SI20863A - Procedure of manufacture of multilayer product, multilayer product resulted and its use - Google Patents

Abstract

The submitted invention refers to a procedure for the manufacture of a multilayer product which comprises an inorganic underlay, especially of glass, coated by a metallic layer, and a layer containing a polymer system, where this polymer layer is coated by a system belonging to the group of fluorinated polymers, and is intended for the protection of the metallic layer.

Description

Postopek za izdelavo večslojnega produkta, dobljeni večslojni produkt in njegova uporabaA process for the manufacture of a multilayer product, the resultant multilayer product and its use

Predloženi izum se na splošno nanaša na večslojne elemente, izdelane iz vsaj ene anorganske podlage, zlasti iz stekla, prevlečene s slojem, ki obsega polimerni sistem, kot sloj barve.The present invention generally relates to multilayer elements made of at least one inorganic substrate, in particular glass coated with a layer comprising a polymer system, as a layer of paint.

Natančneje se izum lahko nanaša na izdelavo zrcal, izdelanih zlasti iz podlage iz stekla, iz kovinskega sloja, kije tudi sam prevlečen s slojem barve.More specifically, the invention may relate to the manufacture of mirrors, made in particular of a glass substrate, of a metal layer, which is itself coated with a layer of paint.

Običajno zrcala izdelajo na naslednji način:Usually mirrors are made as follows:

steklo najprej sperejo, polirajo (stopnja poživljanja), senzibilizirajo, npr. z obdelavo s SnCl₂ v HCI mediju. Po splakovanju površino stekla običajno aktivirajo npr. z raztopino PdCl₂, tudi v HCI mediju ali pa z obdelavo z amoniakalnim srebrovim nitratom.glass is first rinsed, polished (rate of invigoration), sensitized, e.g. by treatment with SnCl ₂ in HCI medium. After flushing, the glass surface is usually activated by e.g. with PdCl ₂ solution, also in HCI medium or by treatment with ammonia silver nitrate.

Raztopine za posrebrenje, ki vsebujejo srebrovo sol in njen reduktant, nato apliciramo za izdelavo sloja srebra. Tako dobljena opačna srebrova prevleka je lahko ali pa ne prekrita s slojem bakra. Zaščito srebra lahko prav tako dobimo z obdelavo s SnCl₂, HCI, ki ji sledi obdelava s silanom, ki omogoča boljši oprijem barv, ki so potrebne v vseh primerih za izdelavo zrcala; upoštevati je treba, da je sloj (sloji) barve v bistvu namenjen za zaščito sloja srebra proti mehanskim agresijam (razenje, zarezovanje) in kemičnim agresijam (korozija).Silver plating solutions containing silver salt and its reducing agent are then applied to produce a layer of silver. The thus obtained silver coating may or may not be covered with a layer of copper. Silver protection can also be obtained by treating with SnCl ₂ , HCl followed by treatment with silane, which provides better adhesion of the colors required in all cases to produce a mirror; it should be borne in mind that the paint layer (s) is essentially intended to protect the silver layer against mechanical aggression (scattering, notching) and chemical aggression (corrosion).

V številnih patentih je opisan ta tip izdelave refleksivnih izdelkov kot tudi dobljeni izdelki.Many patents describe this type of manufacturing reflexive products as well as the products obtained.

Problem, inherenten temu tipu izdelave, se nanaša na zaščito refleksivne kovinske prevleke, zlasti na zaščito proti koroziji.The problem inherent in this type of fabrication concerns the protection of the reflective metal coating, in particular the corrosion protection.

Dejansko vemo, da so refleksivne kovinske prevleke občutljive na agresijo z atmosfersko polucijo, posledica pa je motnost kovinskega sloja in izguba zahtevanih optičnih lastnosti.In fact, we know that reflective metal coatings are sensitive to aggression by atmospheric half-life, resulting in opacity of the metal layer and loss of required optical properties.

Ta problem običajno rešijo s prisotnostjo vsaj enega sloja barve na sloju srebra.This problem is usually solved by the presence of at least one layer of paint on the silver layer.

Vendar je za taka zrcala potreben debel sloj barve, če želimo dobiti trajno zaščito in se v naj večji meri izogniti problemom korozije.However, such mirrors require a thick coat of paint in order to obtain permanent protection and to avoid corrosion problems to the greatest extent possible.

Seveda ima to svojo ceno in torej iščemo cenejšo rešitev.Of course, this has its price and so we are looking for a cheaper solution.

Sicer so ugotovili, da ima en sam sloj zaščite pomanjkljivosti, kot razpokanost, prekomerna poroznost, kraterje..., kar ima za učinek, da se močno zmanjša zaščita spodaj ležečega sloja srebra.Otherwise, they found that a single layer of protection had deficiencies, such as cracking, excessive porosity, craters ... which had the effect of greatly reducing the protection of the underlying silver layer.

Razen tega so že realizirali dva sloja, položena drug na drugega, z različnimi in/ali komplementarnimi lastnostmi.In addition, they have already realized two layers, laid on top of each other, with different and / or complementary properties.

Ta rešitev ne samo, da je draga zaradi cene samih barv, ampak se je razen tega izkazala z zahtevno izvedbo, kajti podvoji postopek aplikacije barv, ki je sam po sebi težak.Not only is this solution costly because of the price of the colors themselves, it has also proven to be a challenging implementation, as it duplicates the color application process, which is difficult in itself.

Te rešitve torej uporabljajo enega ali več slojev, imenovanih bariera, kajti le-ti tvorijo (fizično) oviro za zunanje agresivne vplive.These solutions therefore use one or more layers, called barriers, because they constitute a (physical) barrier to external aggressive influences.

Drug tip rešitve obstoji iz tega, da v samo barvo vključijo sredstva proti koroziji. Sredstva so pogosto na osnovi težkih kovin, kar predstavlja neugodnost za okolje in za zdravje ljudi.Another type of solution is to include anti-corrosion agents in the paint itself. The agents are often heavy metal based, which is a disadvantage to the environment and human health.

Sredstva proti koroziji, dispergirana v sloju barve, imajo zaviralno funkcijo za agresivne vplive na spodaj ležeč kovinski sloj. Njihova ukinitev bi torej ustvarila slabšo zaščito tega sloja; to izgubo učinkovitosti lahko kompenzirajo z izboljšanjem bariemih lastnosti sloja barve.The anti-corrosion agents dispersed in the paint layer have a retardant function for aggressive effects on the underlying metal layer. Their abolition would therefore create less protection for this layer; this loss of performance can be compensated by improving the barium properties of the paint layer.

Vendar se je izkazalo, da je ta tip rešitve drag in zahteven po izvedbi, kot smo že dejali.However, this type of solution has proven to be expensive and demanding to implement, as we said earlier.

S predloženim izumom se izognemo zgoraj prikazanim problemom s predlaganjem zanesljive rešitve, ki je cenejša, lahko izvedljiva..., glede problema korozije kovinskega sloja, ki ga vsebuje zrcalo.The present invention avoids the problems shown above by proposing a reliable solution that is less expensive, easily feasible ..., with respect to the problem of corrosion of the metal layer contained in the mirror.

Tako je predmet predloženega izuma postopek za izdelavo večslojnega produkta, ki obsega anorgansko podlago, zlasti iz stekla, prevlečeno s kovinskim slojem in slojem, ki obsega polimerni sistem.Thus, it is an object of the present invention to provide a process for the manufacture of a multilayer product comprising an inorganic base, in particular glass coated with a metal layer and a layer comprising a polymer system.

V skladu z izumom je ta polimerni sloj prekrit s sistemom, ki pripada skupini fluoriranih polimerov, kije namenjen za zaščito tega kovinskega sloja.According to the invention, this polymer layer is covered by a system belonging to the group of fluorinated polymers intended to protect this metal layer.

Prednostno sistem na osnovi fluoriranega polimera apliciramo bodisi v vodni fazi bodisi v topilni fazi, do deleža med 1,5 in 10%.Preferably, the fluorinated polymer based system is applied, either in the aqueous phase or in the solvent phase, to a proportion between 1.5 and 10%.

Prednostno izberemo sistem na osnovi fluoriranega polimera izmed fluoriranih kopolimerov, neionskih fluoropolimerov ali fluoriranih vodnih disperzij.Preferably, the fluorinated polymer-based system is selected from fluorinated copolymers, non-ionic fluoropolymers or fluorinated aqueous dispersions.

Izum se razen tega nanaša na večslojni produkt preje navedenega tipa, označen s tem, da razen tega vsebuje sloj, ki obsega sistem, ki pripada skupini fluoriranih polimerov, pri čemer ta sloj razporedimo na polimerni sloj.The invention furthermore relates to a multilayer yarn product of the aforementioned type, characterized in that it further comprises a layer comprising a system belonging to a group of fluorinated polymers, this layer being arranged on a polymer layer.

Kot smo že povedali zgoraj, lahko postopek v smislu izuma s pridom uporabimo pri izdelavi zrcal.As stated above, the process of the invention can advantageously be used in the manufacture of mirrors.

Torej gre v skladu z izumom za apliciranje sloja, namenjenega za izboljšanje korozijske odpornosti kovinskega sloja (npr. iz srebra) zrcala, pri čemer je kovinski sloj prevlečen z barvo. Zrcalo torej obsega sloj barve, apliciran na zadnjo površino tega zrcala. Zlasti želimo impregnirati to površino barve, tako da bi postala kar najbolj vodoodbojna. Barva je zlasti alkidnega, akrilnega, epoksiestrskega tipa.Thus, according to the invention, it is an application of a layer intended to improve the corrosion resistance of a metal layer (e.g. silver) of a mirror, the metal layer being coated with paint. The mirror therefore comprises a layer of paint applied to the back surface of that mirror. In particular, we want to impregnate this surface of paint so that it becomes as water-repellent as possible. The paint is of particular alkyd, acrylic, epoxy ester type.

Po prednostni izvedbeni obliki lahko aplikacijo v vodni fazi opišemo na naslednji način: na pobarvano površino napršimo raztopino, razredčeno med 1 in 10%, npr. z brizganjem raztopine s pomočjo razporeditve šob. Dobitek je reda 1,7 1/min pod tlakom 1 bar pri sobni temperaturi.According to a preferred embodiment, the application in the aqueous phase can be described as follows: spray a solution diluted between 1 and 10% on the painted surface, e.g. by spraying the solution using a nozzle arrangement. The yield is on the order of 1.7 l / min at a pressure of 1 bar at room temperature.

Površina za prevlečenje poteka pod razporeditvijo šob.The coating surface runs below the nozzle arrangement.

Aplikacija je enaka v topilni fazi, vendar z varnostnimi ukrepi, kot je vsesavanje organskih hlapov, ki so nastali okoli cone brizganja.The application is the same in the solvent phase, but with safety measures such as suction of organic vapors generated around the injection zone.

Testirali smo številne impregnime dodatke v naslednjih pogojih:We have tested a number of impregnation supplements under the following conditions:

Testirali smo dodatek iz družine fluoriranih kopolimerov, ki se običajno prodajajo pod imenom Foraperle 225, izdeluje in prodaja jih firma ELF ATOCHEM. Ta dodatek smo razredčili do 5 % v butil acetatu. Raztopino nanesemo na polimerno površino bodisi z naprševanjem bodisi na mokro. Nato produkt sušimo s pihanjem.We tested the additive from a family of fluorinated copolymers, commonly sold under the name Foraperle 225, manufactured and sold by ELF ATOCHEM. This additive was diluted to 5% in butyl acetate. The solution is applied to the polymeric surface either by spraying or by wet. Then the product is dried by blowing.

Da bi določili impregnimi učinek tega dodatka, nato merimo z goniometrom kontaktni kot kapljice vode na podlagi, zaščiteni v skladu z izumom. Ta parameter je dejansko značilen za stopnjo impregniranja obdelane površine, ker večja kot je, večji je odboj vode na nosilni površini: drugače rečeno, večji kot je kot a, večja je impregnacija površine.In order to determine the impregnation effect of this additive, the contact angle of the water droplets on the substrate protected according to the invention is then measured with a goniometer. This parameter is actually characteristic of the degree of impregnation of the treated surface, because the larger it is, the greater the water repulsion on the bearing surface: in other words, the greater the angle a, the greater the surface impregnation.

Z dodatkom Foraperle 225 je izmerjeni kontaktni kot reda 120°, kar kaže na dobro stopnjo impregnacije, upoštevajoč, da kaže sloj standardne barve, t.j. neprekrit, kontaktni kot reda 75°.With the addition of Foraperle 225, the measured contact angle is of the order of 120 °, indicating a good degree of impregnation, considering that it shows a layer of standard color, i.e. unbroken, 75 ° contact angle.

Drugi test smo izvedli z impregnimim dodatkom, ki se imenuje Zonyl 7040, ki ga prodaja firma SPCI. Ta impregnimi dodatek je bil razredčen do 5% v vodi. Pogoji tega testa so enaki kot za prejšnjega.The second test was performed with an impregnated additive called Zonyl 7040 sold by SPCI. This impregnated additive was diluted up to 5% in water. The conditions of this test are the same as those of the previous one.

Na koncu je kontaktni kot reda 90°.Finally, the contact angle is 90 °.

Drugi test istega tipa smo izvedli z vodno fluorirano disperzijo, ki jo prodaja firma SPCI pod imenom Zonyl 8740, kot dodatkom. Ta dodatek smo razredčili do deleža med 2 in 10%. Operativni pogoji tega testa so bili enaki kot v preje navedenih testih.A second test of the same type was performed with an aqueous fluorinated dispersion sold by SPCI under the name Zonyl 8740 as an additive. We diluted this additive to between 2 and 10%. The operating conditions of this test were the same as in the tests mentioned above.

Meritve, izvedene na osnovi tega testa s pomočjo goniometra, kažejo kontaktni kot reda 110°.Measurements performed on the basis of this test using a goniometer show a contact angle of the order of 110 °.

Drugi test smo izvedli ob uporabi sloja neionskega fluoropolimera, ki ga trži firma SPCI pod imenom Aquamol 650, razredčenega v vodi do deleža med 1,5 in 3% ob enakih pogojih kot prej.The second test was performed using a layer of non-ionic fluoropolymer marketed by SPCI under the name Aquamol 650, diluted in water to between 1.5% and 3% under the same conditions as before.

Sicer pa smo za okarakterizacijo same antikorozijske zaščite izvedli na zrcalih teste staranja, imenovane BSC (Brouillard Salin Cuproacetique - kuproocetna slana megla), katerih operativne pogoje definirajo norme EN 1036 in ISO 9227.In addition, to characterize the corrosion protection itself, we performed aging tests, called BSC (Brouillard Salin Cuproacetique), whose operating conditions are defined by EN 1036 and ISO 9227.

Referenčni vzorec, t.j. ki nima sloja v smislu izuma, kot tudi tri vzorce, obdelane v smislu izuma, smo podvrgli temu testu, katerega namen je, da pospešeno korodira površine.The reference sample, i.e. which has no layer according to the invention, as well as three samples treated according to the invention, were subjected to this test, which is intended to accelerate corrosion of the surfaces.

Nato smo s spektrofotometrom merili deleže odboja za vsakega od vzorcev.Then, the reflectance ratios for each of the samples were measured with a spectrophotometer.

Medtem ko ima referenčni vzorec delež odboja reda 65%, je pri vzorcih, obdelanih v smislu izuma, ta delež 80% in več.While the reference sample has a reflectance ratio of 65%, in the samples treated according to the invention this proportion is 80% and more.

Sicer je standardna deviacija meritve na referenčnem vzorcu zelo velika v primerjavi z vzorci, obdelanimi v smislu izuma, kar pomeni, da ima referenčni vzorec heterogenost z vidika svoje površine.Otherwise, the standard deviation of the measurement on the reference sample is very large compared to the samples treated according to the invention, which means that the reference sample has heterogeneity in terms of its surface area.

V skladu z izumom dobimo relativno homogene površine.According to the invention, relatively homogeneous surfaces are obtained.

Ti rezultati so sicer vidni s prostim očesom.These results are otherwise visible to the naked eye.

Predloženi izum torej omogoča, da na preprost in cenejši način z lahko izvedbo znatno izboljšamo korozijsko odpornost zrcal proti zunanjim agresivnim vplivom.The present invention, therefore, enables the corrosion resistance of mirrors to be exterminated in a simple and less costly manner by means of a simple and cost effective implementation.

Claims (6)

Patentni zahtevkiPatent claims 1. Postopek za izdelavo večslojnega produkta, ki obsega anorgansko podlago, zlasti iz stekla, prevlečeno s kovinskim slojem in slojem, ki obsega polimerni sistem, označen s tem, da je ta polimerni sloj prekrit s sistemom, ki pripada skupini fluoriranih polimerov, ki je namenjen za zaščito tega kovinskega sloja.A process for the manufacture of a multilayer product comprising an inorganic base, in particular glass coated with a metal layer and a layer comprising a polymeric system, characterized in that said polymeric layer is covered by a system belonging to a group of fluorinated polymers, which is intended to protect this metal layer. 2. Postopek po zahtevku 1, označen s tem, da sistem na osnovi fluoriranega polimera apliciramo bodisi v vodni fazi bodisi v topilni fazi, do deleža med 1,5 in 10%.Process according to claim 1, characterized in that the fluorinated polymer-based system is applied either in the aqueous phase or in the solvent phase, to a proportion between 1.5 and 10%. 3. Postopek po kateremkoli od prejšnjih zahtevkov, označen s tem, da sistem na osnovi fluoriranega polimera izberemo izmed fluoriranih kopolimerov, neionskih fluoropolimerov, fluoriranih vodnih disperzij.Process according to any one of the preceding claims, characterized in that the system based on a fluorinated polymer is selected from fluorinated copolymers, non-ionic fluoropolymers, fluorinated aqueous dispersions. 4. Večslojni produkt, ki obsega vsaj eno anorgansko podlago, zlasti iz stekla, prevlečeno s kovinskim slojem, s slojem, ki obsega polimerni sistem, označen s tem, da razen tega vsebuje sloj, ki obsega sistem, ki pripada skupini fluoriranih polimerov, pri čemer je ta sloj nanesen na polimerni sloj.4. A multilayer product comprising at least one inorganic base, in particular glass-coated glass, with a layer comprising a polymeric system, characterized in that it further comprises a layer comprising a system belonging to the group of fluorinated polymers, whereby this layer is applied to the polymer layer. 5. Večslojni produkt po zahtevku 4, označen s tem, da sistem na osnovi fluoriranega polimera izberemo izmed fluoriranih kopolimerov, neionskih fluoropolimerov, vodilih fluoriranih disperzij.Multilayer product according to claim 4, characterized in that the system based on the fluorinated polymer is selected from fluorinated copolymers, non-ionic fluoropolymers, guides of fluorinated dispersions. 6. Uporaba postopka po kateremkoli od zahtevkov 1 do 3 za izdelavo zrcal.Use of the process according to any one of claims 1 to 3 for the manufacture of mirrors.