DK149976B - METAL PLATE COATED ON AT LEAST ONE SIDE WITH LATEX OF A POLYMER - Google Patents

METAL PLATE COATED ON AT LEAST ONE SIDE WITH LATEX OF A POLYMER Download PDF

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DK149976B
DK149976B DK032577AA DK32577A DK149976B DK 149976 B DK149976 B DK 149976B DK 032577A A DK032577A A DK 032577AA DK 32577 A DK32577 A DK 32577A DK 149976 B DK149976 B DK 149976B
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latex
steel
plate
coated
polymer
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DK032577AA
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DK149976C (en
DK32577A (en
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Herbert Talsma
Jr William Martin Giffen
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Standard Oil Co Ohio
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18Homopolymers or copolymers of nitriles
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/04Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to rubbers

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Description

149976149976

Den foreliggende opfindelse angår en metalplade belagt på mindst den ene side med latex af en polymer.The present invention relates to a metal plate coated on at least one side with a latex of a polymer.

Før den foreliggende opfindelse var det ikke praktisk at anvende en polymer latex som sådan som belægningsmiddel til dåser. Dåser fremstillet af metal, såsom fortinnet stål og aluminium, belægges normalt med en korrosionsresistent belægning for at beskytte indholdet ved længere tids lagring. Dette gælder især, når fødevarer og drikkevarer skal lagres i dåserne. Fordi belægningerne, der i reglen fremkommer ved anvendelse af polymere latexer som belægningsmiddel, ikke er kontinuerlige belægninger fri for nålehuller, hulrum og lignende, påføres polymere belægninger i reglen på dåser ved hjælp af organiske opløsningsmidler. Brugen af organiske opløsningsmidler er både kostbar og farlig. Fra beskrivelsen til dansk patentansøgning nr. 2119/74 kendes overtræk til metaldåser, som kan påføres uden anvendelse af 2 149976 opløsningsmidler. Disse kendte overtræk er latexer af acrylpolymere med bestemte partikelstørrelser, og de kan indeholde mindre mængder acrylnitril. Copolymere med højt nitrilindhold modificeret med kaut-sjuk har hidtil kun været påført på metaller ved anvendelse af organ-5 iske opløsningsmidler.Prior to the present invention, it was not practical to use a polymer latex as such as a coating agent. Cans made of metal, such as tinned steel and aluminum, are usually coated with a corrosion resistant coating to protect the contents during prolonged storage. This is especially true when food and beverages need to be stored in the cans. Because the coatings, which are usually obtained by using polymeric latexes as a coating agent, are not continuous coatings free of needle holes, voids and the like, polymeric coatings are usually applied to cans by means of organic solvents. The use of organic solvents is both costly and dangerous. From the specification of Danish patent application No. 2119/74 coatings are known for metal cans which can be applied without the use of 2 149976 solvents. These known coatings are latexes of acrylic polymers of particular particle sizes and may contain smaller amounts of acrylonitrile. Highly nitrile copolymers modified with cautious disease have so far only been applied to metals using organic solvents.

Det har vist sig, at kontinuerlige beskyttende film med god kemisk resistens kan fremstilles af latexer af visse nitrilcopolymer latexer, som er nærmere beskrevet nedenfor.It has been found that continuous protective films of good chemical resistance can be made from latexes of certain nitrile copolymer latexes, which are further described below.

1010

Metalpladen ifølge opfindelsen er ejendommelig ved, at den polymere er fremstillet ved polymerisation af en større mængde af en monou-mættet nitril og en mindre mængde af en anden monovinyl monomer komponent, som er copolymeriserbar med nitrilen, i nærværelse af en for-15 ud dannet dienkautsjuk.The metal sheet according to the invention is characterized in that the polymer is made by polymerizing a larger amount of a monounsaturated nitrile and a smaller amount of another monovinyl monomeric component copolymerizable with the nitrile in the presence of a preform formed diene rubber.

I reglen vil latexen (eller blandingen af latexer), der anvendes ifølge opfindelsen, indeholde fra ca. 20 til 45% fast stof og vil have en gennemsnitspartikelstørrelse fra 500 til 3000 Å.As a rule, the latex (or mixture of latexes) used according to the invention will contain from ca. 20 to 45% solids and will have an average particle size of 500 to 3000 Å.

2020

Konjugerede dienmonomere, der er nyttige som dienkautsjuk ifølge opfindelsen indbefatter butadien-1,3, isopren, chloropren, bromopren, cyanopren, 2,3-dimethylbutadien-l,3, 2-ethylbutadien-l,3, 2,3-di= ethylbutadien-1,3 og lignende. Mest foretrukket til opfindelsens for-25 mål er butadien-1,3 og isopren, fordi de er let tilgængelige og har udmærkede polymerisationsegenskaber.Conjugated diene monomers useful as diene rubber according to the invention include butadiene-1,3, isoprene, chloroprene, bromoprene, cyanoprene, 2,3-dimethylbutadiene-1,3,2-ethylbutadiene-1,3,3,3-di-ethylbutadiene -1,3 and the like. Most preferred for the purposes of the invention are butadiene-1,3 and isoprene because they are readily available and have excellent polymerization properties.

De olefinisk umættede nitriler, der er nyttige ifølge opfindelsen, er α,β-olefinisk umættede mononitriler med strukturen CH2=C-CN, hvor 30 RThe olefinically unsaturated nitriles useful according to the invention are α, β-olefinically unsaturated mononitriles having the structure CH 2 = C-CN where 30 R

R er hydrogen, en lavere alkylgruppe med 1-4 kulstofatomer eller halogen. Disse forbindelser indbefatter acrylnitril, α-chloracrylni= 35 5 149976 tril, α-fluoracrylnitril, methacrylnitril, ethacrylnitril og lignende. De mest foretrukne olefinisk umættede nitriler ifølge opfindelsen er acrylnitril og methacrylnitril og blandinger deraf.R is hydrogen, a lower alkyl group having 1-4 carbon atoms or halogen. These compounds include acrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, methacrylonitrile, ethacrylonitrile and the like. The most preferred olefinically unsaturated nitriles of the invention are acrylonitrile and methacrylonitrile and mixtures thereof.

5 Den anden monovinyl monomere komponent, som er copolymeriserbar med de olefinisk umættede nitriler og konjugerede diener, indbefatter en eller flere af esterne af olefinisk umættede carboxylsyrer, vinyl= estere, vinylethere, oc-olefiner, vinylaromatiske monomere og andre.The second monovinyl monomeric component copolymerizable with the olefinically unsaturated nitriles and conjugated dienes includes one or more of the esters of olefinically unsaturated carboxylic acids, vinyl esters, vinyl ethers, oc olefins, vinyl aromatic monomers and others.

10 Esterne af olefinisk umættede carboxylsyrer indbefatter de med struk- 2 1 turen CH5=0-C00R , hvor R er hydrogen, en alkylgruppe med 1-4 kul-Rl 2 stofatomer eller et halogen, og R er en alkylgruppe med fra 1 til 6 kulstofatomer. Eorbindelser af denne type indbefatter methylacrylat, 15 ethylacrylat, propylacrylaterne, butylacrylaterne, amylacrylaterne, hexylacrylaterne, methylmethacrylat, ethylmethacrylat, propylmetha= crylaterne, butylmethacrylaterne, amylmethacrylaterne og hexylmetha= crylaterne, methyl-a-chloracrylat, ethyl-a-chloracrylat og lignende. Mest foretrukket ifølge opfindelsen er methylacrylat, ethylacrylat, 20 methylmethacrylat og ethylmethacrylat.The esters of olefinically unsaturated carboxylic acids include those with the structure 2 L of the CH5 = O-C00 R wherein R is hydrogen, an alkyl group having from 1 to 4 carbon-R 12 substance atoms or a halogen and R is an alkyl group having from 1 to 6 carbon atoms. Compounds of this type include methyl acrylate, ethyl acrylate, propyl acrylates, butyl acrylates, amyl acrylates, hexyl acrylates, methyl methacrylate, ethyl methacrylate, propyl methacrylates, butyl methacrylates, amyl methacrylates, hexyl acrylates, hexyl methacrylates and hexyl methacrylates, Most preferred according to the invention are methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate.

α-olefinerne, der er nyttige ifølge opfindelsen, er de, der har mindst R* f 4 og op til 10 kulstofatomer og med strukturen 01^=0 , hvor R' og R" 25 i« er alkylgrupper med 1-7 kulstofatomer og specielt isobutylen, 2-me= thylbuten-1, 2-methylpenten-l, 2-methylhexen-l, 2-methylhepten-l, 2-methylocten-l, 2-ethylbuten-1, 2-propylpenten-l og lignende. Mest foretrukket er isobutylen.The α-olefins useful in the invention are those having at least R * f 4 and up to 10 carbon atoms and having the structure 01 ^ = 0, where R 'and R "25 i" are alkyl groups of 1-7 carbon atoms and especially isobutylene, 2-methylethylbutene-1,2-methylpenten-1,2-methylhexene-1,2-methylhepten-1,2-methyloctene-2-ethylbutene-1,2-propylpenten-1 and the like. isobutylene is preferred.

3030

Vinyletherne indbefatter methylvinylether, ethylvinylether, propylvi= .The vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vin =.

nylethere, butylvinyletherne, methylisopropenylether, ethylisoprope= nylether og lignende. Mest foretrukket er methylvinylether, ethyl= vinylether, propylvinyletherne og butylvinyletherne.nyl ethers, butyl vinyl ethers, methyl isopropenyl ether, ethyl isopropyl nyl ether and the like. Most preferred are methyl vinyl ether, ethyl = vinyl ether, propyl vinyl ether and butyl vinyl ether.

Vinylesterne indbefatter vinylacetat, vinylpropionat, vinylbutyraterne og lignende. Mest foretrukket er vinylacetat.The vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrates and the like. Most preferred is vinyl acetate.

35 4 14997635 4 149976

Vinylaromatiske monomere indbefatter styren, α-me thyls tyren, vinyl= toluenerne, vinylxylenerne og lignende. Mest foretrukket er styren.Vinyl aromatic monomers include styrene, α-me thyls tyrene, vinyl = toluene, vinyl xylenes and the like. Most preferred is styrene.

Specielle polymere, der er nyttige ifølge opfindelsen, er de, der 5 fremstilles ved polymerisation af 100 vægtdele af (A) fra 60 til 90 vægt$ af mindst én nitril med strukturen CH9=0-CR, hvor R har denParticular polymers useful in the invention are those prepared by polymerizing 100 parts by weight of (A) from 60 to 90% by weight of at least one nitrile having the structure CH9 = O-CR, where R has the

RR

førnævnte betydning, og (B) fra 10 til 40 vægt<fo beregnet på den samlede vægt af (A) og (B) af mindst én repræsentant af gruppen bestå-10 ende af (1) en ester med strukturen CH9=C-C00R , hvor R og R har ^ ’i R1 R» den. førnævnte betydning, (2) en α-olefin med strukturen CH^C , hvor R" og R' R"and (B) from 10 to 40% by weight based on the total weight of (A) and (B) of at least one representative of the group consisting of (1) an ester of structure CH9 = C-C00R , where R and R have ^ 'in R1 R »den. the aforementioned meaning, (2) an α-olefin having the structure CH 2 C, wherein R "and R 'R"

har den førnævnte betydning, (3) en vinylether af gruppen bestående 15 af methylvinylether, ethylvinylether, propylvinyletherne og butylvi= nyletherne, (4) vinylacetat og (5) styren, i nærværelse af fra 0 til 40 vægtdele af (C) en kautsjukagtig polymer af en konjugeret dienmo-nomer af gruppen bestående af butadien og isopren og eventuelt en comonomer af gruppen bestående af styren, en nitrilmonomer med struk-20 turen CH9=C-CH, hvor R har den førnævnte betydning, og en ester med Rhas the aforementioned meaning, (3) a vinyl ether of the group consisting of methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether, (4) vinyl acetate and (5) styrene, in the presence of from 0 to 40 parts by weight of (C) a rubbery polymer of a conjugated dienomonomer of the group consisting of butadiene and isoprene and optionally a comonomer of the group consisting of styrene, a nitrile monomer of the structure CH9 = C-CH where R has the aforementioned meaning, and an ester of R

2 12 strukturen 0H9=0-C00R , hvor R og R har den førnævnte betydning, C I Ί R1 hvilken kauts jukagtige polymer indeholder fra 50 til 100 vægtfo poly-25 meriseret konjugeret dien og fra 0 til 50 vægt$ comonomer.2 12 is the structure 0H9 = 0-C00R, wherein R and R have the aforementioned meaning, C I hvilken R1, which rubber's yolk-like polymer contains from 50 to 100 wt. Of polymerized conjugated diene and from 0 to 50 wt. Comonomer.

De polymere latexer, der er nyttige ifølge opfindelsen, kan fremstilles i vandig emulsion ved polymerisationsteknik, der indebærer portionsvis, kontinuerlig eller intermitterende tilsætning af monomere 30 og andre komponenter. Polymerisationen udføres fortrinsvis i vandigt medium i nærværelse af et emulgeringsmiddel og en polymerisationsigangsætter, der udvikler frie radikaler, ved en temperatur fra ca.The polymeric latexes useful in the invention can be prepared in aqueous emulsion by polymerization technique which involves portionwise, continuous or intermittent addition of monomers 30 and other components. The polymerization is preferably carried out in aqueous medium in the presence of an emulsifier and a free radical polymerization initiator, at a temperature of about

0 til’ 100°C i hovedsagen i fravær af molekalær oxygen. Fremstillingen af typiske latexer, der er nyttige ifølge opfindelsen, er nærmere 35 beskrevet i de amerikanske patentskrifter nr. 3.426.102, nr. 3.586.737 og rir. 31763.278.0 to 100 ° C substantially in the absence of molecular oxygen. The preparation of typical latexes useful in accordance with the invention is described in greater detail in U.S. Patent Nos. 3,426,102, No. 3,586,737 and Rir. 31,763.278.

latexerne ifølge opfindelsen påføres på det affedtede metal i den dåse, som skal belægges, ved hjælp af en spredekniv, en trådstang, 5 149976 en valse, en sprøjtepistol, ved dypning af metallet i latexen, ved overskylningsbelægning eller på andre kendte måder indenfor "belægnings teknikken.the latexes of the invention are applied to the degreased metal in the can to be coated by means of a spreading knife, a wire rod, a roller, a spray gun, by dipping the metal into the latex, by rinsing or in other known ways within "coating". art.

5 Efter at latexbelægningen er blevet tørret, tørres den polymere belægning ved en temperatur i intervallet fra 200 til 300°0. Enhver af de sædvanlige metalplader, der anvendes til fremstilling af dåser, kan benyttes, herunder stål, fortinnet stål og aluminium.After the latex coating has dried, the polymeric coating is dried at a temperature in the range of 200 to 300 ° 0. Any of the usual metal sheets used in the manufacture of cans can be used, including steel, tinned steel and aluminum.

10 Opfindelsen illustreres nærmere af følgende eksempler, hvori mængderne af bestanddelene er i vægtdele, med mindre andet er anført.The invention is further illustrated by the following examples in which the amounts of the constituents are in parts by weight, unless otherwise stated.

Eksempel 1 15 A. Der blev fremstillet en gummilatex ved at polymerisere under kontinuerlig omrøring ved 45°0 i hovedsagen i fravær af oxygen en blanding af følgende bestanddele:Example 1 A. A rubber latex was prepared by polymerizing with continuous stirring at 45 ° 0 essentially in the absence of oxygen a mixture of the following ingredients:

Bestanddele Bele 20 acrylnitril 40 butadieh-1,3 60 G-afac EE-610* 2,4 azobisisobutyronitril 0,3 t-dodecylmerkaptan 0,5 25 vand 200 * En blanding af R-O-tCHgCHgO-^PO^Mg og ^R-O-iCHgCHgO-)^72^2^ kvor n er e"^ fra 1 til 40, E er en alkyl- eller alkaryl= 30 gruppe og fortrinsvis en nonylphenylgruppe, og M er hydrogen, ammoniak eller et alkali= metal, hvilket middel sælges af GAP Corporation.Ingredients Bele 20 acrylonitrile 40 butadieh-1.3 60 G-afac EE-610 * 2.4 azobisisobutyronitrile 0.3 t-dodecyl mercaptan 0.5 25 water 200 * A mixture of RO-tCHgCHgO- ^ PO ^ Mg and ^ RO- CH2 CH2 O -) ^ 72 ^ 2 ^ quor n is e 'from 1 to 40, E is an alkyl or alkaryl = 30 group and preferably a nonylphenyl group, and M is hydrogen, ammonia or an alkali metal, which agent is sold by GAP Corporation.

Eør reaktionen blev startet, blev blandingens pH-værdi indstillet til 3^ ea. 8 med EOH. Polymerisationen blev udført i 22 1/2 time til en omdannelse på 92$ og et samlet indhold af fast stof på 33,1$.Once the reaction was started, the pH of the mixture was adjusted to 3 ^ ea. 8 with EOH. The polymerization was carried out for 22 1/2 hours to a conversion of $ 92 and a total solids content of $ 33.1.

B. En harpiks med høj slagstyrke og gasspærrende egenskaber blev fremstillet ved polymerisation af en blanding af følgende bestanddele: 40 6 149976B. A high impact resin and gas blocking properties were prepared by polymerizing a mixture of the following ingredients: 40 6 149976

Bestanddele Dele acrylonitril 75 methylacrylat 25 latex A (se ovenfor) 31,9 5 kaliumpersulfat 0,06Ingredients Parts of acrylonitrile 75 methyl acrylate 25 latex A (see above) 31.9 5 potassium persulfate 0.06

Gafac BE-610 3 n-dodecylmerkaptan 1 ethyldiamintetraeddikesyre 0,05 vand 200 10 pH-værdien "blev indstillet til ca. 7 med KOH. Polymerisationen "blev udført i Hovedsagen i fravær af molekulær oxygen ved 60°C i 20 timer til frembringelse af en omdannelse på 97$ af en latex med 33$ fast 15 stof.Gafac BE-610 3 n-dodecyl mercaptan 1 ethyl diamine tetraacetic acid 0.05 water 200 The pH value "was adjusted to about 7 with KOH. The polymerization" was carried out in the main case in the absence of molecular oxygen at 60 ° C for 20 hours to produce a $ 97 conversion of a latex with $ 33 solids.

Eksempel 2Example 2

Fremgangsmåden i eksempel IB blev gentaget under udelukkelse af bestanddelen latex A. Der fremkom en latex af den copolymere af aeryl= 20 nitril og methylacrylat.The procedure of Example 1B was repeated to exclude the component latex A. A latex of the copolymer of aeryl = 20 nitrile and methyl acrylate was obtained.

Eksempel 3Example 3

En copolymer af acrylnitril og styren blev fremstillet i nærværelse 25 af en latex af en kautsjukagtig butadien-styrencopolymer (72 vægt$ butadien, 28 vægt$ styren) under anvendelse af følgende sammensætning:A copolymer of acrylonitrile and styrene was prepared in the presence of a latex of a rubbery butadiene-styrene copolymer (72% by weight butadiene, 28% by weight styrene) using the following composition:

Bestanddele Dele vand 419 30 Gafac BE-610 6,3 t-dodecylmerkaptan 0,6 azobisisobutyronitril 0,5 acrylnitril 91,05 35 styren 8,95 s tyren-butadienlatex 10,8 (faste stoffer)Ingredients Parts of water 419 30 Gafac BE-610 6.3 t-dodecyl mercaptan 0.6 azobisisobutyronitrile 0.5 acrylonitrile 91.05 35 styrene 8.95 s tyrene-butadiene latex 10.8 (solids)

Polymerisationen blev udført ved 60°0 i en nitrogenatmosfære. Det molære forhold mellem acrylnitril og styren i fødematerialet var 20/1.The polymerization was carried out at 60 ° 0 in a nitrogen atmosphere. The molar ratio of acrylonitrile to styrene in the feedstock was 20/1.

7 1499767 149976

Polymerisationstiden var 130 minutter, og i løbet af denne tid blev der yderligere ført 53 dele styren til reaktionsblandingen. Der fremkom et udbytte på 73$ polymer. En prøve af det polymere faste stof viste sig at have et nitrogenindhold på 11,19 vægt$, hvilket 5 svarer til et molforhold aerylnitril/styren i den polymere på 1,44/1.The polymerization time was 130 minutes, and during this time 53 parts of styrene were added to the reaction mixture. A yield of $ 73 polymer was obtained. A sample of the polymeric solid was found to have a nitrogen content of $ 11.19, which corresponds to a molar ratio of aeryl nitrile / styrene in the polymer of 1.44 / 1.

Eksempel 4Example 4

En latex af en copolymer af acrylnitril og styren blev fremstillet 20 ved fremgangsmåden i eksempel 3 med undtagelse af, at latexen af bu-tadien og styren blev udeladt af sammensætningen.A latex of a copolymer of acrylonitrile and styrene was prepared by the procedure of Example 3 except that the latex of butadiene and styrene was omitted by the composition.

Eksempel 5 A. En prøve af den polymere latex beskrevet i eksempel IB blev omhyggeligt filtreret gennem groft filterpapir (eller osteklæde) for at fjerne eventuelle små partikler af polymer, som kunne være til stede. latexen blev så fortyndet ved tilsætning af fra 0 til 3 vægtdele destilleret vand for hver vægtdel filtreret latex. Almindelig-2g vis blev anvendt 3 dele vand pr. del latex. Den fortyndede latex blev så anbragt i en sprøjtepistol (Binks, model nr. 26). Stålplade, fortinnet stålplade og aluminiumplade blev alle belagt ved sprøjtning af latexen på pladen. I hvert tilfælde blev overfladen af den flade metalplade først renset for eventuel olie og fedt, der kunne være blevet tilbage fra metalvalsningen. Tetrachlorkulstof eller et lignende opløsningsmiddel blev anvendt til at rense metaloverfladen.Example 5 A. A sample of the polymeric latex described in Example 1B was carefully filtered through coarse filter paper (or cheese cloth) to remove any small particles of polymer that might be present. the latex was then diluted by adding from 0 to 3 parts by weight of distilled water for each part by weight of filtered latex. Ordinary-2 g of fish was used 3 parts water per day. of latex. The diluted latex was then placed in a spray gun (Binks, model # 26). Steel plate, tinned steel plate and aluminum plate were all coated by spraying the latex onto the plate. In each case, the surface of the flat metal plate was first cleaned of any oil and grease that might have remained from the metal rolling. Tetrachloro carbon or a similar solvent was used to clean the metal surface.

De fremkomne rene, tørre metaloverflader blev så sprøjtebelagt med latexen. Sprøjtepistolen blev indstillet til at give en ret let, 3Q fin stråle. 1-5 tynde, jævne belægninger af latex på metaloverfladen blev fremstillet, idet hver belægning fik lov at lufttørre i ca. 1 minut, før den næste belægning blev påført. Efter at det øverste lag var lufttørret, blev den belagte metalplade anbragt i en luftcirkulationsovn, som blev holdt ved ca. 200-220°C i 1 eller 2 minut-35 ter. Den belagte metalplade blev så fjernet fra ovnen og fik lov at afkøle til stuetemperatur. Der må drages omsorg for at undgå overhedning af belægningen, fordi nedbrydning af polymer kan ske ved længere tids udsættelse for høj temperatur.The resulting clean, dry metal surfaces were then spray coated with the latex. The spray gun was set to give a fairly light, 3Q fine jet. 1-5 thin, even, latex coatings on the metal surface were prepared, each coating being allowed to air dry for approx. 1 minute before the next coating was applied. After the top layer was air dried, the coated metal plate was placed in an air circulation oven which was held at approx. 200-220 ° C for 1 or 2 minutes. The coated metal plate was then removed from the oven and allowed to cool to room temperature. Care must be taken to avoid overheating of the coating because degradation of polymer can occur by prolonged exposure to high temperature.

40 8 14997640 8 149976

Tykkelsen af den endelige "belægning var ca. 0,0125 mm - 0,0025 mm.The thickness of the final coating was about 0.0125 mm - 0.0025 mm.

I de fleste tilfælde var tykkelsen af de påførte belægninger i intervallet 0,0025 til 0,025 mm. Selv om det belagte metal kan have hvilke som helst ønskede dimensioner, blev der til afprøvningsformål 3 anvendt metalplader fra 0,1 til 0,175 mm i tykkelse og i rektangulære stykker på 12,5 x 20 cm.In most cases, the thickness of the applied coatings was in the range of 0.0025 to 0.025 mm. Although the coated metal can have any desired dimensions, for test purposes 3, metal plates of 0.1 to 0.175 mm in thickness and in rectangular pieces of 12.5 x 20 cm were used.

B. Sejheden af den polymere belægning påført på forsøgsmetalstykkerne ifølge A ovenfor samt adhæsionen af belægningen til metalover- L0 fladen blev bestemt ved en bøjningsprøve.B. The toughness of the polymeric coating applied to the test metal pieces of A above, as well as the adhesion of the coating to the metal surface, were determined by a bending test.

Ved bøjningsprøven blev den med polymer belagte metalplade anbragt i en skruestik. Pladen blev bøjet bort fra den belagte side, den blev så fjernet fra skruestikken og bøjet hele vejen i samme ret-L5 ning, således at den blev foldet sammen. Ben belagte side blev således bøjet 180° og skarpt foldet. På dette punkt blev foldningen på den belagte side undersøgt for afskalning af polymer belægning fra metaloverfladen.In the bending test, the polymer-coated metal plate was placed in a vice. The plate was bent away from the coated side, it was then removed from the vice and bent all the way in the same direction so that it was folded. Leg coated side was thus bent 180 ° and sharply folded. At this point, the folding on the coated side was examined for peeling off polymer coating from the metal surface.

*° herefter blev den med polymer belagte metalplade igen anbragt i skruestikken og bøjet på et andet sted. Benne gang blev den belagte overflade bøjet mod sig selv. Ber blev igen foretaget en 180° bøjning af metalpladen med den belagte overflade på indersiden af pladen. Igen blev foldningsarealet undersøgt for afskalning af polymer. 25 Med alle de tre typer belagt metalplade, stål, fortinnet stål og aluminium, der er beskrevet ovenfor, blev der ikke sporet nogen afskalning af belægningen ved bøjningsprøven.Then the polymer coated metal plate was again placed in the vice and bent in another place. Once, the coated surface was bent towards itself. Ber was again made a 180 ° bend of the metal plate with the coated surface on the inside of the plate. Again, the folding area was examined for polymer peeling. With all the three types of coated metal sheet, steel, tinned steel and aluminum described above, no peeling of the coating by the bending test was detected.

C. Ber blev udarbejdet en prøve med udstanset hul, som er en for-!0 holdsvis hurtig og mere krævende prøve end den ovenfor under B beskrevne bøjningsprøve.C. Ber was prepared a punched hole test which is a relatively quicker and more demanding test than the bending test described above under B.

Yed prøven med udstanset hul blev en belagt metalplade fra B ovenfor anbragt fladt over en delvis åbnet skruestik eller over en metalplade med hul i. I begge tilfælde blev en hård, massiv overflade anbragt under den belagte plade undtagen under et lille område, som var et åbent rum direkte under pladen. Birekte over dette ikke understøttede område af pladen blev anbragt en dorn, og dornen blev drevet gennem pladen ved et skarpt slag med en hammer. Ben polymere belæg- :0 9 149976 ning i området omkring det fremkomne takkede hul blev undersøgt for afskalning. Fravær af afskalning betyder, at belægningen er god. Dårlige belægninger vil vise afskalning eller revning af overfladen i vidt omfang omkring det udstansede hul og selv så langt tilbage som 5 3-6 mm fra kanten af hullet.During the punched hole sample, a coated metal plate from B above was placed flat over a partially opened vice or over a metal plate with a hole in it. In both cases, a hard, solid surface was placed under the coated plate except under a small area which was a open space directly below the plate. Directly over this unsupported area of the plate was placed a mandrel and the mandrel was driven through the plate by a sharp blow with a hammer. Bone polymeric coating in the area around the resulting thanked hole was examined for peeling. Absence of peeling means that the coating is good. Poor coatings will show peeling or tearing of the surface extensively around the punched hole and even as far back as 5 3-6 mm from the edge of the hole.

Prøven med udstanset hul blev udført begge veje, først med den belagte side af pladen øverst og derefter med den belagte side af pladen nedad. Yed første del af prøven går dornen ned gennem belægnin-10 gen, og ved den anden del går dornen faktisk op gennem belægningen.The punched hole test was performed both ways, first with the coated side of the plate at the top and then with the coated side of the plate facing down. In the first part of the sample, the mandrel goes down through the coating, and at the second part the mandrel actually goes up through the coating.

De belagte prøver af metalplade fremstillet ved B ovenfor udviste alle i hovedsagen ingen afskalning eller revning og viste således, at der var tale om gode belægninger.The coated metal sheet samples prepared at B above all showed essentially no peeling or tearing and thus showed that these were good coatings.

15 D. En prøve kaldet nålehulsprøven blev udarbejdet for at afgøre, om de polymere belægninger på prøvepladerne, der er beskrevet under B ovenfor, var kontinuerlige og fri for nålehuller og hulrum i overfladen af belægningen.D. A sample called the needle punch sample was prepared to determine if the polymeric coatings on the sample plates described under B above were continuous and free of needle holes and voids in the surface of the coating.

20 En 2 vægtfo opløsning af CuSO^,5H20 i destilleret vand blev fremstillet. pH-værdien af denne opløsning blev indstillet til 1 med en ringe mængde HgSO^. Den belagte metalplade blev så neddykket i denne opløsning, og på kort tid blev den ubelagte side af metalpladen (stål eller fortinnet stål) belagt med kobbermetal. På den belagte side 25 var der imidlertid ingen aflejring af metallisk kobber, hvis der ikke var nogen nålehuller, hulrum eller ridser i den polymere belægning. Hvis den med polymer belagte side havde nålehuller, ridser eller hulrum i kunststofbelægningen, blev en lille overflade af metaloverfladen blotlagt og metallisk kobber aflejret på den blotlagte 30 overflade. Mr fine ridser med forsæt blev skabt i gode polymere belægninger, og pladerne blev neddykket i kobbersulfatopløsningen, viste disse ridser sig uvægerligt hurtigt som fine, mørkerøde linier på den belagte side af stålet eller de fortinnede stålplader.A 2% by weight solution of CuSO4, 5H2 O in distilled water was prepared. The pH of this solution was adjusted to 1 with a small amount of HgSO4. The coated sheet metal was then immersed in this solution and in a short time the uncoated side of the sheet metal (steel or tinned steel) was coated with copper metal. However, on the coated side 25 there was no metallic copper deposition if there were no needle holes, cavities or scratches in the polymeric coating. If the polymer-coated side had needle holes, scratches, or voids in the plastic coating, a small surface of the metal surface was exposed and metallic copper deposited on the exposed surface. Mr. fine scratches were intentionally created in good polymeric coatings and the plates immersed in the copper sulfate solution, these scratches invariably appeared as fine, dark red lines on the coated side of the steel or the tinned steel sheets.

3535

En ændring af nålehulsprøven var nødvendig til prøver af aluminiumplade belagt med polymer. Den ovenfor beskrevne kobbersulfatopløs-ning blev indstillet til pH 1 med saltsyre i stedet for svovlsyre.A change of needle punch test was necessary for aluminum plate coated with polymer samples. The copper sulphate solution described above was adjusted to pH 1 with hydrochloric acid instead of sulfuric acid.

Med denne ændring viste det sig, at kobber pletterer bedre på alumi-nium, når det er neddykket i opløsningen.With this change, it appeared that copper plated better on aluminum when immersed in the solution.

10 14997610 149976

Kobbersulfat nålehulsprøven kan også anvendes på plader belagt med polymer, som er undergået bøjningsprøven og prøven med udstanset hul, der er beskrevet ovenfor. De med polymer belagte metalplader, der er beskrevet under B ovenfor, viste sig alle at have udmærkede kon-, tinuerlige belægninger ved prøverne med kobbersulfat og nålehul.The copper sulphate needle punch test may also be used on polymer coated sheets which have undergone the bending test and the punched punch test described above. The polymer-coated metal sheets described under B above were all found to have excellent continuous tin coatings in the copper sulphate and needle hole samples.

Eksempel 6Example 6

En prøve af den polymere latex, der er beskrevet i eksempel IB, blev omhyggeligt filtreret gennem groft filtrerpapir og anvendt ufortyn-det. Der blev foretaget dyppebelægning under anvendelse af aluminiumplade og den filtrerede latex.A sample of the polymeric latex described in Example 1B was carefully filtered through coarse filter paper and used undiluted. Dip coating was done using aluminum plate and the filtered latex.

De rene, olie- og fedtfrie aluminiumplader blev neddyppet i latexen 5 ved stuetemperatur og blev holdt nede i ca. 5-10 sekunder. Pladerne blev så taget op af latexen og ophængt,for at overskud af latex kunne dryppe af, i ca. 5-15 sekunder og blev lufttørret i ca. 5 minutter . De fremkomne belagte plader blev anbragt i en luftcirkulationsovn i ca. 1-2 minutter ved 200-220°0.The pure, oil and grease-free aluminum sheets were immersed in latex 5 at room temperature and held down for approx. 5-10 seconds. The plates were then taken out of the latex and suspended so that excess latex could drip off, for approx. 5-15 seconds and was air dried for approx. 5 minutes . The resulting coated plates were placed in an air circulation oven for approx. 1-2 minutes at 200-220 ° 0.

!0! 0

Ved dyppebelægningen blev begge sider af aluminiumpladen belagt, i stedet for kun den ene side som beskrevet ved sprøjtebelægningen i eksempel 5A. (Tykkelsen af belægningen blev bestemt med et mikrometer, !5At the dip coating, both sides of the aluminum plate were coated, rather than just one side as described by the spray coating of Example 5A. (The thickness of the coating was determined with one micrometer,! 5

Der blev fremstillet belægninger med en gennemsnits tykke Ise på den ene side på 0,0075 til 0,01 mm over det meste af pladens overflade.Coatings were made with an average thick ice on one side of 0.0075 to 0.01 mm above most of the plate surface.

Med dyppebelægning er belægningens tykkelse tilbøjelig til at variere, jq idet den er tyndest i den øvre ende af pladen og tykkest i den nedre ende af pladen (hvor afløbende latex er tilbøjelig til at opsamle sig). Eor at få en mere ensartet tykkelse på en plade anbefales det, at pladen roteres under tørringen. Ben dyppebelagte aluminiumplade fremstillet på denne måde viste sig at have en udmærket belægning (5 ved de prøver, der er beskrevet i eksempel 5B-B.With dip coating, the thickness of the coating tends to vary, as it is thinnest at the upper end of the plate and thickest at the lower end of the plate (where draining latex tends to accumulate). To obtain a more uniform thickness on a plate, it is recommended that the plate be rotated during drying. Bone dip-coated aluminum sheet made in this way proved to have an excellent coating (5 in the tests described in Example 5B-B.

Eksempel 7Example 7

En latexprøve beskrevet i eksempel IB blev filtreret og fortyndet som beskrevet i eksempel 5A. latexen blev belagt ved valsebelægningA latex sample described in Example 1B was filtered and diluted as described in Example 5A. the latex was coated by roller coating

Claims (4)

11 149976 på rent stål og fortinnet stål. Pladen blev anbragt på en flad, jævn overflade og blev fastgjort med klæbebånd i begge ender. Fortyndingsfaktoren destilleret vand/filtreret latex var 1:1 efter vægt. latexen kan altså anvendes ufortyndet efter filtrering. En ringe 5 mængde fortyndet latex blev hældt ud over den ene ende af den flade metalplade. Derefter blev en gummivalse langsomt rullet over pladen, således at den hele tiden skubbede en ganske lille bølge af latexen foran sig. Et tyndt lag af latexen klæbede til metaloverfladen, efter at valsen var passeret derover. Denne belægning fik lov at luft-10 tørre i flere minutter ved stuetemperatur. Den belagte plade blev så opvarmet til 200-220°C i en lufteirkulationsovn. Eksempel 811 149976 on pure steel and tinned steel. The plate was placed on a flat, even surface and was secured with adhesive tape at both ends. The dilution factor of distilled water / filtered latex was 1: 1 by weight. The latex can thus be used undiluted after filtration. A small amount of diluted latex was poured over one end of the flat metal plate. Then a roll of rubber was slowly rolled over the plate so that it kept pushing a very small wave of latex in front of it. A thin layer of the latex adhered to the metal surface after the roller had passed over it. This coating was allowed to air-dry for several minutes at room temperature. The coated plate was then heated to 200-220 ° C in an air circulation oven. Example 8 15 Fremgangsmåden i eksempel 1 blev gentaget under anvendelse af latexen der er beskrevet i eksempel 2. Der fremkom udmærkede belægninger på stål, fortinnet stål og aluminium. Eksempel 9 20 Fremgangsmåden i eksempel 1 blev gentaget under anvendelse af latexen beskrevet i eksempel 3. Der fremkom udmærkede belægninger på stål, fortinnet stål og aluminium.The procedure of Example 1 was repeated using the latex described in Example 2. Excellent coatings were obtained on steel, tinned steel and aluminum. Example 9 The procedure of Example 1 was repeated using the latex described in Example 3. Excellent coatings were obtained on steel, tinned steel and aluminum. 25 Eksempel 10 Fremgangsmåden i eksempel 1 blev gentaget under anvendelse af latexen beskrevet i eksempel 4. Der fremkom udmærkede belægninger på stål, fortinnet stål og aluminium. Patentkrav.Example 10 The procedure of Example 1 was repeated using the latex described in Example 4. Excellent coatings were obtained on steel, tinned steel and aluminum. Claims. 1. Metalplade belagt på mindst den ene side med latex af en polymer, kendetegnet ved, at den polymere er fremstillet ved poly-merisation af en større mængde af en monoumættet nitril og en mindre mængde af en anden monovinyl monomer komponent, som er copoly-meriserbar med nitrilen, i nærværelse af en forud dannet dienkaut-sjuk.Metal plate coated on at least one side with a latex of a polymer, characterized in that the polymer is made by polymerizing a greater amount of a monounsaturated nitrile and a smaller amount of another monovinyl monomer component which is copolymeric. mercurable with the nitrile, in the presence of a pre-formed diencote disease.
DK032577A 1976-02-17 1977-01-26 METAL PLATE COATED ON AT LEAST ONE SIDE WITH LATEX OF A POLYMER DK149976C (en)

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