate better in order to make above-mentioned performance; Under the preferable case, be benchmark with the gross weight of said compsn, the content of said polyester is 10-25 weight %; The content of said Nitrocellulose is 10-20 weight %; The content of said linking agent is 5-20 weight %, and the content of said pigment is 5-20 weight %, and the content of said organic solvent is 25-60 weight %.
According to the present invention; Said polyester is meant the polymkeric substance that is formed by divalent alcohol or polyvalent alcohol and diprotic acid or polyprotonic acid polycondensation; Said polyester can be commercially available; Also can prepare, as long as to satisfy said polyester be hydroxyl value greater than 120 collateralization hydroxyl polyester according to the method for well known to a person skilled in the art.Said divalent alcohol for example can be selected from terepthaloyl moietie, 1, ammediol, 1,4-butyleneglycol, 1, one or more in 5-pinakon and the NSC 6366; Said polyvalent alcohol for example can be selected from one or more in TriMethylolPropane(TMP), tetramethylolmethane, glycerine, Xylitol and the sorbyl alcohol; Said diprotic acid for example can be selected from one or more in oxalic acid, hexanodioic acid, Succinic Acid, m-phthalic acid and the terephthalic acid; Said polyprotonic acid for example can be trimellitic acid and/or PMA.The condition of said divalent alcohol or polyvalent alcohol and diprotic acid or polyprotonic acid polycondensation is conventionally known to one of skill in the art, gives unnecessary details no longer one by one at this.
According to the present invention, said polyester is the film-forming components of metal protection layer composition as the matrix resin of said metal protection layer composition and add, and plays crucial effects.Hydroxyl value through controlling said polyester is greater than 120; Under condition of cure; Just can make said polyester and the linking agent generation cross-linked network structure that reacts, thereby make said metal protection layer composition and metal have preferably binding property, effectively prevent the corrosion of corrosive fluid metal level.Under the preferable case, when the hydroxyl value of said polyester is greater than 120 to 150 the time, the adhesivity of said metal protection layer composition is more excellent with the consistency of each material.Need to prove, said hydroxyl value refer to amount of hydroxyl groups in the 1g polyester sample the milligram number of suitable Pottasium Hydroxide (KOH), represent with mgKOH/g.
According to the present invention; Although the number-average molecular weight of said polyester can not cause influence significantly to the performance of said metal protection layer composition; But, for viscosity and the dispersiveness of other components in said polyester of taking into account system, under the preferable case; The number-average molecular weight of said polyester is 200-2000, more preferably 300-1000.
As a rule, each glucose molecule contains three free hydroxyls, after handling with concentrated nitric acid, can be converted into Nitrocellulose.Said Nitrocellulose is little yellow, and outward appearance is as fiber, and its character and purposes depend primarily on nitrated degree, i.e. nitrogen content.According to the difference of nitrogen content, in the industry Nitrocellulose be divided into No. 1 strong cotton (nitrogen content >=13.13 weight %), No. 2 strong cotton (nitrogen content is 11.9-12.4 weight %), a little less than No. 3 cotton (nitrogen content is 11.8-12.1 weight %), quick-fried collodion (nitrogen content is 11.94-12.3 weight %), pyroxylin (nitrogen content is 12.5-12.7 weight %), varnish with cotton (nitrogen content is 11.6-12.2 weight %), zylonite cotton (nitrogen content is 10.8-11.2 weight %) etc.For the ease of understanding, there is document to claim collodion the NC of nitrogen content≤12.4 weight % again, the title guncotton of nitrogen content＞12.4 weight %.Said low nitrogen Nitrocellulose is called low nitration Mierocrystalline cellulose again, is meant the Nitrocellulose of nitrogen content less than 12.4 weight %.
According to the present invention; The nitrogen content of said Nitrocellulose can guarantee that less than 12.4 weight % the metal protection layer composition that obtains can have higher hardness and solvability concurrently as long as satisfy; Under the preferable case; When the nitrogen content of said Nitrocellulose was 10-12 weight %, the over-all properties of the metal protection layer composition that obtains was more excellent.
The present invention is to the not restriction especially of viscosity of said Nitrocellulose; As long as can make said Nitrocellulose be dissolved in the system preferably; For example; Adopt falling ball method to measure the viscosity of said Nitrocellulose, the falling sphere time under 25 ℃ was preferably 1/20 second-1/16 second for being not more than 1/16 second.
According to the present invention; Under condition of cure; Can do not reacted with the hydroxyl in the polyester in the said linking agent aliphatic isocyanates, therefore, saidly can reasonably do not selected according to the hydroxyl value of said polyester by the content of aminating-NCO by aminating-NCO.Under the preferable case, be not 10-25 weight % in the said aliphatic isocyanates by the content of aminating-NCO.Need to prove that said " aliphatics " is meant mainly by carbon atom and Wasserstoffatoms and forms straight chain, side chain or cyclic, saturated or undersaturated hydrocarbon; That is can be that carbonatoms is straight chain aliphatic hydrocarbon, chain aliphatic hydrocarbon and the cycloaliphates of 3-8.
The present invention can be existing various aliphatic isocyanates to the not restriction especially of kind of said aliphatic isocyanates.Under the preferable case, said aliphatic isocyanates is selected from hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), with in bornylane vulcabond and the tolylene diisocyanate one or more; More preferably, said isocyanic ester is hexamethylene diisocyanate and/or isophorone diisocyanate.
The present invention is to the not restriction especially of number-average molecular weight of said aliphatic isocyanates; But for the dispersiveness of the adhesivity that makes the metal protection layer composition that obtains and each component more excellent; Under the preferable case, the number-average molecular weight of said aliphatic isocyanates is 100-800.
According to the present invention; The purpose that adds pigment in the said compsn is in order to improve said metal protection layer composition in the online differentiability that is used for preparing metal hollow out anti-false sign; Promptly printing in the process of various fine patterns with metal protection layer composition provided by the invention, can be through naked eyes intuitive judgment printing situation.Said pigment can be selected from and existingly variously can make said metal protection layer composition have the pigment of color; For example; Said pigment can be selected from one or more in titanium oxide, red stone, silicon-dioxide, kaolin, talcum and the phthalocyanine blue, perhaps can also be for containing one or more the material in titanium oxide, red stone, silicon-dioxide, kaolin, talcum and the phthalocyanine blue.Under the preferable case, said pigment is titanium oxide or the material that contains titanium oxide, for example, can be white titanium pigment, chalk etc.
According to the present invention; Said organic solvent can be selected from the existing various organic solvent that can dissolve said polyester, Nitrocellulose and linking agent; For example, said organic solvent can be in fatty ester series solvent, ketone series solvent and the benzene series solvent one or more.Said fatty ester series solvent for example can be selected from one or more in methyl acetate, ETHYLE ACETATE, propyl acetate and the butylacetate; Said ketone series solvent for example can be selected from one or more in acetone, butanone, methylethylketone, pimelinketone, espeleton, mibk, methylpentanone and the pimelinketone; Said benzene series solvent for example can be selected from one or more in benzene, toluene and the YLENE.Contriver of the present invention finds; When said organic solvent is the mixed solvent of fatty ester series solvent and ketone series solvent; Said polyester, linking agent and Nitrocellulose are dissolved each other together well, thereby improve the adhesivity and the film-forming properties of said metal protection layer composition.The part by weight of said fatty ester series solvent and ketone series solvent is as being 1: 0.5-2.5; Be preferably 1: 0.6-2.
According to the present invention, can also contain auxiliary agent in the said metal protection layer composition.The kind of said auxiliary agent and consumption can add according to actual needs, not restriction especially.Said auxiliary agent specifically can be selected from one or more in siccative, flow agent, inhibitor and the skimmer; Gross weight with said metal protection layer composition is a benchmark, and the content of said auxiliary agent can be 0.1-5 weight %.Wherein, Said siccative for example can be the metallic soap of naphthenic acid or isocaprylic acid (2 ethyl hexanoic acid); Metal commonly used can be selected from one or more among Co, Mn, Ce, V, Fe, Li, K, Ca, Sr, Ba, Al, Sn, Pb, Bi, Ti, Cr, Ni, Cu, Zn, Zr, Mo and the Nd in the metallic soap; Gross weight with said metal protection layer composition is a benchmark, and the content of said siccative can be 0-5 weight %, is preferably 0.1-1 weight %.The kind of said flow agent and consumption are conventionally known to one of skill in the art, and for example said flow agent can be selected among EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, BYK307 and the DEGO410 one or more; Wherein EFKA series is Dutch Ai Fuka Company products, and BYK series is the BYK Company products, and DEGO series is the high Company products of German enlightening, more than its trade mark be conventionally known to one of skill in the art; Gross weight with said metal protection layer composition is a benchmark, and the content of said flow agent can be 0-1.5 weight %, is preferably 0.1-1 weight %.The kind of said inhibitor and consumption are conventionally known to one of skill in the art; For example; Said inhibitor can be selected from DBPC 2,6 ditertiary butyl p cresol, 2,4-ditertbutylparacresol, butylated hydroxy anisole and 1; In two (3, the 5-di-t-butyl-4-hydroxyl-phenylpropionic acid) hydrazines of 2-one or more; Gross weight with said metal protection layer composition is a benchmark, and the content of said flow agent can be 0-1.5 weight %, is preferably 0.1-1 weight %.The kind of said skimmer and consumption are conventionally known to one of skill in the art, and for example, said skimmer can be selected among EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354 and the BYK357 one or more; Gross weight with said metal protection layer composition is a benchmark, and the content of said skimmer is 0-2 weight %, is preferably 0.1-1.5 weight %.
According to coat of metal preparation of compositions method provided by the invention; The mixing of said polyester, Nitrocellulose, linking agent, pigment and organic solvent can be carried out also simultaneously can proceed step by step; Under the preferable case; With polyester, Nitrocellulose, linking agent, pigment and organic solvent method of mixing for successively said Nitrocellulose, polyester, linking agent and pigment being mixed with organic solvent; Promptly earlier Nitrocellulose is mixed with organic solvent, stirring is fully dissolved said Nitrocellulose, obtains containing the solution of Nitrocellulose; Polyester is mixed with the above-mentioned solution that contains Nitrocellulose, after stirring, add linking agent successively again and pigment mixes.
In method provided by the invention; The consumption of each material should make in the metal protection layer composition that obtains, and is benchmark with the gross weight of said compsn, and the content of said polyester is 10-30 weight %; The content of said Nitrocellulose is 5-25 weight %; The content of said linking agent is 5-30 weight %, and the content of said pigment is 5-25 weight %, and the content of said organic solvent is 10-60 weight %; Under the preferable case; The consumption of each material should make in the metal protection layer composition that obtains, and is benchmark with the gross weight of said compsn, and the content of said polyester is 10-25 weight %; The content of said Nitrocellulose is 10-20 weight %; The content of said linking agent is 5-20 weight %, and the content of said pigment is 5-20 weight %, and the content of said organic solvent is 25-60 weight %.
The kind of said polyester, Nitrocellulose, linking agent, pigment and organic solvent is selected as indicated above, repeats no more at this.
In addition, the present invention also provides the application of above-mentioned metal protection layer composition in going metal hollow out anti-counterfeiting technology.Particularly, cover on the PET film that is coated with metallic aluminium with the mask of being with the little literal of hollow out, then said metal protection layer composition is coated on (thickness of coating is generally the 1-2 micron) on the said mask, remove mask, little literal is printed on the aluminium plating film; What will have little literal places baking oven to aluminium plating film, after second, above-mentioned aluminium plating film is soaked 5-20 second at 80-120 ℃ of held 5-20 in corrosive fluid, takes out aluminium plating film, with flushing with clean water, dry up the anti-false sign that can obtain with little literal.Said " removing metal " refers to and is being coated with the metal that is not coated with the zone of said metal protection layer composition on the material of the metal corrosion that is corroded, and the metal that is coated with the zone of said metal protection layer composition still keeps.
Below will describe the present invention through embodiment.
Embodiment 1
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Under 25 ℃, the 13g Nitrocellulose is mixed with 37g ETHYLE ACETATE and 19g methylethylketone, be stirred to no post precipitation, add the 19g polyester, stir; Add 13g aliphatic isocyanates and 25g chalk again, stir, obtain metal protection layer composition X1.
Embodiment 2
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Under 25 ℃, the 17g Nitrocellulose is mixed with 12g butylacetate and 19g methylethylketone, be stirred to no post precipitation, add the 28g polyester, stir; Add 23g aliphatic isocyanates and 15g white titanium pigment again, stir, obtain metal protection layer composition X2.
Embodiment 3
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Under 25 ℃, the 25g Nitrocellulose is mixed with 22g ETHYLE ACETATE and 54g pimelinketone, be stirred to no post precipitation, add the 13g polyester, stir; Add 6g aliphatic isocyanates and 6g chalk again, stir, obtain metal protection layer composition X3.
Embodiment 4
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Method according to embodiment 1 prepares the metal protection layer composition, and different is that 37g ETHYLE ACETATE replaces with the mixture of 20g ETHYLE ACETATE and 17g pimelinketone, obtains metal protection layer composition X4.
Embodiment 5
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Method according to embodiment 3 prepares the metal protection layer composition, and different is that the consumption of said ETHYLE ACETATE is that the consumption of 16g, said pimelinketone is 60g, obtains metal protection layer composition X5.
Embodiment 6
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Method according to embodiment 3 prepares the metal protection layer composition, and different is, the consumption of said ETHYLE ACETATE is 65g, and the consumption of said pimelinketone is 11g, obtains metal protection layer composition X6.
Embodiment 7
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Method according to embodiment 3 prepares the metal protection layer composition, and different is that said organic solvent is a toluene all, obtains metal protection layer composition X7.
Embodiment 8
This embodiment is used to explain metal protection layer composition provided by the invention and preparation thereof.
Method according to embodiment 1 prepares the metal protection layer composition, and different is, using hydroxyl value is that 160 polyester (680BA, Bayer Material Science ltd) replaces the polyester among the embodiment 1.Obtain metal protection layer composition X8 of the present invention.
Embodiment 9
This embodiment is used to explain metal provided by the invention
Method according to embodiment 1 prepares the metal protection layer composition; Different is; The use nitrogen content is that the Nitrocellulose (available from Dongguan City Triratna chemical industry ltd) of 9.5 weight % replaces the Nitrocellulose among the embodiment 1, obtains metal protection layer composition X9 of the present invention.
Comparative Examples 1
This Comparative Examples is used to explain the metal protection layer composition and the preparation thereof of reference.
Method according to embodiment 1 prepares the metal protection layer composition, and different is, using OH value is that 80 polyester (870BA, Bayer Material Science ltd) replaces the polyester among the embodiment 1.Obtain metal protection layer composition D1.
Comparative Examples 2
This Comparative Examples is used to explain the metal protection layer composition and the preparation thereof of reference.
Method according to embodiment 1 prepares the metal protection layer composition, and different is that the use nitrogen content is that the Nitrocellulose (available from Dongguan City Triratna chemical industry ltd) of 14 weight % replaces the Nitrocellulose among the embodiment 1, obtains metal protection layer composition D2.
Test case 1-9
Clarity, online differentiability and the drying property of the little literal of band hollow out that test case 1-9 is used to adhesivity, adhesivity, the recoatability of metal protection layer composition provided by the invention and metal level to be described and to be contained said metal protection layer composition.
(1) preparation of specimen:
Mask with the little literal of band hollow out covers on the aluminized PET film; The metal protection layer composition X1-X9 for preparing embodiment 1-9 then carries out blade coating on mask; Coating thickness is 1.5 microns, removes mask, and little literal is printed on the aluminium plating film; Aluminium plating film was placed 8 seconds in 100 ℃ baking oven; And then aluminium plating film soaked 8 seconds in corrosive fluid (corrosive fluid for preparing according to the method among the US3647508), take out aluminium plating film, with flushing with clean water, dry up and be the specimen of being with the little literal of hollow out.
(2) literal clarity:
(model is MG10081-2 with 40 times of reading lenses; Available from power source, Shenzhen detecting instrument ltd) observe facing to little literal of specimen; If little literal svelteness, neat in edge then are cited as " good ", if literal is fuzzy or literal line edge irregularity then is cited as " poor ".The gained result is as shown in table 1.
(3) adhesivity:
Observe facing to little literal of specimen with 40 times of reading lenses,, have no to peel off then to be cited as " good ", otherwise be cited as " poor " if the resist and the melts combine at specimen literal place are complete.The gained result is as shown in table 1.
(4) online differentiability:
In print the process of various fine patterns to the metal-plated membrane with the present composition, if through naked eyes can intuitively distinguish or equipment can online detection text printout quality and Fine Mapping printing situation then be cited as " good ", otherwise be cited as " poor ".The gained result is as shown in table 1.
(5) drying property:
The specimen doubling (coated face is to coated face) that step (1) is obtained, and firmly open gently after the compacting, if having no the sign of adhesion then to be cited as " good ", otherwise be cited as " poor ".The gained result is as shown in table 1.
(6) alkali resistance:
The specimen that step (1) is obtained is immersed in immersion taking-up after 30 minutes in the sodium hydroxide solution that concentration is 2 weight %, with drying after the washed with de-ionized water.If also complete the remaining on the cheque paper of aluminium lamination then is cited as " good "; If aluminium lamination also has major part to remain on the cheque paper then to be cited as " in "; If having disappeared, aluminium lamination completely dissolve or major part then be cited as " poor ".The gained result is as shown in table 1.
(7) film-forming properties:
Utilize the trans anilox roll coating method of end charging that the metal protection layer composition among the embodiment 1-9 is coated on the PET transparent plastic film; Coating thickness is 1.5 microns; If coating ability complete drying also formed smooth, even, successive rete before complete drying, then be cited as film-forming properties " good "; If coating can complete drying also before complete drying, formed the successive rete, but smooth inadequately and even, then be cited as film-forming properties " in "; If coating ability complete drying, but before complete drying, can not form the successive rete, then be cited as film-forming properties " poor ".The gained result is as shown in table 1.
(8) recoatability
Utilize the trans anilox roll coating method of end charging that the metal protection layer composition among the embodiment 1-9 is coated on the PET transparent plastic film; Coating thickness is 1.5 microns; After treating the coating complete drying; Be coated with above that and scrape one deck acrylate coatings, coating thickness is 1.5 microns, and dry back is bonded on this coating with the 3M600 scotch tape peels off.If acrylate coatings and base material are (promptly; The coat of metal composition layer) do not separate fully and then be cited as recoatability " good "; If acrylate coatings has small portion to separate then with base material to be cited as " in ", if acrylate coatings separates then fully with base material and is cited as " poor ".The gained result is as shown in table 1.
Contrast test example 1-2
According to the method for test case 1-9 film-forming properties and the recoatability of the metal protection layer composition D1 that prepared by Comparative Examples 1-2 and D2 and the clarity, adhesivity, online differentiability, drying property and the alkali resistance that contain the little literal of band hollow out of said metal protection layer composition are tested.
Table 1
| Numbering | The literal clarity | Online differentiability | Adhesivity | Drying property | Alkali resistance | Film-forming properties | Recoatability |
| Embodiment 1 | Good | Good | Good | Good | Good | Good | Good |
| Embodiment 2 | Good | Good | Good | Good | Good | Good | Good |
| Embodiment 3 | Good | Good | Good | Good | Good | Good | Good |
| Embodiment 4 | Good | Good | Good | Good | Good | Good | Good |
| Embodiment 5 | Good | Good | Good | Good | Good | In | Good |
| Embodiment 6 | Good | Good | Good | Good | Good | In | Good |
| Embodiment 7 | In | Good | Good | Good | Good | In | Good |
| Embodiment 8 | Good | Good | In | In | In | Good | Good |
| Embodiment 9 | In | Good | Good | Good | In | In | Good |
| Comparative Examples 1 | Good | Good | Difference | Difference | Difference | Good | Good |
| Comparative Examples 2 | Good | Good | Difference | Good | Difference | Difference | Difference |
Can find out that from the result of table 1 metal protection layer composition provided by the invention and metal level binding property be good, can effectively prevent the corrosion of corrosive fluid to metal level, and have good recoatability and film-forming properties.
Claims (14)
1. a metal protection layer composition is characterized in that, is benchmark with the gross weight of said compsn, and said compsn contains following component:
(1) polyester of 10-30 weight %, said polyester are hydroxyl value greater than 120 collateralization hydroxyl polyester;
(2) Nitrocellulose of 5-25 weight %, said Nitrocellulose are the low nitrogen Nitrocellulose of nitrogen content＜12.4 weight %;
(3) linking agent of 5-30 weight %, said linking agent are aliphatic isocyanates;
(4) pigment of 5-25 weight %; And
(5) organic solvent of 10-60 weight %.
2. metal protection layer composition according to claim 1; Wherein, be benchmark with the gross weight of said compsn, the content of said polyester is 10-25 weight %; The content of said Nitrocellulose is 10-20 weight %; The content of said linking agent is 5-20 weight %, and the content of said pigment is 5-20 weight %, and the content of said organic solvent is 25-60 weight %.
3. metal protection layer composition according to claim 1 and 2, wherein, the hydroxyl value of said polyester is greater than 120 to 150.
4. metal protection layer composition according to claim 1 and 2, wherein, the number-average molecular weight of said polyester is 200-2000.
5. metal protection layer composition according to claim 1, wherein, the nitrogen content of said Nitrocellulose is 10-12 weight %.
6. according to claim 1,2 or 5 described metal protection layer compositions, wherein, adopt falling ball method to measure the viscosity of said Nitrocellulose, the falling sphere time under 25 ℃ is for being not more than 1/16 second.
7. metal protection layer composition according to claim 1 and 2 wherein, is not 10-25 weight % by the content of aminating-NCO in the said aliphatic isocyanates; The number-average molecular weight of said aliphatic isocyanates is 100-800.
8. metal protection layer composition according to claim 1 and 2, wherein, said pigment is selected from one or more in titanium oxide, red stone, silicon-dioxide, kaolin, talcum and the phthalocyanine blue.
9. metal protection layer composition according to claim 1 and 2, wherein, said organic solvent is selected from one or more in fatty ester series solvent, ketone series solvent and the benzene series solvent.
10. metal protection layer composition according to claim 9, wherein, said organic solvent is the mixed solvent of fatty ester series solvent and ketone series solvent; The weight ratio of said fatty ester series solvent and ketone series solvent is 1: 0.5-2.5; Said fatty ester series solvent is selected from one or more in methyl acetate, ETHYLE ACETATE, propyl acetate and the butylacetate, and said ketone series solvent is selected from one or more in acetone, butanone, methylethylketone, pimelinketone, espeleton, mibk, methylpentanone and the pimelinketone.
11. metal protection layer composition according to claim 1 and 2, wherein, said compsn also contains auxiliary agent; Gross weight with said compsn is a benchmark, and the content of said auxiliary agent is 0.1-5 weight %; Said auxiliary agent is selected from one or more in siccative, flow agent, inhibitor and the skimmer.
12. coat of metal preparation of compositions method; This method comprises polyester, Nitrocellulose, linking agent, pigment and organic solvent is mixed, and it is characterized in that, the consumption of each material makes; Gross weight with said compsn is a benchmark; The content of said polyester is 10-30 weight %, and the content of said Nitrocellulose is 5-25 weight %, and the content of said linking agent is 5-30 weight %; The content of said pigment is 5-25 weight %, and the content of said organic solvent is 10-60 weight %; And said polyester is a hydroxyl value greater than 120 collateralization hydroxyl polyester, and said Nitrocellulose is the low nitrogen Nitrocellulose of nitrogen content＜12.4 weight %, and said linking agent is an aliphatic isocyanates.
13. method according to claim 12, wherein, with polyester, Nitrocellulose, linking agent, pigment and organic solvent method of mixing for successively said Nitrocellulose, polyester, linking agent and pigment being mixed with organic solvent.
14. the application of metal protection layer composition in going metal hollow out anti-counterfeiting technology is characterized in that, said metal protection layer composition is any described metal protection layer composition among the claim 1-11.
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| CN102433059B (en) | 2013-08-28 |
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Address after: 100070 No. 6 Spark Road, Science City, Beijing, Fengtai District Patentee after: ZHONGCHAO SPECIAL SECURITY TECHNOLOGY Co.,Ltd. Patentee after: China Banknote Printing and Minting Group Co.,Ltd. Address before: 100070 No. 6 Spark Road, Science City, Beijing, Fengtai District Patentee before: ZHONGCHAO SPECIAL SECURITY TECHNOLOGY Co.,Ltd. Patentee before: China Banknote Printing and mint General Company |