EP1129157A1 - Composition de conservation / lubrification / appret pour surfaces metalliques - Google Patents

Composition de conservation / lubrification / appret pour surfaces metalliques

Info

Publication number
EP1129157A1
EP1129157A1 EP99949458A EP99949458A EP1129157A1 EP 1129157 A1 EP1129157 A1 EP 1129157A1 EP 99949458 A EP99949458 A EP 99949458A EP 99949458 A EP99949458 A EP 99949458A EP 1129157 A1 EP1129157 A1 EP 1129157A1
Authority
EP
European Patent Office
Prior art keywords
plp
epoxidized
edenol
curing
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99949458A
Other languages
German (de)
English (en)
Inventor
Gerhardus Antonius Roescher
Albertus Jozef Huis In 't Veld
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Original Assignee
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority to EP99949458A priority Critical patent/EP1129157A1/fr
Publication of EP1129157A1 publication Critical patent/EP1129157A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/08—Epoxidised polymerised polyenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Definitions

  • the present application relates to compositions for the protection and treatment of metallic substrates, in particular of steel substrates such as strip steel. More particular, the invention relates to such a composition which can function as a preservative during storage, as a lubricant during processing, and as a primer for subsequent application of a coating.
  • British Patent 1,094,053 describes a method for rolling steel sheet of tin plate gauges in which a film of an epoxidized soyabean oil is applied to the steel sheet "while rolling it to final gauge".
  • soyabean oil "affords the lubrication between the strip and the rolls of the cold rolling mill and remains on the steel sheet when reduced to final gauge.
  • the epoxidized oil film also "does not cause eyeholing or dewetting of the laquer coating or lithographing inl " - which provides for improved quality of a subsequently applied (decorative) coating - and imparts "a limited degree of corrosion resistance to the product before decorating' ' '.
  • the epoxidized soyabean oil is applied - by any suitable means - as a fine spray or mist of neat epoxidized soyabean oil or of an emulsion thereof in water.
  • GB 1,094,053 does not describe the use of presence of any cross-linking components in the epoxidized oil or the aqeuous emulsion thereof.
  • the composition of US-A-3,582,368 can also serve as a primer under latex paint.
  • US-A-3,582,368 does not mention or suggest the use of the composition described therein as a lubricant during forming processes, nor as a preservative prior to forming.
  • US-A-3,582,368 does not describe the use of a cross-linking component, whereas according to US-A-3,582,368, the presence of both casein and the toxic chromium compound .are mandatory.
  • US-A-2,930,708 describes a coating composition for inhibiting corrosion in metals containing an oleoresinous material prepared from a fatty oil material selected from the group consisting of drying and semi-drying oils containing long chain fatty acid radicals and a resinous material and a corrosion inhibiting epoxidized oil dervied from a drying or semi-drying oil. For obtaining the desired corrosion resistance, it is suggested to add the epoxidized oil to the final composition in amounts of 0,5%, 1%, 2% and up to 5%. US-A-2,930,708 also mentions that the epoxididized oil can be added - in essentially the same amount - to a red lead primer.
  • compositions of US-A-2,930,708 have a very low epoxidized oil content, in particular compared to the compositions of the present invention. Also,
  • US-A-5,318,808 describes a UV-curable composition for coating aluminium cans comprising 30-90 parts of an epoxidized vegetable oil, 10-70 parts of a low molecular weight epoxy resin, 2-6 parts of a photo-initiator for cationic polymerisation, and 1-5 parts of a wax or mixture of waxes.
  • the coating is applied to the formed cans and UN-cured in order to protect the cans from abrasion and scratching during handling.
  • US-A-5,318,808 does not disclose or suggest the use of an epoxidized oil as a lubricant during forming, nor as a preservative prior to forming.
  • thermosetting polyester resins obtained by curing epoxidized soybean oils with dicarboxylic anhydrides in the presence of cure catalysts.
  • the thermosetting polyester resins thus obtained can be used for the manufacture of rubber-like low Tg polymeric articles. Coating of metallic substrates is neither mentioned or suggested.
  • Strip steel is often produced in the form of "strip steel” or “coil", a sheet or band of metal which can be rolled up and as such can easily be stored and/or transported.
  • Strip steel can also easily be formed, for instance by cold forming processes such as deep drawing, rolling, stretching or bending.
  • strip steel is usually coated with a preservative composition in order to prevent corrosion during storage. Prior to further processing, this preservative is removed, i.e. by means of degreasing. The metal surface is then treated with a lubricant composition, which facilitates further processing and improves throughput. After forming, this lubricant composition is also removed, i.e. by washing.
  • a primer composition is applied to the metal, upon which the final coating is applied.
  • the known methods for processing strip steel therefore involve the use of three different compositions and several processing steps, i.e.: 1. applying the preservative composition;
  • the object of the invention is to improve the above methods, by reducing the number of processing steps required and/or by reducing the number of different compositions used. More particular, the object of the invention is to provide a composition which can function as a preservative for storage/transportation, as a lubricant for draw processing, and also as a primer for application for the final coating. Other objects of the invention will become clear from the description hereinbelow.
  • compositions of the invention which comprises at least an epoxidized oil, more particular of a cross-linkable composition containing at least an epoxidized oil, and at least one cross linking component.
  • compositions of the invention can serve as a preservative, as a lubricant and as a primer, they will be indicated hereinbelow as "Preservation Lubricant Primers” or "PLP-compositions”.
  • a PLP -composition comprising an epoxidized oil and at least one cross-linking component provides significant advantages compared to the use of an epoxidized oil alone according to GB patent specification 1,094,053 discussed above.
  • the invention therefore relates to the use of a composition containing at least one epoxidized oil as a preservative for metallic substrates, in particular for steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • the invention relates to the use of a composition containing at least one epoxidized oil as a lubricant for metallic substrates, in particular for steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • the invention relates to the use of a composition containing at least one epoxidized oil as a primer on metallic substrates, in particular on steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • the invention relates to the use of a composition containing at least one epoxidized oil both as a preservative and as a lubricant for metallic substrates, in particular of steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • the invention relates to the use of a composition containing at least one epoxidized oil both as a lubricant for and as a primer on metallic substrates, in particular for/on steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • a composition containing at least one epoxidized oil both as a preservative for and as a primer on metallic substrates, in particular for/on steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one epoxidized compound.
  • a further aspect of the invention relates to use of a composition containing at least one epoxidized oil as a preservative for, as a lubricant for, and as a primer on, metallic substrates, in particular for/on steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil further comprises at least one cross-linking component.
  • the invention also relates to a method for treating and/or processing of metallic substrates, said method comprising applying a composition containing at least one epoxidized oil to the metallic substrate, in which the composition [] containing the at least one epoxidized oil further comprises at least one cross-linking component; as well as to a composition for the protection and treatment of metallic substrates, in particular of steel substrates such as strip steel, comprising at least one epoxidixed oil and at least one cross-linking component.
  • the invention relates to the use of a composition containing at least one epoxidized oil as a preservative for metallic substrates, in particular for steel substrates such as strip steel, in which the composition containing the at least one epoxidized oil is applied and used as a preservative after the initial rolling of the metallic substrate, and prior to the further rolling and/or forming of the metallic substrate, for instance during storage, handling and/or transportation of the steel prior to forming or rolling to final guage.
  • the composition may or may not contain the at least one epoxidized oil. Subsequently, in this aspect of the invention, the composition
  • -i.e. as present on the substrate as a preservative- may then further be used as a lubricant for the further rolling or forming of the substrate and/or may be used as a primer for a subsequently applied topcoat, i.e. essentially as described herein.
  • epoxidized oil generally refers to an epoxidized derivative of an unsaturated fat or oil.
  • fats and oils generally comprise a glycerol molecule linked by ester bonds to (usually) three fatty acid residues, in which the fatty acid residues comprise long hydrocarbon chains with generally 6-32, usually 9-24, often 16 or 18, carbon atoms.
  • unsaturated fats and oils one or more of these hydrocarbon chains further contain(s) generally 3 or less, and usually 2 (conjugated or non-conjugated) or only 1 unsaturated bond(s) per chain.
  • the epoxidized oils used according to the invention at least one, preferably two or more, and possibly up to essentially all the unsaturated bonds in the fatty acid triglyceride are replaced by epoxide-bonds.
  • the epoxidized oils used in the invention will contain on average at least two epoxy-groups per molecule.
  • any epoxidized derivative of unsaturated fats and oils known per se can be used.
  • epoxidized derivatives of natural unsaturared oils such as fatty oils, vegetable oils or animal oils are used, although the invention is not limited thereto.
  • synthetic epoxidized oils with specifically tailored properties can be used.
  • Such synthetic oils can contain specific functional groups on the epoxidized fatty acid chains, or may contain one or even two different side chain(s) or groups on the glycerol molecule instead of the epoxidized fatty acid residue(s), as long as the final oil can still be crosslinked as described herein.
  • drying oils such as soyabean oil, linseed oil and fish oil, as well as epoxidized derivatives of so-called “synthetic” drying oils such as dehydrated castor oil, and/or modifications of such drying oils.
  • the epoxidized oils of the invention will generally have a degree of epoxidation of 50-100 %, more particular 80-100 %, depending upon the oil on which they are based.
  • the oils are epoxidized until an "epoxy-equivalent weight" or "EEW" (molecular weight per epoxy group) of at least 100, and prefeably about 200 is reached, in which the latter corresponds to 20% by weight epoxy groups (based on a M w of 42 for the epoxy group).
  • EW molethoxy-equivalent weight per epoxy group
  • Suitable mixtures of two or more epoxidized oils as described herein may also be used.
  • epoxidized oils of the invention are commercially available or can be prepared by in a manner known per se, i.e. by chemical synthesis usually involving
  • epoxidized oils examples include epoxidized soya oils or ESO's (Edenol D81, Edenol D82, Estabex 2307, Drapex 6.8 and Reoplast 39), epoxidized linseed oils or ELO's (Edenol B316) and alkyl esters of unsaturated fatty acids, such as epoxidized alkyl esters of oleic acid (Estabex 2386, Drapex 3.2 and
  • Reoplast 38 These epoxidized oils have been used as stabilizers and plastisizers in plastic compositions, in particular for PNC.
  • the epoxidized oils may be used as such, or after suitable modification or derivatization, for instance to provide the epoxidized oils with one or more desired properties.
  • the epoxidized oils may be modified with a compound that provides for hydrophilic groups of side-chains, such as a Jeffamine, in order to improve their solubility in water, e.g. for use in aqueous systems and in particular in (aqueous) emulsions.
  • the PLP-emulsions may be prepared using one or more separate surfactants, such as DisponilTM 23, Tween 20, SpanTM 20,
  • AtsurfTM 3969 and/or Atsurf 3300B or a suitable cellulose derivative such as ⁇ atrosol or hydroxyethylcellulose (HEC); or a suitable combination thereof.
  • a suitable cellulose derivative such as ⁇ atrosol or hydroxyethylcellulose (HEC); or a suitable combination thereof.
  • Known systems for treating metal substrates generally comprise components such as fatty esters, wetting improvers, soaps, viscosity controllers, anti-corrosion agents such as chromium compounds, or a combination thereof.
  • these known systems do not provide the combined function of a preservative, a lubricant and a primer.
  • known lubricants can sometimes be highly viscous.
  • they must be removed prior to coating (i.e. after forming) by the use of organic solvents or water-based systems followed by drying, as primers/coatings will generally "spread" poorly over lubricant-treated surfaces.
  • the adhesion of primers to substrates treated with known lubricants is very poor.
  • Dutch application 7802712 tries to avoid these washing steps by the use of a lubricant composition that comprises at least a curable liquid component which is hardened after processing and prior to further coating.
  • a curable liquid component (meth)acrylates, liquid epoxy resins, alkyd resins or aminoplasts are mentioned, which are cured thermally, by radiation or by free radicals.
  • these compositions are not suggested or suitable as preservatives and also can be very toxic and consequently difficult to handle.
  • the imsaturated materials of NL-A-7802712 can show poor stability, particularly when the thus coated coils are subjected to sunlight and outside air during storage. This may also detract from their lubricating properties.
  • European application 0 283 912 describes a cooling and lubricant composition
  • a cooling and lubricant composition comprising an aqueous emulsion of a film-forming binder, more particular an emulsion polymerisate or a heat-curable binder.
  • Specific examples given comprise aqueous emulsions of epoxy resins, acrylate resins, phenol-modified polyesters, and of blockpolymers based on such resins, as well as heat-curable resins comprising melamin, urea or phenolics as cross-linkers.
  • these compositions are not suggested or suitable as preservatives -probably because they may be insufficiently water-repellant to prevent corrosion- and are sticky when applied, which detracts from their lubricating properties.
  • solid systems are known, for instance based on acrylate-, epoxy- or polyester resins. However, layers formed of such solid materials generally have poor lubricating properties and are not self-sealing.
  • the use of the epoxidized oils provides for final PLP- compositions that are liquid at room temperature and/or at the temperature at which the PLP is to be applied onto the metal substrate.
  • their advantageous viscosity not only makes the PLP-compositions easier to apply -leading to a more uniform coating- and provides good lubricating properties, but also has the advantage that minor defects to the coating layer (scratches, pitting) as may occur during handling, transportation or processing of the treated substrate can be easily repaired by the coating itself (“self-sealing”), by "touching up” the existing layer or by applying a further coating layer.
  • the PLP-compositions of the invention must be cross-linkable (curable), by which is meant that the molecules of the epoxidized oils must be able to form covalent bonds with each other other and/or with the molecules of other suitable cross-linking components of the PLP-composition (if any) to form a crosslinked structure.
  • any curing technique known per se can be used.
  • UV-curing or thermal curing will be used, as will be further discussed hereinbelow.
  • the PLP-compositions used in the invention will contain at least one "cross- linking component" as described herein, i.e.
  • a component which is involved in, initiates or facilitates the cross-linking reaction may be an initiator for the cross-linking reaction, for instance when UN-curing is used; a component involved in the formation of cross-linkages, such as a cross-linker (for example di-esters of di-acids such as dimethylsebacate) or a catalyst; or a further component of the PLP-composition capable of reacting with the epoxidized oil to form a crosslinked structure, such as the fatty polyacids described below.
  • a cross-linker for example di-esters of di-acids such as dimethylsebacate
  • a catalyst for example di-esters of di-acids such as dimethylsebacate
  • a further component of the PLP-composition capable of reacting with the epoxidized oil to form a crosslinked structure, such as the fatty polyacids described below.
  • the PLP-compositions of the invention can also contain one or more further components known per se for preservatives, lubricants and/or primers, depending upon the desired properties of the composition and/or the coating and upon the curing technique used.
  • they can contain adhesion- improvers, surfactants, anti-corrosion additives, viscosity controllers, flow improvers, stabilizers etc, in suitable amounts known per se.
  • They may also contain minor amounts of unsaturated oils, in particular of those oils from which the epoxidized oils have been derived.
  • the PLP-compositions of the invention can further contain a flash rust inhibitor such as SER-AD FA 179 or SER-AD FA 579 (both from Servo) or Alcophor AC (Henkel), in usual amounts.
  • compositions of the invention are usually essentially free of solvent.
  • the epoxidized oils of the invention and/or the optional other components of the PLP-compositions can also carry or be modified with further functional groups, if required, for instance to confer desired properties and/or to improve cross-linking.
  • the epoxidized oils and the further major components used in the PLP-compositions -such as the fatty acid component- will form a water-repellant coating.
  • the compositions of the invention are in the form of an aqueous emulsion of at least the epoxidized oil. This may be a O/W- (preferred), W/O-, ternary or even quaternary emulsion. Such emulsions may have the advantage of a very low viscosity, which may be desired for certain applications.
  • the PLP-emulsions can be used in the same manner as non-aqueous PLP- compositions described herein.
  • the method of the invention as set out below generally will comprise at least one drying step for removal of the aqueous phase, preferably directly after the emulsion has been applied to the substrate.
  • a stabilizer for the emulsion not only improves the stability/shelf life of the emulsion, as well as its handling properties, but also improves the adhesion of a topcoat that is subsequently applied to the PLP -coated substrates, and these and other advantages will become clear from the Experimental Part hereinbelow.
  • one or more surfactants may be incorporated, such as those mentioned above.
  • the PLP-compositions can be prepared in a manner known per se, generally by mixing the components in the amounts indicated herein.
  • the PLP- emulsions can for instance be obtained by emulgating the at least one epoxidized oil and the further components of the PLP-composition in an aqueous medium such as water, optionally using stabilizers and/or emulsifiers, or by emulgating a finished PLP-composition an with aqueous medium, again optionally using stabilizers and/or emulsifiers.
  • the emulsions can be prepared using the "inversion method", e.g. as illustrated in the Experimental Part below.
  • the PLP-compositions of the invention combine the properties of a preservative, a lubricant and a primer.
  • the PLP-compositions show a good adhesion to metallic substrates without being (too) sticky when applied and/or (fully or partially) cured.
  • the use of the epoxidized oils provides a suitable balance between the adhesion to the metallic (steel) surface on the one hand and the "fatty" behaviour of the composition on the other.
  • the PLP-compositions in uncured, partially cured or fully cured form
  • the PLP-compositions are not only compatible with known primers or coatings, but can even chemically bind such further coatings, for instance via residual epoxy-groups, in particular when (further or post-)curing of the PLP-composition occurs during the hardening of the further coating. This may lead to the formation of a two-layered coating system with a diffuse intermediate layer.
  • the good lubrication by the PLP systems may be explained by the higher viscosity of the systems next to efficient wetting of metal substrate (strong interaction of functional groups such as epoxy or carboxyl with the metal surface), although the invention is not limited to any specific explanation.
  • the PLP-compositions have been shown to possess the ability of undergoing chemical reactions with commercially available primer resins, such as primers based on epoxy resins or epoxy-functional crosslinkers, primers based on resins or crosslinkers containing carboxyl-functionalities, primers based on resins or crosslinkers containing hydroxyl-functionalities, and amine-functional resins and hardeners. Nevertheless, the applied PLP-compositions are generally relatively inert, even when not or partially cured, which contribrutes to their good preservation and lubricating properties.
  • the PLP-compositions of the invention also provide the following advantages: - the PLP-compositions provide for rapid curing, even at low or moderate temperature; - the PLP-compositions have good chemical and physical stability. They generally have a pot-life of at least several weeks at room temperature;
  • the PLP-compositions are non-toxic and not (too) damaging to the environment. Also, they are not expected to release harmful substances such as toxic fumes when the metal substrates on which they have been applied are formed, processed or worked in any other way such as by welding.
  • the PLP-compositions provide good wetting of the metal surface and appropriate viscosity
  • the PLP-compositions have excellent film-forming properties, providing a uniform, sealed layer that provides good protection against corrosion, for instance as determined by the salt spray test ASTM B 117;
  • the PLP-compositions provide tribological and protective properties which are equal or better than those of conventional systems, even when fully or partially cured; - by appropriate choice of the epoxidized oil(s) and the further components as described above, the intrinsic properties of the PLP-compositions can be fine-tuned to a specific application and/or to meet the demands of applicators and end-users;
  • compositions of the invention show good resistance to oxygen, even when applied to the metallic substrate. This in contrast to coatings based on the corresponding unsaturated oils, in particular drying oils, which are known to polymerise when exposed to outside air.
  • the adhesion of a topcoat to the PLP-coated substrates is further improved; the combination of an epoxidized oil in combination with a crosslinking component allows for the application/use of coating layers with increased thickness, for instance of more than 5 ⁇ m. These cannot be achieved successivefully/reliably with an epoxidized oil per se (vide the Experimental Part below).
  • the invention provides advantages with respect to the welding of the coated metallic substrates.
  • the PLP-coatings of the invention do not release harmful or toxic chemicals/vapours.
  • the epoxidized oils of the invention can be cured by any chemical or physical curing mechanism or curing technique known per se, such as via curable functional groups, the presence of amine compounds or the presence of phenol and phenolic derivatives, or a similar chemical reaction.
  • any chemical or physical curing mechanism or curing technique known per se such as via curable functional groups, the presence of amine compounds or the presence of phenol and phenolic derivatives, or a similar chemical reaction.
  • UV-curing of at least one epoxidized oil or thermal curing of a mixture of a mixture of at least one epoxidized oil an at least one fatty acid are preferred.
  • the PLP-compositions used preferably contain at least one UN-initiator as the "crosslinking component".
  • Suitable UV-initiators are known per se, and include those which are referred to most frequently in connection with the photoinitiated polymerization of epoxy resins, such as onium salts possessing a non- nucleophilic anion such as PF 6 " , SbF 6 " , AsF 6 " or BF 4 " .
  • Suitable commercial photoinitiators are UNI 6990 (Union Carbide), Cyracure UNI-6974, Cyracure UVI-690 and Rhodorsil Photoinitiator 2074.
  • the UV-initiator is used in an effective amount, preferably 1-5% by weight of the total composition.
  • the UV-curable PLP's composition can be cured by irradiation with ultraviolet radiation of a suitable wavelength, generally between 200 and 350 nm, generally at temperatures of between 0°C up to 150°C, preferably room temperature up to 110°C, and using irradiation times of less than 1 minute, usually less than 10 seconds.
  • a suitable wavelength generally between 200 and 350 nm, generally at temperatures of between 0°C up to 150°C, preferably room temperature up to 110°C, and using irradiation times of less than 1 minute, usually less than 10 seconds.
  • the UV-curable PLP-compositions essentially comprise only the one or more epoxidized oils and an UV-initiator, although other additives (such as those mentioned above) can be present in minor amounts.
  • the UV-curable PLP-compositions provide the following advantages:
  • the lubrication/coating properties can optionally be fine-tuned by adding a fatty polyol or by combining different epoxy compounds;
  • UN-curing can optionally be combined with a thermal post-cure, for instance by 100°C during 10 min. This post-cure can also take place during the curing of the metal primer/topcoat, to provide even further increased inter-coat adhesion.
  • Another preferred embodiment of the invention comprises the thermal curing of a combination of epoxidized oils and a cross-linking component capable of reacting with the epoxidized oil to form crosslinked structure.
  • a particularly preferred class of cross-linking components are the so-called fatty polyacids. In general, these comprise dimers, trimers or higher mers (including “intermediate” mers, such as the "1.5 mers") of unsaturated fatty acids, or mixtures thereof, containing an average at least two functional groups, in particular at least two carboxylgroups, per mer.
  • Suitable mixtures of dimeric and trimeric fatty acids for use in the invention are commercially available under the name of Pripol 1040 (trimer fatty acid), Pripol 1013 (dimer fatty acid), or can be obtained in manner known per se by dimerisation, trimerisation of oligomerisation of unsaturated fatty acids, optionally followed by isolation/purification of a desired fraction, such as by distillation.
  • the polyacids used in the invention are preferably based on/obtained from natural unsaturated fatty acids, such as can be obtained from the saponification of natural fats and oils.
  • These unsaturated acids will generally comprise (in monomeric form) 6-32, usually 9-24, often 16 or 18, carbon atoms, and generally 3 or less, and usually 2 (conjugated or non-conjugated) or only 1 unsaturated bond(s) per chain.
  • the epoxidized oil and the fatty polyacid are used in a suitable ratio, generally from 1-99%) to 99-1%), depending on the relative molecular weights.
  • the amounts of oil and polyacid are chosen such that the amount of epoxygroups and carboxylgroups is between 10: 1 to 1 : 10, preferably about stoichiometric.
  • the resulting PLP-compositions are generally non-sticky, and can be cured under moderate conditions (20-30 min. at 160-180°C).
  • fatty polyacids instead of the fatty polyacids, other suitable cross-linking components may be used, such as suitable derivatives of fatty acids, including esters thereof
  • suitable cross-linking components are the amino-resins, for instance based on ureum, melamine or benzoguanidine or derivatives thereof, including urea/formaldehyde and melamine/forrnaldehyde resin.
  • the use of one or more resins based on melamine and/or derivatives thereof, such as CymelTM 303 is preferred, and may provide for an improved pot life for the final PLP-compositions.
  • the above crosslinking components may be used by themselves or in a suitable combination.
  • the PLP-compositions containing the aforementioned crosslinking components may again be formulated as emulsions, e.g. as described hereinabove.
  • one or more catalysts for the reaction between the epoxidized oil and the crosslinking components may be incorporated, e.g. those which promote the reaction between the epoxy-group(s) and one or more functional groups on the crosslinking component, such as a hydroxyl or a carboxyl group.
  • Examples are basic catalysts such as are inorganic alkaline salts (e.g., sodium carbonate), organometallic salts (e.g., lithium stearate, stannous octoate, zirconium octoate), and basic organic compounds (e.g., tertiary amines and phosphines, such as benzyl dimethylamine, tributylamine, triphenyl phosphine), etc.
  • inorganic alkaline salts e.g., sodium carbonate
  • organometallic salts e.g., lithium stearate, stannous octoate, zirconium octoate
  • basic organic compounds e.g., tertiary amines and phosphines, such as benzyl dimethylamine, tributylamine, triphenyl phosphine
  • the PLP-compositions of the invention may be applied to any metallic substrate, but is specifically suited for metal surfaces which are subject to chemical attack or corrosion, such as iron, steel, aluminium, in particular strip steel.
  • the invention is particularly applicable to the field of metalworking.
  • the invention is in particular suited for metals which are to be stored, transported, formed and/or coated. They are also suitable as preservatives/lubricants for machine tools and steel cables; in such applications, the cured PLP-composition may be the only coating present.
  • the invention further relates to a method for treating metallic substrates using a PLP-composition as described herein, which method comprises at least the step of:
  • the least one step in which the PLP-composition is (at least partly) cured can be carried out after the PLP-application has been applied onto the metallic substrate, but prior to storage, transportation and/or forming of the substrate; after the metallic substrate has been formed but prior to application of the final or topcoat; or both. Also, curing, additional curing and/or post-curing of the PLP-coating can take place during curing of the final (top)coat.
  • the post-curing of the PLP can be combined with the curing of the primer applied on the PLP layer after the metal forming has been performed.
  • the end user may combine the curing of PLP and primer by appropriate choice of the primer (i.e., selection of a primer requiring comparable curing conditions).
  • the method of the invention preferably does not comprise any step in which the applied PLP-composition is removed.
  • the PLP-composition can be applied in any manner known per se for applying a coating, such as spraying, rolling, dipping, brushing, pouring, by doctor blade or doctor roll; and in any suitable thickness which is at least sufficient to cover and protect the metallic surface and to fill up or coat any surface irregularities so as to provide the lubricating action of the coating.
  • the thickness of the PLP-layer will be 0.1-10 ⁇ m, preferably 1-10 ⁇ m, more preferably 1-2 ⁇ m. This is less than the usual thickness for conventional metallic primer layers, which is in the range of 20-200 ⁇ m.
  • the forming of the metallic substrate carrying the PLP-compositions can be carried out in any manner known per se, including cold forming processes such as drawing, deep drawing, rolling, stretching or bending; and extrusion techniques.
  • the further, final or top-coat can then be applied in any manner known per se, such as those described above for application of the PLP-composition.
  • the topcoat can also be cured in a manner known per se, which may be the same as of different from the method used for curing the PLP-composition.
  • the invention further relates to the use of a composition comprising at least one epoxidized oil, more preferably a PLP-composition as described herein, in the treatment of metallic substrates and/or surfaces.
  • the invention relates to the use of a composition comprising at least one epoxidized oil, more preferably a PLP-composition as described herein, as a preservative, as a lubricant or as a primer for metallic substrates/surfaces; more preferably as a combination of any two thereof, and most preferably as a combination of all three thereof.
  • the invention further relates to metallic substrates treated with the (non-cured, partly cured or fully cured) PLP-application.
  • the metallic substrates or surfaces may be formed and may also carry a further coating on the PLP-layer.
  • the application relates to semi-finished products such as metal (steel) bars, plates, cable etc. or strip steel treated with the PLP-composition.
  • FIG. 1 shows a graph of viscosity vs temperature for different PLP-compositions of the invention.
  • FIG. 2 shows the influence of UV irradiation dose on surface energy for a PLP coating based on Edenol B316.
  • FIG. 3 shows the potiife (measured as the change of viscosity in time at 22°C) of a PLP-mixture of Edenol B316 and Pripol 1040.
  • FIG. 4 shows the general principle of the TNO-slide/sheet-tribometer.
  • Figure 8 is a diagram showing gelation time of a stoichiometric mixture of Edenol
  • - Figure 10 is a graph showing viscosity at 25°C as a function of shear rate for water and different emulsions containing different Edenol contents, stabilized by 10 wt%> Atsurf 3969 (with respect to Edenol)
  • FIG. 11 is a graph showing surface wetting of P-G21032N (PPG) coatings on non- cured Edenol B316 as a function of film thickness
  • Figure 12 is a graph showing the tacky/non-tacky transition temperatures for Edenol
  • B316/Cymel 303 mixtures of different composition as a function of curing time.
  • the Cymel contains 1 wt%> p-toluene sulphonic acid before addition.
  • Figure 13 is a graph showing the Brookfield viscosity at 50°C as a function of time for Edenol B316/Cymel 303, Pripol 1040/Cymel 303 and Edenol B316/Sovermol Pol 1072 mixtures (10 wt% Cymel, containing 1 wt%> p-toluenesulphonic acid).
  • FIG. 14 and 15 show photographs of MAG welding in presence of 2 different PLP's, with in each Figure from left to right: 1) reference without PLP, 2) rope on metal sheet with thick PLP layer, 3) rope on sheet with thin PLP layer, 4) corner welding on sheet with thin PLP layer.
  • FIG. 16 and 17 show photographs of TIG welding in presence of 2 different PLP's, with in each Figure from left to right: 1) reference without PLP, 2) rope on metal sheet with thick PLP layer, 3) rope on sheet with thin PLP layer, 4) T- welding on sheet with thin PLP layer.
  • FIGS 18 and 19 are photographs showing coatings of steel substrates with ( Figure
  • EXAMPLE I General properties of fatty compounds.
  • Viscosity is an important issue, not only considering the lubricative properties, but from the application point of view as well. Namely, in order to apply thin layers (around 1 ⁇ m), viscosity of the PLP should not be too high. On the other hand, too low viscosities would lead to poor lubrication.
  • Another important parameter is the surface energy of the PLP, both before and after curing. For good wetting of a PLP-wetted surface by a metal primer, the surface energy of the primer should be lower than that of the PLP. Due to the fatty and apolar character of the PLP's, these compounds are generally expected to possess rather low surface energy values.
  • a stoichiometric mixture of Edenol B316 and Pripol 1040 was prepared.
  • the viscosity of this mixture was measured with a Brookfield Model DV-II+ Viscometer (Spindle 4, 100 RPM) at three different temperatures, resp. 25, 50 and 75°C.
  • spindle 4 100 RPM
  • the viscosity of Edenol B316 was measured using the same procedure.
  • Excessive UV irradiation might be a method for increasing the polarity of the surface and hence increasing the wetting and adhesion by the primer which will be applied on this PLP.
  • a dose should be chosen at which the surface is sufficiently attacked, while the bulk coating is not the subject of degradation reactions.
  • the PLP-compositions of the invention would not be particularly suited in the invention. Namely, no good wetting of paints is generally be expected on substrates (in this case the PLP layer) of significant lower surface energy. In practice, however, it was surprisingly found that the PLP-compositions of the invention provide good properties, as demonstrated by the results given below.
  • Example II Systems based on epoxy-functional compounds and cationic UV-initiators.
  • Sample preparation Samples were prepared by weighing determined amounts of epoxide, UV initiator, additives and coreagants in a flask. After vigourously stirring, thin films of defined thickness were prepared on glass or metal plates by means of a doctor blade.
  • UV Irradiation Samples were lead past a Philips HOK 20/100 UV lamp by means of a conveyor belt. The distance between lamp and sample was kept constant at 14 cm. The radiation dosis amounted to 610-630 mJ/cm unless described differently. Due to the intensity of the UN lamp, temperature of the samples increased to circa 60°C upon irradiation. Eventually, samples were preheated prior to UV irradiation. After UV irradiation, samples were postcured in an aircirculated oven at 100°C.
  • a cotton-endcapped hammer was soaked with methyl ethyl ketone, and double rubs of about 5 cm were performed while keeping the exerted pressure constant at ca. 90 N/m 2 . The number of double rubs were counted, which were required to reach the substrate.
  • adhesion improvers can be required particularly in the case of UV curing resins.
  • the influence of three different adhesion improvers on cationic curing of Edenol B316 was investigated. Selected adhesion improvers were: Silquest A- 187, A- 189 and A- 1100 (Union Carbide). Table 5 overviewes curing experiments of Edenol B316 in presence of these adhesion promotors.
  • Silquest A- 1100 leads to severe inhibition of the cationic curing process. This is due to the basic amine groups, which react with the acid formed upon UV irradiation of the photoinitiator. For that reason, Silquest A- 1100 is not suitable as adhesion promotor in the cationic curing process.
  • Silquest A- 189 The basicity of the thiol groups in Silquest A- 189 is apparently high enough to show a significant degree of inhibition as well. Silquest A- 187 does not affect the cationic curing reaction, and is additionally compatible with epoxy resins due to its epoxy functionality.
  • Comparative Example I Systems based on polycarboxylic acids and polyols.
  • Sovermol Pol 1072 polyol
  • Pripol 1040 fatty trimer acid
  • 2.1 g Pripol 1040 was mixed with 3.9 g Sovermol Pol 1072 and vigourously stirred with a glass bar. Thin films of ca. 80 ⁇ m were cast on glass plates. Curing was performed at different temperatures during different times in an aircirculated oven. Appearance and resistance against MEK double rubs were investigated as a function of curing time.
  • the curing reaction of Sovermol Pol 1072 with Pripol 1040 was also momtored by thin film FT-IR spectroscopy.
  • the yellow starting formulation was characterised by a fatty non-interacting behaviour which is favourable for lubricant applications.
  • Table 6 shows the results of curing experiments.
  • Comparative Example II Systems based on polyols and polydimethylesters. Concerning their lubricating behaviour, dimethylester compounds were expected to be suitable candidates as base materials for PLP systems, as illustrated by the large amount of commercial available lubricants which are based on ester compounds. However, no efficient curing reaction could be performed using dimethylester compounds with fatty polyols. Addition of different basic catalysts appeared to be ineffective. Only at very high temperatures (>220°C), a rapid crosslinking could be observed. However, this can probably be ascribed to degradation reactions as illustrated by the strong brown discoloration of the products.
  • Pripol 1040 methyl ester with Pripol 2033 0.45 g Pripol 2033 was mixed with 0.57 g Pripol 1040 methyl ester. Thin films of the yellow-brown mixture were casted on glass plates. The films were cured in an air-circulated oven at 200°C during different times. The curing reaction was extremely slow. Also, a gradual brown discoloration could be observed.
  • Sovermol Pol 1072 with dimethyl sebacate 0.45 g Pripol 2033 was mixed with 0.57 g Pripol 1040 methyl ester. Thin films of the yellow-brown mixture were casted on glass plates. The films were cured in an air-circulated oven at 200°C during different times. The curing reaction was extremely slow. Also, a gradual brown discoloration could be observed.
  • Sovermol Pol 1072 with dimethyl sebacate 0.45 g Pripol 2033 was mixed with 0.57 g Pripol 1040 methyl ester. Thin films of the yellow-brown mixture were casted
  • titaniumisoproxide was investigated as a catalyst. Amounts of catalyst upto 5 wght% ⁇ did not show any significant improvement compared to the system without catalyst. At 220°C, a rapid cure was observed resulting in fully cured films within 0.5 hrs. However, severe brown discoloration indicated a crosslinking mechanism different from the transesterification reaction (e.g., partial degradation).
  • UV-curable coating on the basis of an epoxidized oil.
  • a mixture of Edenol B316 (Henkel) with 3 wt.%> UV-6990 (Union Carbide) is applied as a thin layer (about 1 ⁇ m) on degreased strip steel using a doctor blade.
  • the metal plate is then led under an UV-source (HOK 20/100) at a distance of 14 cm. The speed is such that the UV-dose is 610-630 mJ/cm .
  • a primer Sigma Moffelprimer 67 EU
  • UV-curable formulation on the basis of epoxidized oils and fatty polyols.
  • the metal plate is led under an UV-source (HOK 20/100) at a range of 14 cm. The speed is such that the UV-dose is 610-630 mJ/cm 2 .
  • a primer (Sigma Moffelprimer 67 EU) is applied at a thickness of a 35 ⁇ m.
  • the system is thermally cured in an oven (170°C/15 min.).
  • V Thermal-curable formulation on the basis of epoxidized oils and only fatty acids.
  • a stoichiometric mixture (ratio epoxy/carboxylated acid is 1/1) of Edenol B316 (Henkel) and Pripol 1040 (Unichema International) is applied as a thin layer (about 2 tim) on degreased steel.
  • a primer (Sigma Moffelprimer EU 67) is applied.
  • the combined system is then cured in an oven (180°C/20 minutes). Adhesion between the top layer and the lubricant layer and the adhesion between the steel substrate and the coating were scored as zero.
  • a (partial) thermal curing is carried out before the primer is applied, the choice of the primer is less critical with a view to defects in the coating. Also, in this manner, an "overbake" of the primer can be avoided.
  • the viscosity of liquid-permanent PLP systems can be decreased by using emulsions.
  • thermally curable formulations can be dispersed in water.
  • a stoichiometric mixture (ratio epoxy/carboxylic acid is 1/1) of Edenol 2316 (Henkel) and Pripol 1040 (Unichema International) is mixed with 10 wt.% surfactant (for example a mixture of Disponyl 23 (Henkel) and Tween 20 (Merck)). Water is added as described above. After drying, the primer is also applied as described above.
  • the potiife of an epoxidized oil fatty acid mixture of the invention (a mixture of Edenol B316 and Pripol 1040) was determined by measuring the change of viscosity in time at 22°C. The results are given in Figure 3.
  • EXAMPLE NIII thermal curing of epoxidized oils with fatty polyacids.
  • EXAMPLE LX UV-curing of epoxidized oils.
  • Adhesion improver l wght% A-189 Photoinitiator: UVI-6990
  • PLP and topcoat 15 min 150°C (Flexine) or 170°C (Sigma)
  • EXAMPLE X Lubrication measurements. The tribology of the PLP-compositions of the invention was determined on a
  • TNO-slide sheet - tribological system the general principle of which is shown in Figure 4.
  • a ring is slid under defined conditions (speed, force, etc.) over a metal plate.
  • the friction coefficient is dete ⁇ nined as a function of distance. As a limiting value for the friction coefficient 0.2 is taken.
  • test conditions were as follows:
  • Deep drawing involves clamping a metal sheet between a blank holder and a die. Subsequently, a punch is rammed into the sheet, forcing it into the die. The metal sheet adapts to the shape of the die.
  • FIGs 6a and 6b the process is schematically shown, in which 1 is the punch, 2 is the blank holder and 3 is the blank.
  • the clamping force on the blank is adjusted since a too high force may result in tearing of the product, while a too low force causes wrinkling of the product.
  • An important parameter in the deep drawing process is the drawing ratio:
  • t p ⁇ is the initial radius of the blank (before deep drawing)
  • r p is the radius of the product after deep drawing, as shown in Figure 7.
  • the limiting drawing ratio is dependent on material properties, blank thickness and lubrication. For a given blank and tool material, an impression of the efficiency of a particular lubricant can be obtained by determining the limiting drawing ratio.
  • This Example describes experiments in which different catalysts were tested for application in thermally curing PLP's based on epoxidized oils and fatty polyacids.
  • a catalyst is used which is very active at the curing temperature ( ⁇ 180°C), but shows no activity at lower temperatures (typical for storage and metal processing).
  • Basic catalysts of different types were tested: Sodium carbonate and zinc oxide (inorganic alkaline salts), zinc- and magnesium stearate (organometallic salts), and benzyl dimethylamine and triphenylphosphine (organic basic compounds).
  • EXAMPLE XIV Emulsions of Edenol B316 in water stabilised with a surfactant.
  • Atsurf 3969 was added to Edenol B316.
  • the mixture was heated to 50°C and stirred by means of a Dispermat provided with a dissolver blade.
  • Demineralised water was slowly added until the inversion point was reached. The temperature was gradually decreased to room temperature and further water was added at a slightly higher rate until the desired oil/water ratio was reached.
  • typical conditions are given: e.g.: 0.5 g Atsurf 3969 was added to 5 mL epoxidized oil and heated to 50°C. The mixture was stirred at 4000 rpm and 10 mL water was slowly added with 0.250 mL/min. The heating was turned off, and further 35 mL of water was added at a speed of 0.333 mL/min. 2. Viscosity measurements:
  • Measurements were performed at 25°C on a Paar Physica UDS200 using a cone and plate geometry with a truncated cone (Measuring system Zl DIN (double gap), Device MC200 SN253581).
  • the stability of an emulsion was determined by measuring the time until precipitation of the oil phase was visible by eye. Furthermore, samples were taken from the aqueous phase of emulsions which were stored while avoiding movement of the sample. By weighing the sample before and after evaporation of the water in vacuum at 50°C overnight, the oil content in the aqueous at the time of sample taking could be calculated.
  • the viscosity of Edenol emulsions was measured using a rheometer provided with a cone and plate geometry. The viscosity was measured as a function of shear rate varying between 1 and 1000 s-1.
  • Figure 10 shows the results for water and 3 emulsions with different Edenol contents. The results show that stable emulsions can be obtained which possess viscosities which are comparable to that of water.
  • EXAMPLE XV UV-curing of PLP's applied from emulsion.
  • This Example is directed towards UV curing of epoxidized oil which has been applied from emulsion.
  • Edenol B316 was chosen as the epoxidized compound, while HEC and Atsurf 3969 were used as the emulsion stabilizers.
  • the emulsions were prepared essentially as described in Example XIN.
  • UV-curing was carried out as follows: Emulsions were applied on metal sheet by means of a doctor blade with a thickness of circa 35 ⁇ m. The layers were dried during 10 minutes (unless described differently) under an infrared lamp. The temperature was controlled by thermocouples attached to the metal substrate, and was kept at 60°C. The dried films were lead past a Philips HOK 20/100 UV lamp by means of a conveyor belt. The distance between lamp and sample was kept constant at 14 cm. The radiation dose amounted to 610-630 mJ/cm2. Due to the intensity of the lamp, temperature of the samples increased to circa 60°C upon irradiation.
  • Atsurf 3969 is a suitable emulsion stabilizer that does not disturb the cationic curing reaction.
  • UVR were stabilized by 10 wt%> Atsurf. Results are given in Table 15.
  • Non-tacky coatings with excellent solvent-resistance were obtained when 5 wt% UV initiator was applied. Although curing proceeds to a significant degree when lower amounts of initiator were used, coatings were tacky and sensitive towards ethanol when 3 wt% or less initiator was applied. It must be noted however, that for PLP applications no complete solvent resistance is required, because the PLP layers are completely covered by a top layer. After the curing, the PLP should have been formed into a solid layer, which can provide good adhesion with the top layer resulting in a mechanically stable coating system.
  • Drying of the emulsions by means of infrared lamps proved to be efficient. This method provides selective heating of the surface of substrates. Furthermore, ventilation is well possible.
  • a cationic UV initiator (UVI-6974, Union Carbide) was added to Edenol B316 (Henkel) epoxidized oil. The initiator content was varied. Concentrations are mentioned in the text. The mixture was homogenized by vigorous stirring. In the case of emulsions, 10 wt% of Atsurf 3969 (ICI) was added to the PLP mixture, and an emulsion was prepared by means of the inversion method as described in the previous chapter.
  • PLP metal substrates were carefully degreased using heptane/hexane vapour. A thin PLP layer was applied by means of a doctor blade (ca. 30 ⁇ m). PLP's from emulsion were dried under an infra red lamp during 10 minutes at 60°C. Excessive PLP was removed with a tissue. PLP systems were UV irradiated by a Philips HOK 20/100 UV lamp in nitrogen atmosphere prior before the commercial primer was applied.
  • the UV dose generally amounted to 610-630 mJ/cm2.
  • Samples were transported along the UV lamp by means of a conveyor belt at a distance of 14 cm of the lamp. Due the light intensity, temperature of the samples increased to circa 60°C.
  • a metal primer was applied. Commercial primers in all cases were applied by a doctor blade. The thickness was varied. The system was thermally cured in an air-circulated oven at conditions according to technical specifications of the metal primer used:
  • a cotton-endcapped hammer was soaked with methyl ethyl ketone, and double rubs of about 5 cm were performed while keeping the exerted pressure constant at ca. 90 N/m2. The number of double rubs was counted, which were required to reach the substrate.
  • Atsurf 3969 in a PLP based on epoxidized oil results in a more polar surface. Since the commercial coatings generally possess a rather polar nature as well, presence of surfactant in the PLP leads to improved compatibility between the PLP and top coating. Hence, the surfactant is able to perform both as emulsion stabilizer and as adhesion improver.
  • Table 18 shows adhesion experiments for different commercial coatings on PLP's which were applied from emulsion.
  • Edenol B316 was either mixed with UVR-6110 or UVR-6128.
  • the PPG coating contained no bare patches after curing the system, although some differences in coating thickness could be observed by eye.
  • the percentage wetted surface decreased with increasing Edenol thickness.
  • the thickness of the PLP layer is of the same order of magnitude as the roughness of the steel substrate, no curing of the PLP before application of the commercial coating is required for obtaining good adhesion of the top coating. However, it appeared that the optical appearance of the top coating is improved when the PLP is cured before the commercial coating is being applied.
  • a mixture of Cymel 303 containing 1 wt%> para-toluene sulphonic acid was prepared. A determined amount of the catalysed mixture was added to a weighed amount of either Edenol B316, Sovermol Pol 1072, Pripol 1013 or Pripol 1040. Ratio and/or amounts are given in the text. The mixture was homogenised by vigorously stirring.
  • the viscosity of Edenol B316/Cymel 303, Sovermol Pol 1072/Cymel 303 and Pripol 1013/Cymel 303 was measured at 50°C after different times of storage at 50°C. All mixtures contained 10 wt%> Cymel 303 to which 1 wt%> para-toluene sulphonic acid had been added. The viscosity of Edenol/Pripol mixtures was measured with a Brookfield Model DV-II+ Viscometer (Spindle 5, 100 RPM).
  • Coatings were generally applied by means of a doctor blade. Coating thicknesses were varied as mentioned in the text. In the case of aqueous emulsions, layers were dried under an infrared lamp at 60°C during 10 minutes. The temperature was controlled by means of a thermocouple. In particular cases, excess coating was removed with a tissue after application in order to obtain coatings with thicknesses of order of magnitude of the roughness of the metal substrate.
  • the transition temperature was determined at which the coating changed from tacky to non-tacky and from liquid to solid. Subsequently, the plate was placed at one side in methyl-ethyl kettle for one hour, and the curing temperature was determined, at which the coating did not disappear from the aluminium substrate upon the solvent exposure.
  • non-tacky coatings can be obtained by curing around 235°C for 2 minutes.
  • the Edenol/Cymel mixture did not show a viscosity increase during the first two weeks of storage at 50°C.
  • the same Edenol/Cymel mixture was prepared without acid catalyst. In this case, no inhomogenities and no viscosity increase were observed over a longer period of several months.
  • the stability of the emulsions was further confirmed by measurement of the non-volatile content of the emulsion as a function of time. Also, the emulsions showed excellent adhesion on both P-G21032N (PPG) and Flexine MM commercial coatings, both with a non-cured and a pre-cured PLP. The adhesion also proved essentially not to be dependant on the Cymel content.
  • Tungsten Inert Gas (TIG) welding processes are used.
  • TIG welding was both performed in T-geometry and ropes on steel sheet (2 mm). In both cases, the average current amounted to 127 An and the average charge was 12.3 V.
  • Figure 14 shows MAG welding in presence of PLP-1, with from left to right: 1) reference without PLP, 2) rope on metal sheet with thick PLP layer, 3) rope on sheet with thin PLP layer, 4) corner welding on sheet with thin PLP layer.
  • Figure 15 shows MAG welding in presence of PLP-2, with from left to right: 1) reference without PLP, 2) rope on metal sheet with thick PLP layer, 3) rope on sheet with thin PLP layer, 4) corner welding on sheet with thin PLP layer.
  • FIG. 16 shows TIG welding in presence of PLP-1, with from left to right:
  • FIG. 17 shows TIG welding in presence of PLP-2, with from left to right:
  • Figure 18 shows a P-G21032N coating (PPG) on UV- cured PLP layer: cured film without defects.
  • Figure 19 P-G21032N coating (PPG) on non-cured PLP layer: Although the PPG is crosslinked, the PLP underground still is liquid, and dewetting has occurred.

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Abstract

L'invention a trait à une composition de conservation / lubrification / apprêt pour substrats métalliques, notamment pour substrats d'acier tels que de l'acier feuillard, qui comporte au moins une huile époxydisée. La composition peut contenir en outre au moins un constituant de réticulation, tel un initiateur d'UV ou un polyacide gras. L'huile époxydisée est de préférence un dérivé époxydisé d'une graisse ou d'une huile insaturée, notamment un dérivé époxydisé d'une « huile siccative » naturelle. La composition peut être utilisée comme agent de conservation, lubrifiant et/ou apprêt pour substrats métalliques, notamment en vue d'un stockage/transport, d'un traitement de formage/étirage, et/ou d'une application de revêtement. Grâce à l'invention, il n'est plus nécessaire d'utiliser des compositions séparées pour chacune de ces étapes de traitement.
EP99949458A 1998-10-05 1999-10-05 Composition de conservation / lubrification / appret pour surfaces metalliques Withdrawn EP1129157A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99949458A EP1129157A1 (fr) 1998-10-05 1999-10-05 Composition de conservation / lubrification / appret pour surfaces metalliques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98203365 1998-10-05
EP98203365A EP0992569A1 (fr) 1998-10-05 1998-10-05 Composition pour préserver, lubrifier et apprêter des surfaces métalliques
EP99949458A EP1129157A1 (fr) 1998-10-05 1999-10-05 Composition de conservation / lubrification / appret pour surfaces metalliques
PCT/NL1999/000617 WO2000020538A1 (fr) 1998-10-05 1999-10-05 Composition de conservation / lubrification / appret pour surfaces metalliques

Publications (1)

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EP1129157A1 true EP1129157A1 (fr) 2001-09-05

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EP98203365A Withdrawn EP0992569A1 (fr) 1998-10-05 1998-10-05 Composition pour préserver, lubrifier et apprêter des surfaces métalliques
EP99949458A Withdrawn EP1129157A1 (fr) 1998-10-05 1999-10-05 Composition de conservation / lubrification / appret pour surfaces metalliques

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EP98203365A Withdrawn EP0992569A1 (fr) 1998-10-05 1998-10-05 Composition pour préserver, lubrifier et apprêter des surfaces métalliques

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WO (1) WO2000020538A1 (fr)

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Publication number Priority date Publication date Assignee Title
AU2012376541B2 (en) * 2012-04-09 2016-05-12 Avery Dennison Corporation Pressure sensitive adhesives based on renewable resources, UV curing and related methods
WO2016033603A1 (fr) * 2014-08-29 2016-03-03 Iowa State University Research Foundation, Inc. Produits et matériaux asphaltiques améliorés et leurs procédés de production
US10961395B2 (en) 2016-02-29 2021-03-30 Iowa State University Research Foundation, Inc. Rejuvenation of vacuum tower bottoms through bio-derived materials
US10570286B2 (en) 2016-08-30 2020-02-25 Iowa State University Research Foundation, Inc. Asphalt products and methods of producing them for rejuvenation and softening of asphalt
CA3149052A1 (fr) 2019-09-18 2021-03-25 Eric W. Cochran Biosolvants utiles pour des produits asphaltiques ameliores utilisant un revetement d'asphalte recycle ou d'autres liants d'asphalte fragiles tels que le fond de tour sous vide

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Publication number Priority date Publication date Assignee Title
DE1068408B (de) * 1956-03-19 1959-11-05 A. Boake, Roberts & Company Limited, Stratford, London (Großbritannien) Herstellung von Korrosionsschufczüberzügen auf Metallen mittels öligen oder ölharzhal'tigen Anstrichmitteln
DE1452105A1 (de) * 1964-04-07 1969-10-23 United States Steel Corp Verfahren zum Walzen von Stahlblech
US3582368A (en) * 1968-12-30 1971-06-01 Borden Inc Corrosion-inhibiting composition
CA2038936A1 (fr) * 1989-08-09 1991-02-10 Rainer Frische Methode de production de plastiques a partir d'huiles et de graisses brutes
US5318808A (en) * 1992-09-25 1994-06-07 Polyset Company, Inc. UV-curable coatings

Non-Patent Citations (1)

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Title
See references of WO0020538A1 *

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EP0992569A1 (fr) 2000-04-12
WO2000020538A1 (fr) 2000-04-13
AU6232599A (en) 2000-04-26

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