CA2225027A1 - Coating substrates - Google Patents
Coating substrates Download PDFInfo
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- CA2225027A1 CA2225027A1 CA002225027A CA2225027A CA2225027A1 CA 2225027 A1 CA2225027 A1 CA 2225027A1 CA 002225027 A CA002225027 A CA 002225027A CA 2225027 A CA2225027 A CA 2225027A CA 2225027 A1 CA2225027 A1 CA 2225027A1
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- Prior art keywords
- meth
- coating
- acrylate
- monomers
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- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/06—Processes, 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 wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/06—Processes, 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 wood
- B05D7/08—Processes, 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 wood using synthetic lacquers or varnishes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Abstract
In a method for coating a substrate, preferably a cellulosic substrate, an aqueous coating comprising a polymer having carbonyl functional moities may be tandem coated directly onto or beneath an UV cured coating. The method provides a low VOC system which offers good adhesion between the two coatings.
Description
CA 0222~027 1997-12- 18 Coating Substrates This invention concerns a method for tandem coating substrates with both highly crosslinked thermoset coatings and aqueous based coatings. In particular,though not exdusively, the invention concerns a method for tandem coating losic sul,sll~lles with both high solids W curable coatings and waterborne paints.
Cellulosic substrates, particularly composite cellulosic substrates such as MDF, hardboard and particle board, are extensively used in the manufacture of interior furniture and other board applications. Often, to prevent water penetration into the substrate which otherwise might cause damage to the substrate by fiber swelling due to hydration, the substrate is coated with a low VOC, high solids Wcurable coating which, once cured, seals the substrate and provides an effectivebarrier against water ingress.
Unfortunately, high solids W curable coatings tend to be more suited to clear, rather than pigmented, applications. Accordingly, when required for decorative purposes, substrates sealed with clear W cured coatings would normally be subsequently painted with a pigmented, organic solvent based topcoat.
With increasing environmental and governmental regulatory pressure, there is a strong desire to reduce or eliminate volatile organics in paints. However, currently, in many coatings markets, organic solvent borne paints still dominatebecause alternative water-based, low VOC paints fail to meet the performance criteria required of them. In particular, in the case of cellulosic substrates, though -the combination of a high solids W curable sealer in conjunction with a waterborne, pigmented topcoat would appear to offer a route to low VO~,- low energy coatingswith attractive economics, because of the severe adhesion problems typically encountered between waterborne topcoats and highly crosslinked undercoats, the successful implementation of this system has not been realised.
A number of prior art documents disclose waterborne compositions for coating various substrates. For example:
JP-A-7102218 (Nippon Carbide Industries KK) discloses an aqueous coating composition comprising a core/shell polymer, having acetoacetyl groups in the shell . CA 0222~027 1997-12-18-polymer, hydrazine derivatives with residual hydrazine groups and/or amines withtwo or more amine groups, and pigments. The composition is described to be suitable for coating many substrates induding metal sub~ les, plastics substrates, wood, leather and inorganic substrates sudh as concrete or mortar, and over old films such as on vinyl chloride, alkyd resins and other old paint films. The plastics substrates ~ ose~l are ABS sheet, poly~Ly~e,le sheet and vinyl d~loride covered steel sheets, whidh plastics are generally known to be thermoplastics materials DE-A-4344391 (Rohm GmbH) discloses aqueous dispersions of film-forming polymers based on polymethyl(meth)acrylate esters for coating surfaces of thermoplastic parts. The film-forming polymer may be polymerised from a monomer system comprising up to 15% crosslinkable monomer with an acetoacetyl group, such as acetoacetoxyethylmethacrylate (AAEM).
U~A-5213901 and U~A-5227423 (Rohm and Haas Company) disclose an aqueous binder composition comprising a copolyrner formed from a monomer system including 10 to 35% by weight of a wet adhesion promoting monomer selected from the group consisting of ethyleneureido-, cyanoacetoxy- and acetoacetoxy- containing monomers and hydroxymethyldiacetoneacrylamide. The binder is disclosed for use in a paint.
U~A-5278225 (Wacker-Chemie GmbH) discloses aqueous dispersions of copolymers - comprising acetoacetoxy functional groups and aminooxy crosslinking agents useful as binders for producing coverings, coatings and impregnations in the coating field.
It is disclosed that the dispersions are particularly suitable as adhesives forbonding to corona- and flame- pretreated polyolefin surfaces.
EP-A-0697417 (Rohm and Haas Company) discloses a latex-binder for producing a high gloss coating on a weathered substrate, which substrate may be a chalky, wood or cement substrate. The binder is disclosed to comprise a latex polymer bearing an acid functional pendant moiety and an enamine functional pendant moiety resulting from the reaction of acetoacetyl functional pendant moity on the latex polymer with ammonia or amine.
Whilst the prior art documents generally teach the use of aqueous coatings on various substrates, none of these documents disclose or suggest that the aqueous CA 0222~027 1997-12-18 coatings may be successfully applied to highly crosslinked polymeric surfaces, such as are formed when a substrate is coated with a thermoset material, and thereby replace the solvent-borne coatings which are so commonly used for this very specific application. Where lefelellces to coating polymeric surfaces have beerl made in the above prior art documents, the polymeric s-lrfAres have been thermoplastic materials, which materials are generally understood to be not highly crosslinkedmaterials.
It is an object of the present invention to provide a low VOC system for tandem coating substrates with both a highly crosslinked coating and a waterbased coating.
In accordance with the present invention there is provided a method co~ g tandem coating a substrate with (i) a highly crosslinked coating formed from a W curable composition, and (ii) a cured coating formed from an aqueous composition comprising a polymer comprising, as polymerised units, 0.1 to 100%, preferably 1 to 50% and even more preferably 5 to 20%, by weight of the polymer of at least one monomer capable of producing carbonyl functional moities in the polymer. The substrate may be coated first with the highly crosslinked coating (i) followed by the cured coating (ii), or the substrate may be coated first with the cured coating (ii) followed by the highly crosslinked coating (i). The method of the present invention provides a low VOC system for tandem coating substrates with both a highly crosslinked coating and a waterbased coating.
The highly crosslinked coating (i) is preferably formed from a thermoset materiaL Such material may be a W curable composition, which before cure may be a high solids composition or a waterborne composition cornp-rising appropriate Wcurable components. W curable coatings can be generally divided into two main categories: 1) free radical polyrnerised (meth)acrylate functionalised polymers and 2) cationically polymerised epoxies. Methacrylate and acrylate functionalised polymers generally comprise (meth)acrylate-functional oligomers and monomers combined with a photoinitiator to facilitate W cure. These (meth)acrylate-functional oligomers are typically prepared by a) reaction of difunctional epoxies with methacrylic or acrylic acid, b) the condensation product of difunctional . CA 0222~027 1997-12-18 isocyanates with hydroxy-functional (meth)acrylates, or c) the condensation product of (meth)acrylic acid and hydroxyl groups on a polyester backbone, or an hydroxyacrylate with residual acid groups on a polyester backbone. Cationic systems arebased on cycloaliphatic epoxies and a photoinitiator which decomposes to give a "super" acid with W radiation. The super acid catalyses the cationic polyrn~ri.c~tiQn of the epox~y. (See Radiation Curing In Polymer Science And Technology, Vol 1: Fundamentals in Methods, Edited by J.P. Fouassier and J.E.
Rabek, published by Elsevier Applied Science (1993). The W curable coatings after exposure to W radiation produce highly crosslinked coatings which have traditionally proved difficult to adhere waterbased topcoats onto without the use of an intermediate coating. Preferably, the coating (i) is cured in the presence ofoxygen, more pre~e,dbly in the presence of air.
The cured coating (ii) is formed from an aqueous composition co~ rising a carbonyl functional polyrner preferably comprising polymerised units of one or more monomers selected from the group consisting of ethyleneureido-containing monomers, cyanoacetoxy-containing monomers, acetoacetoxy-containing monomers, acrolein, methacrolein, vinyl (C,-C20)alkyl ketones and keto-containing amides such as diacetone acrylamide. The ethyleneureido-containing monomers, cyanoacetoxy-containing monomers, and acetoacetoxy-containing monomers are described in detail in US-A-5213901 on column 3, line 48, to column 4, line 38.
In a particularly ~,efelled embodiment, the aqueous composition comprises a polymer comprising from 0.1 to 100%, more preferably 1 to 50%, and most preferably 5 to 20% by weight polymerised units of one or more acetoacetyl functional monomers having the structure:
O R,O
A-(-C -C -C-)-B
H
wherein R, is either H, alkyl having 1 to 10 carbon atoms or phenyl;
A is either:
CA 0222~027 1997-12- 18 C=C- (- R~,-)a-(-X-)n-(-C-Y-)m-(-Rs-)q H
or R2 R~, O
~C=C-(-R4-)a-(-X-)n-(-C-Y-)-(-Rs-)q-O-H
wherein R2 is either H, alkyl having 1 to 10 carbon atorns or phenyl, substituted phenyl, halo, CO2CHy or CN, R3 is eitherH, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl or halo, R4 is either alkylene or substituted alkylene having 1 to 10 carbon atorns or phenylene, or substituted phenylene, Rs is either alkylene or substituted alkylene having 1 to 10 carbon atoms;
a, m, n and q are independently either 0 or 1, X and Y are independently either -NH- or -O-;
B is either A, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, or heterocyclic, preferably a (C4 to C10) heterocyclic.
Particularly preferred monomers are acetoacetoxyethylmethacrylate (AAEM), acetoacetoxyethylacrylate (AAEA), acetoacetoxypropylmethacrylate, allylacetoacetate, acetacetoxybutylmethacrylate, 2,3-di(acetoacetoxy)~ro~yl methacrylate, vinyl acetoacetate, or combinations thereof.
Optionally, the polymer used in coating (ii) is a copoIymer comprising carbonyl functionality wherein the copolymer comprises, as polymerised units, from 0 to 99.9%, preferably 50 to 99%, more preferably 80 to 95%, by weight of one or more copolymerisable monomers. Preferably, the copolymerisable monomers are selected from the group consisting of substituted and unsubstituted, saturated and monoethylenically unsaturated carboxylic acid ester monomers, such as methyl(meth) acrylate, ethyl(meth) acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, CA 0222~027 1997-12- 18 isodecyl(meth)acrylate, oleyl(meth)acrylate, palmityl(meth)acrylate, stearyl(meth)acrylate, methyl itaconate, methylfumarate, butyl fumarate, glycidyl methacrylate, dicydopentadienyl(meth)acrylate, isocyanatoethylmethacrylate hydroxyethyl(meth)acrylate, hydroxy~ro~yl(meth)acrylate, N,N'- .
rlimethylarnino(meth)acrylate and vinyl acetate; subsituted and unsubstituted call,oxylic acid monomers and anhydrides thereof, such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydide;
substituted and unsubstituted (meth)acrylamide monomers; styrene and substitutedstyrene monomers; other substituted or unsubstituted vinyl monomers such as vinyl chloAde, vinylidene chlorAde and N-vinylpyrrolidone; other substituted and unsubstituted alkylene monomers such as ethylene, propylene, butylene, and is~pr~ylene; and acrylonitrile and methacrylonitrile.
If desired, the polymer used in coating (ii) may also comprise, as polymeAsed units, 0.1 to 25% by weight substituted and unsubstituted polyfunctional ethylenically unsaturated monomers such as allylmethacrylate, diallylphthalate, 1,4-butyleneglycol di(meth)acrylate, 1,6-hexanediol diacrylate and divinylbenzene.
Such monomers tend to induce premature crosslinking or gelling of the copolymer.The copolymer used in coating (ii) is preferably a thermoplastic or substantially uncrosslinked copolymer when it is applied (in its uncured state) to the substrate.
The polymer used in coating (ii) may comprise acid functional pendant moiety sufficient to provide the polymer with an acid number of from 1 to 325, preferably from 3 to 130. The desired acid number is achieved by controlling theamount of acid functional monomer utilized in the polymer by a known method.
The polymer used in coating (ii) ~refelably has a glass transition temperature of from ~0 ~C to 120~C, as measured by differential scanning calorimetry. The Tg is is reported at the mid-point of the inflection using the half-height method. A polymer having a Tg of from 0~C to 90~C is most preferred. Preferably, the polymer has aGPC weight average molecular weight of 500 to 5,000,000. The GPC weight average molecular weight can be adjusted through the appropriate use of methods known inthe art such as by the use of chain transfer agents. "GPC" weight average molecular . CA 0222~027 1997-12-18 _ weight means the average molecular weight as determined by gel permeation d~romatography as described on page 4 of The Characterization of Polymers published by Rohm and Haas Company in 1976, utilizing polymethymethacrylate as the standard. The average partide size on the diameter of the polymer particles suitable for use in the coating (ii) is preferably from 20 to 1000 nm, more ~re~elably 30 to 500 nm.
The aqueous composition in coating (ii) may comprise at least two mutually incomratible copolymers, at least one of which is the polymer having carbonyl functional moities described above. These mutually incompatible copolymers may be present in the following morphological configurations, for example, core/shell partides with complete shell phases surrounding a single core, core/shell particles with shell phases incompletely encapsulating the core, core/shell particles with a multiplicity of cores, interpenetrating network particles, and multilobal particles de~ribed in the commonly assigned U~A~791151. In all these cases, the majority of the surface area of the particle will be occupied by at least one outer phase and the interior of the particle will be occupied by at least one inner phase. The mutual incompatibility of the two polymer compositions may be determined in various ways known in the art. The use of ~anning electron microscopy using staining techniques to emphasise the differenoe between the appearance of the phases, forexample, is such a technique.
In a further embodiment of the invention, the polymer used in coating (ii) may be blended with other polymers, such as those polymers normally found in paints and other coatings. For example, the copolymer (ii) may be blended with apolyurethane, a polyester, a polyamide, an acrylic copolymer, a styrene-acrylic copolymer or another polymer, or mixtures of two or more of such polymers.
The polymerisation techniques which may be used to prepare the polymer are well known in the art. The polymer may be prepared by aqueous, solution or emulsion polymerisation, with emulsion polymerisation being preferred. The polymerisation may be a redox or thermal initiation process employing conventional free radical initiators, such as, for example, ammonium and alkyl sulphates, hydrogen peroxide, benzoyl peroxide or t-butyl peroctoate at levels typically of from CA 0222~027 1997-12- 18-0.05 to 3% by weight based on the total weight of monomer. Redox systems using the same initiators coupled with suitable reducing agents such as for example isoascorbic acid, sodium bisulphite or sodium sulphoxylate formaldehyde may be used a similar levels.
The polymer ~refelably comprises from 1 to 100% of the total solids in coating (ii). Typically, the coating (ii) will ~r~elably comprise 80 to 30% water.
The coating (ii) may comprise additional ingredients, such as thickeners, sl1rf~ctAnts, pigments, flatting aids, waxes, slip aids, coalescents and/or plasticisors, such materials being typical ingredients of waterbased paints and coatings. The coating may also include a post crosslinking agent such as polyaziridine, polyisocyanate, polycarbodiimide, polyepoxide, polyaminoplast, polyalkoxysilane,polyoxazolidine, polyamine and polyvalent metal compounds, to improve the cure time of the waterbased coating once it has been applied to the s~sl,dLe.
Preferably, the substrate is a cellulosic material, such as wood or paper or a composite material thereof, such as MDF, hardboard, particle board or cardboard.In a particularly preferred embodiment, the cellulosic mateial is selected from the group consisting of wood, MDF, hardboard and particle board. Such materials typically find application in the manufacture of interior furniture and home fittings.
In this embodiment, preferably the cellulosic substrate is first coated with the highly crosslinked coating (i), which may act as a sealer or undercoat to prevent the ingress of water into the fibers of the substrate, and then the substrate, with the highly crosslinked coating, is further coated with the waterbased coating (ii). The waterbased coating may be a paint, including a pigment and other components typically found in such formulations, to give, once cured, the appropriate decorative effect to the substrate. In another embodiment, the cellulosic substrate is a paper material such as may be typically used in a printing or packaging application. Here, the waterbased coating (ii) may first be applied to the substrate, such as in the form of an ink, and then the cured waterbased coating (ii) and substrate are both coated with the highly crosslinked coating (ii).
The invention will now be further described with reference to the following examples:
CA 0222~027 1997-12- 18-Examples Various emulsion polymers A to I as detailed in Table I were prepared by the following procedure:
Procedure for Preparation of Polymer A
A 4-neck, 5-liter round bottom reaction flask containing an Initial Kettle Charge of 850 g DI water and 35.5 g lauryl (EO)~ Na sulfate (30%) was heated to 85 ~C under a nitrogen sweep. At 85 ~C, an aliquot of a Monomer Rm~ n (ME) comprising 750 g DI water, 38.8 g lauryl (EO)~ Na sulfate (30%), 538 g butyl acrylate (BA), 697.9 g methyl methacrylate (MMA), 145.4 g acetoAcetoxy ethyl methacrylate(AAEM), and 72.7 g methacrylic acid (MAA) was charged to the reaction vessel.
The nitrogen sweep was discontinued. A catalyst solution consisting of 3.7 g sodium persulfate (NaPS) was added at a batch temperature of 84~C and the batch exothermed to 88~C. After the peak exotherm, the batch was held for an additional 5 minutes. Then a solution consisting of 3.6 g sodium carbonate (Na2CO3) dissolved in 55 g DI water was charged to the batch.
The remaining monomer emulsion along with a cofeed consisting of 1.8g NaPS dissolved in 90g DI water was then fed to the kettle over 90 minutes. The reaction temperature was held at 85 +/- 2 ~C throughout the feed period. On completion of the monomer emulsion, the monomer emulsion vessel was rinsed with 45g DI water which was fed to the kettle. When all feeds were completed, the batch was held for 15 minutes at temperature. Thirty (30) g of DI water was added to the b,atch before cooling. At 60-65~C, a redox initiator was added (0.05 parts t-butyl hydroperoxide and 0.034 parts isoascorbic acid/ 100 parts). A neutralizer solution consisting of 67 g of 29% ammorlia in 200 g DI water was added. The viscosity was adjusted with 96g DI water.
Procedure for Preparation of Polymers B to I
The process described for Polymer A was used to prepare all additional examples. The exact monomer and kettle charges are described in Table I
The raw materials used in Table I are defined as follows:
BA Butyl Acrylate MMA Methyl Methacrylate AAEM Acetoacetoxy ethyl methacrylate DAAM Diacetone Acrylamide MEEU Methacryloxyethylethyleneurea MAA Methacrylic Acid n-DDM n-Dodecyl Mercaptan Surfactant A Ammoniurn nonoxynol~ sulfate Surfactant B Sodium laureth sulfate ~0~ 0 ~ ~ ~~ ~ ~~
-O ~ ~ ~ ~0 ~ ~~ _ ~ 00 ~ . . ~ ~ ~ 00 ~0 ~ . ~ ~O _ O ~ ' I' ~ 'D ~V~~ ~ Oo~ ~ O ~O ~t ~ _ O
o ~ ~ ~~ '~ ~ v~~ ~ ' ~ '~ ~ '' I' '~Y ~~ '~ 8 ~ ~ ~' ~ ~
_~ o ~ ~ 1-- o ~o ~ ~0 -- ~ x oo ~ ~ o ~ oO o~ ~ I~ -- ~o ,_ o ~ ~ ~ o ~ V~ o ~ I_ . CO o ~ O '~ C~ ~ o~ ~~
O ~ ~ 1-- ~0 ~O ~ ~ -- ' ~7 o ~ ' ' 1~ ' CO 0~ 'O o ~ CJ~
O ~ ~ 1_ ~~ ~~ ~ U~~ ' J O V'l CO ' ' 1- ' CO C70~ CO 1O
O ' v~ 1-- ~~ ~ V~ ~~ ' C~ ~ C~ ' J C7~~ ~- O ~ ~ ~ '~ O
3 ~ a ' 3 ~ O
~ E ~ E ~ E
~ ~? C ~ ~ ~ ~ v ~ C~ C~ v 3 a c ~ ~ a 3 ~ c . _ ,. ~ ~
CA 0222~027 1997-12-18 Examples 1-13 Waterbased coatings comprising one or more of the above emulsion polymers were prepared by adding the listed ingredients while stirring with a conventional labmixer:
Example #1 (Comparative): Example #2:
100g Polymer I 100g Polymer A
Cellulosic substrates, particularly composite cellulosic substrates such as MDF, hardboard and particle board, are extensively used in the manufacture of interior furniture and other board applications. Often, to prevent water penetration into the substrate which otherwise might cause damage to the substrate by fiber swelling due to hydration, the substrate is coated with a low VOC, high solids Wcurable coating which, once cured, seals the substrate and provides an effectivebarrier against water ingress.
Unfortunately, high solids W curable coatings tend to be more suited to clear, rather than pigmented, applications. Accordingly, when required for decorative purposes, substrates sealed with clear W cured coatings would normally be subsequently painted with a pigmented, organic solvent based topcoat.
With increasing environmental and governmental regulatory pressure, there is a strong desire to reduce or eliminate volatile organics in paints. However, currently, in many coatings markets, organic solvent borne paints still dominatebecause alternative water-based, low VOC paints fail to meet the performance criteria required of them. In particular, in the case of cellulosic substrates, though -the combination of a high solids W curable sealer in conjunction with a waterborne, pigmented topcoat would appear to offer a route to low VO~,- low energy coatingswith attractive economics, because of the severe adhesion problems typically encountered between waterborne topcoats and highly crosslinked undercoats, the successful implementation of this system has not been realised.
A number of prior art documents disclose waterborne compositions for coating various substrates. For example:
JP-A-7102218 (Nippon Carbide Industries KK) discloses an aqueous coating composition comprising a core/shell polymer, having acetoacetyl groups in the shell . CA 0222~027 1997-12-18-polymer, hydrazine derivatives with residual hydrazine groups and/or amines withtwo or more amine groups, and pigments. The composition is described to be suitable for coating many substrates induding metal sub~ les, plastics substrates, wood, leather and inorganic substrates sudh as concrete or mortar, and over old films such as on vinyl chloride, alkyd resins and other old paint films. The plastics substrates ~ ose~l are ABS sheet, poly~Ly~e,le sheet and vinyl d~loride covered steel sheets, whidh plastics are generally known to be thermoplastics materials DE-A-4344391 (Rohm GmbH) discloses aqueous dispersions of film-forming polymers based on polymethyl(meth)acrylate esters for coating surfaces of thermoplastic parts. The film-forming polymer may be polymerised from a monomer system comprising up to 15% crosslinkable monomer with an acetoacetyl group, such as acetoacetoxyethylmethacrylate (AAEM).
U~A-5213901 and U~A-5227423 (Rohm and Haas Company) disclose an aqueous binder composition comprising a copolyrner formed from a monomer system including 10 to 35% by weight of a wet adhesion promoting monomer selected from the group consisting of ethyleneureido-, cyanoacetoxy- and acetoacetoxy- containing monomers and hydroxymethyldiacetoneacrylamide. The binder is disclosed for use in a paint.
U~A-5278225 (Wacker-Chemie GmbH) discloses aqueous dispersions of copolymers - comprising acetoacetoxy functional groups and aminooxy crosslinking agents useful as binders for producing coverings, coatings and impregnations in the coating field.
It is disclosed that the dispersions are particularly suitable as adhesives forbonding to corona- and flame- pretreated polyolefin surfaces.
EP-A-0697417 (Rohm and Haas Company) discloses a latex-binder for producing a high gloss coating on a weathered substrate, which substrate may be a chalky, wood or cement substrate. The binder is disclosed to comprise a latex polymer bearing an acid functional pendant moiety and an enamine functional pendant moiety resulting from the reaction of acetoacetyl functional pendant moity on the latex polymer with ammonia or amine.
Whilst the prior art documents generally teach the use of aqueous coatings on various substrates, none of these documents disclose or suggest that the aqueous CA 0222~027 1997-12-18 coatings may be successfully applied to highly crosslinked polymeric surfaces, such as are formed when a substrate is coated with a thermoset material, and thereby replace the solvent-borne coatings which are so commonly used for this very specific application. Where lefelellces to coating polymeric surfaces have beerl made in the above prior art documents, the polymeric s-lrfAres have been thermoplastic materials, which materials are generally understood to be not highly crosslinkedmaterials.
It is an object of the present invention to provide a low VOC system for tandem coating substrates with both a highly crosslinked coating and a waterbased coating.
In accordance with the present invention there is provided a method co~ g tandem coating a substrate with (i) a highly crosslinked coating formed from a W curable composition, and (ii) a cured coating formed from an aqueous composition comprising a polymer comprising, as polymerised units, 0.1 to 100%, preferably 1 to 50% and even more preferably 5 to 20%, by weight of the polymer of at least one monomer capable of producing carbonyl functional moities in the polymer. The substrate may be coated first with the highly crosslinked coating (i) followed by the cured coating (ii), or the substrate may be coated first with the cured coating (ii) followed by the highly crosslinked coating (i). The method of the present invention provides a low VOC system for tandem coating substrates with both a highly crosslinked coating and a waterbased coating.
The highly crosslinked coating (i) is preferably formed from a thermoset materiaL Such material may be a W curable composition, which before cure may be a high solids composition or a waterborne composition cornp-rising appropriate Wcurable components. W curable coatings can be generally divided into two main categories: 1) free radical polyrnerised (meth)acrylate functionalised polymers and 2) cationically polymerised epoxies. Methacrylate and acrylate functionalised polymers generally comprise (meth)acrylate-functional oligomers and monomers combined with a photoinitiator to facilitate W cure. These (meth)acrylate-functional oligomers are typically prepared by a) reaction of difunctional epoxies with methacrylic or acrylic acid, b) the condensation product of difunctional . CA 0222~027 1997-12-18 isocyanates with hydroxy-functional (meth)acrylates, or c) the condensation product of (meth)acrylic acid and hydroxyl groups on a polyester backbone, or an hydroxyacrylate with residual acid groups on a polyester backbone. Cationic systems arebased on cycloaliphatic epoxies and a photoinitiator which decomposes to give a "super" acid with W radiation. The super acid catalyses the cationic polyrn~ri.c~tiQn of the epox~y. (See Radiation Curing In Polymer Science And Technology, Vol 1: Fundamentals in Methods, Edited by J.P. Fouassier and J.E.
Rabek, published by Elsevier Applied Science (1993). The W curable coatings after exposure to W radiation produce highly crosslinked coatings which have traditionally proved difficult to adhere waterbased topcoats onto without the use of an intermediate coating. Preferably, the coating (i) is cured in the presence ofoxygen, more pre~e,dbly in the presence of air.
The cured coating (ii) is formed from an aqueous composition co~ rising a carbonyl functional polyrner preferably comprising polymerised units of one or more monomers selected from the group consisting of ethyleneureido-containing monomers, cyanoacetoxy-containing monomers, acetoacetoxy-containing monomers, acrolein, methacrolein, vinyl (C,-C20)alkyl ketones and keto-containing amides such as diacetone acrylamide. The ethyleneureido-containing monomers, cyanoacetoxy-containing monomers, and acetoacetoxy-containing monomers are described in detail in US-A-5213901 on column 3, line 48, to column 4, line 38.
In a particularly ~,efelled embodiment, the aqueous composition comprises a polymer comprising from 0.1 to 100%, more preferably 1 to 50%, and most preferably 5 to 20% by weight polymerised units of one or more acetoacetyl functional monomers having the structure:
O R,O
A-(-C -C -C-)-B
H
wherein R, is either H, alkyl having 1 to 10 carbon atoms or phenyl;
A is either:
CA 0222~027 1997-12- 18 C=C- (- R~,-)a-(-X-)n-(-C-Y-)m-(-Rs-)q H
or R2 R~, O
~C=C-(-R4-)a-(-X-)n-(-C-Y-)-(-Rs-)q-O-H
wherein R2 is either H, alkyl having 1 to 10 carbon atorns or phenyl, substituted phenyl, halo, CO2CHy or CN, R3 is eitherH, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl or halo, R4 is either alkylene or substituted alkylene having 1 to 10 carbon atorns or phenylene, or substituted phenylene, Rs is either alkylene or substituted alkylene having 1 to 10 carbon atoms;
a, m, n and q are independently either 0 or 1, X and Y are independently either -NH- or -O-;
B is either A, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, or heterocyclic, preferably a (C4 to C10) heterocyclic.
Particularly preferred monomers are acetoacetoxyethylmethacrylate (AAEM), acetoacetoxyethylacrylate (AAEA), acetoacetoxypropylmethacrylate, allylacetoacetate, acetacetoxybutylmethacrylate, 2,3-di(acetoacetoxy)~ro~yl methacrylate, vinyl acetoacetate, or combinations thereof.
Optionally, the polymer used in coating (ii) is a copoIymer comprising carbonyl functionality wherein the copolymer comprises, as polymerised units, from 0 to 99.9%, preferably 50 to 99%, more preferably 80 to 95%, by weight of one or more copolymerisable monomers. Preferably, the copolymerisable monomers are selected from the group consisting of substituted and unsubstituted, saturated and monoethylenically unsaturated carboxylic acid ester monomers, such as methyl(meth) acrylate, ethyl(meth) acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, CA 0222~027 1997-12- 18 isodecyl(meth)acrylate, oleyl(meth)acrylate, palmityl(meth)acrylate, stearyl(meth)acrylate, methyl itaconate, methylfumarate, butyl fumarate, glycidyl methacrylate, dicydopentadienyl(meth)acrylate, isocyanatoethylmethacrylate hydroxyethyl(meth)acrylate, hydroxy~ro~yl(meth)acrylate, N,N'- .
rlimethylarnino(meth)acrylate and vinyl acetate; subsituted and unsubstituted call,oxylic acid monomers and anhydrides thereof, such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydide;
substituted and unsubstituted (meth)acrylamide monomers; styrene and substitutedstyrene monomers; other substituted or unsubstituted vinyl monomers such as vinyl chloAde, vinylidene chlorAde and N-vinylpyrrolidone; other substituted and unsubstituted alkylene monomers such as ethylene, propylene, butylene, and is~pr~ylene; and acrylonitrile and methacrylonitrile.
If desired, the polymer used in coating (ii) may also comprise, as polymeAsed units, 0.1 to 25% by weight substituted and unsubstituted polyfunctional ethylenically unsaturated monomers such as allylmethacrylate, diallylphthalate, 1,4-butyleneglycol di(meth)acrylate, 1,6-hexanediol diacrylate and divinylbenzene.
Such monomers tend to induce premature crosslinking or gelling of the copolymer.The copolymer used in coating (ii) is preferably a thermoplastic or substantially uncrosslinked copolymer when it is applied (in its uncured state) to the substrate.
The polymer used in coating (ii) may comprise acid functional pendant moiety sufficient to provide the polymer with an acid number of from 1 to 325, preferably from 3 to 130. The desired acid number is achieved by controlling theamount of acid functional monomer utilized in the polymer by a known method.
The polymer used in coating (ii) ~refelably has a glass transition temperature of from ~0 ~C to 120~C, as measured by differential scanning calorimetry. The Tg is is reported at the mid-point of the inflection using the half-height method. A polymer having a Tg of from 0~C to 90~C is most preferred. Preferably, the polymer has aGPC weight average molecular weight of 500 to 5,000,000. The GPC weight average molecular weight can be adjusted through the appropriate use of methods known inthe art such as by the use of chain transfer agents. "GPC" weight average molecular . CA 0222~027 1997-12-18 _ weight means the average molecular weight as determined by gel permeation d~romatography as described on page 4 of The Characterization of Polymers published by Rohm and Haas Company in 1976, utilizing polymethymethacrylate as the standard. The average partide size on the diameter of the polymer particles suitable for use in the coating (ii) is preferably from 20 to 1000 nm, more ~re~elably 30 to 500 nm.
The aqueous composition in coating (ii) may comprise at least two mutually incomratible copolymers, at least one of which is the polymer having carbonyl functional moities described above. These mutually incompatible copolymers may be present in the following morphological configurations, for example, core/shell partides with complete shell phases surrounding a single core, core/shell particles with shell phases incompletely encapsulating the core, core/shell particles with a multiplicity of cores, interpenetrating network particles, and multilobal particles de~ribed in the commonly assigned U~A~791151. In all these cases, the majority of the surface area of the particle will be occupied by at least one outer phase and the interior of the particle will be occupied by at least one inner phase. The mutual incompatibility of the two polymer compositions may be determined in various ways known in the art. The use of ~anning electron microscopy using staining techniques to emphasise the differenoe between the appearance of the phases, forexample, is such a technique.
In a further embodiment of the invention, the polymer used in coating (ii) may be blended with other polymers, such as those polymers normally found in paints and other coatings. For example, the copolymer (ii) may be blended with apolyurethane, a polyester, a polyamide, an acrylic copolymer, a styrene-acrylic copolymer or another polymer, or mixtures of two or more of such polymers.
The polymerisation techniques which may be used to prepare the polymer are well known in the art. The polymer may be prepared by aqueous, solution or emulsion polymerisation, with emulsion polymerisation being preferred. The polymerisation may be a redox or thermal initiation process employing conventional free radical initiators, such as, for example, ammonium and alkyl sulphates, hydrogen peroxide, benzoyl peroxide or t-butyl peroctoate at levels typically of from CA 0222~027 1997-12- 18-0.05 to 3% by weight based on the total weight of monomer. Redox systems using the same initiators coupled with suitable reducing agents such as for example isoascorbic acid, sodium bisulphite or sodium sulphoxylate formaldehyde may be used a similar levels.
The polymer ~refelably comprises from 1 to 100% of the total solids in coating (ii). Typically, the coating (ii) will ~r~elably comprise 80 to 30% water.
The coating (ii) may comprise additional ingredients, such as thickeners, sl1rf~ctAnts, pigments, flatting aids, waxes, slip aids, coalescents and/or plasticisors, such materials being typical ingredients of waterbased paints and coatings. The coating may also include a post crosslinking agent such as polyaziridine, polyisocyanate, polycarbodiimide, polyepoxide, polyaminoplast, polyalkoxysilane,polyoxazolidine, polyamine and polyvalent metal compounds, to improve the cure time of the waterbased coating once it has been applied to the s~sl,dLe.
Preferably, the substrate is a cellulosic material, such as wood or paper or a composite material thereof, such as MDF, hardboard, particle board or cardboard.In a particularly preferred embodiment, the cellulosic mateial is selected from the group consisting of wood, MDF, hardboard and particle board. Such materials typically find application in the manufacture of interior furniture and home fittings.
In this embodiment, preferably the cellulosic substrate is first coated with the highly crosslinked coating (i), which may act as a sealer or undercoat to prevent the ingress of water into the fibers of the substrate, and then the substrate, with the highly crosslinked coating, is further coated with the waterbased coating (ii). The waterbased coating may be a paint, including a pigment and other components typically found in such formulations, to give, once cured, the appropriate decorative effect to the substrate. In another embodiment, the cellulosic substrate is a paper material such as may be typically used in a printing or packaging application. Here, the waterbased coating (ii) may first be applied to the substrate, such as in the form of an ink, and then the cured waterbased coating (ii) and substrate are both coated with the highly crosslinked coating (ii).
The invention will now be further described with reference to the following examples:
CA 0222~027 1997-12- 18-Examples Various emulsion polymers A to I as detailed in Table I were prepared by the following procedure:
Procedure for Preparation of Polymer A
A 4-neck, 5-liter round bottom reaction flask containing an Initial Kettle Charge of 850 g DI water and 35.5 g lauryl (EO)~ Na sulfate (30%) was heated to 85 ~C under a nitrogen sweep. At 85 ~C, an aliquot of a Monomer Rm~ n (ME) comprising 750 g DI water, 38.8 g lauryl (EO)~ Na sulfate (30%), 538 g butyl acrylate (BA), 697.9 g methyl methacrylate (MMA), 145.4 g acetoAcetoxy ethyl methacrylate(AAEM), and 72.7 g methacrylic acid (MAA) was charged to the reaction vessel.
The nitrogen sweep was discontinued. A catalyst solution consisting of 3.7 g sodium persulfate (NaPS) was added at a batch temperature of 84~C and the batch exothermed to 88~C. After the peak exotherm, the batch was held for an additional 5 minutes. Then a solution consisting of 3.6 g sodium carbonate (Na2CO3) dissolved in 55 g DI water was charged to the batch.
The remaining monomer emulsion along with a cofeed consisting of 1.8g NaPS dissolved in 90g DI water was then fed to the kettle over 90 minutes. The reaction temperature was held at 85 +/- 2 ~C throughout the feed period. On completion of the monomer emulsion, the monomer emulsion vessel was rinsed with 45g DI water which was fed to the kettle. When all feeds were completed, the batch was held for 15 minutes at temperature. Thirty (30) g of DI water was added to the b,atch before cooling. At 60-65~C, a redox initiator was added (0.05 parts t-butyl hydroperoxide and 0.034 parts isoascorbic acid/ 100 parts). A neutralizer solution consisting of 67 g of 29% ammorlia in 200 g DI water was added. The viscosity was adjusted with 96g DI water.
Procedure for Preparation of Polymers B to I
The process described for Polymer A was used to prepare all additional examples. The exact monomer and kettle charges are described in Table I
The raw materials used in Table I are defined as follows:
BA Butyl Acrylate MMA Methyl Methacrylate AAEM Acetoacetoxy ethyl methacrylate DAAM Diacetone Acrylamide MEEU Methacryloxyethylethyleneurea MAA Methacrylic Acid n-DDM n-Dodecyl Mercaptan Surfactant A Ammoniurn nonoxynol~ sulfate Surfactant B Sodium laureth sulfate ~0~ 0 ~ ~ ~~ ~ ~~
-O ~ ~ ~ ~0 ~ ~~ _ ~ 00 ~ . . ~ ~ ~ 00 ~0 ~ . ~ ~O _ O ~ ' I' ~ 'D ~V~~ ~ Oo~ ~ O ~O ~t ~ _ O
o ~ ~ ~~ '~ ~ v~~ ~ ' ~ '~ ~ '' I' '~Y ~~ '~ 8 ~ ~ ~' ~ ~
_~ o ~ ~ 1-- o ~o ~ ~0 -- ~ x oo ~ ~ o ~ oO o~ ~ I~ -- ~o ,_ o ~ ~ ~ o ~ V~ o ~ I_ . CO o ~ O '~ C~ ~ o~ ~~
O ~ ~ 1-- ~0 ~O ~ ~ -- ' ~7 o ~ ' ' 1~ ' CO 0~ 'O o ~ CJ~
O ~ ~ 1_ ~~ ~~ ~ U~~ ' J O V'l CO ' ' 1- ' CO C70~ CO 1O
O ' v~ 1-- ~~ ~ V~ ~~ ' C~ ~ C~ ' J C7~~ ~- O ~ ~ ~ '~ O
3 ~ a ' 3 ~ O
~ E ~ E ~ E
~ ~? C ~ ~ ~ ~ v ~ C~ C~ v 3 a c ~ ~ a 3 ~ c . _ ,. ~ ~
CA 0222~027 1997-12-18 Examples 1-13 Waterbased coatings comprising one or more of the above emulsion polymers were prepared by adding the listed ingredients while stirring with a conventional labmixer:
Example #1 (Comparative): Example #2:
100g Polymer I 100g Polymer A
2.85g Diethyleneglycol monobutyl ether 2.88g Diethyleneglycol monobutyl ether 8.55g Ethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 17.4g water 21.3g water Example #3: Example #4:
100g Polymer B 100g Polymer C
2.88g Diethyleneglycol monobutyl ether 2.88g Diethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 24.2g water 18.8g water Example #5: Example #6:
100g Polymer D 100g Polymer E
2.88g Diethyleneglycol monobutyl ether 2.88g Diethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 22.4 g water 17.6g water Exampfe #7 Example #8 100g Polymer F 100g Polymer G
2.55g Diethyleneglycol monobutyl ether 2.03g Diethyleneglycol monobutyl ether 7.64g Ethyleneglycol monobutyl ether 6.07g Ethyleneglycol monobutyl ether 16.4g water 15.2g water 1.55g AcrysolrM RM-8W
CA 0222~027 1997-12- 18 ~ 13 Example #9: Example 10:
100g Polymer H 10g Example 1 2.55g Diethyleneglycol monobutyl ether 10.2g Example 3 7.64g Ethyleneglycol monobutyl ether 10.1g water Example 11: Example #12:
10g Example 1 25g Example #1 5.1g Example 3 8.8g Pigment Grind A
Example #13: Pigment Grind A:
25g Exarnple #3 855.4g water 8.5g Pigment Grind A 140.4g TamollM 731 23.8g Triton~ CF-10 11.8g TegolM Foamex 800 2688g Ti-PurerM R-700 Diethyleneglycol monobutyl ether is supplied by Union Carbide, Chemicals and Plastics Company Inc., 39 Old Ridgebury Rd., Danbury CT 06817-0001 Ethyleneglycol monobutyl ether is supplied by Union Carbide, Chemicals and Plastics Company Inc., 39 Old Ridgebury Rd., Danbury CT 06817-0001 AcrysolrM RM-8W is supplied by Rohm and Haas Company, Independence Mall West, Philadelphia PA 19105 TamolrM 731 is supplied by Rohm and Haas Company, Independence Mall West, Philadelphia PA 19105 TritonrM CF-10 is supplied by Union Carbide, Indutrial Chemicals Division, 39 Old Ridgebury Rd., Danbury CT 06817-0001 TegoTM Foamex 800 is supplied by Goldschrnidt Chemical Corp. P.O. Box 1299, 914 Randolph Rd., Hopewell, VA 23860 Ti-Pure~ R-700 is supplied by Dupont Company, Chemi~Al~ and Pigments Division, Wilmington, DE 19898.
CA 0222~027 1997-12-18-Preparation of substrates Five different W curable materials were used to coat the substrate and they are listed below along with the supplier. A #12 wire wound rod was used to apply a 37.5 rnm (microns) wet filrn thickness over a Masonite type hardboard-substrate.The first coat was allowed to dry 10 minutes then irradiated with 2 W lamps ~
200watts/2.5 cm using a W processor from AETEK, Van Dyke Rd Plainfield Illinois 60544. The W line speed was 12 m per minute. The coating was then sanded with 240 grit sand paper. A second coat was applied as above and allowed to dry 10 minutes then irradiated with 2 W lamps lal 200watts/2.5 cm at a line speed of 12 m per minute.
Coating #1: CDG #W-102 is supplied by the Coating Development Group, P.O. Box 14817, Philadelphia PA 19134 Coating #2: CDG #WM0010 is supplied by the Coating Development Group, P.O.
Box 14817, Philadelphia PA 19134 Coating#3: W sealer/filler #107R000 is supplied by Forest Paint Company, 1011 McKinley Ave, Eugene Oregon 97402 Coating#4: Magic Light Clear Sealer #107R014 - is supplied by Forest Paint Company, 1011 McKinley Ave, Eugene Oregon 97402 Coating#5: Off White W Primer #99-4647-07 - is supplied by Forest Paint Company,1011 McKinley Ave, Eugene Oregon 97402 Coating #1 is described by the supplier as a urethane acrylic. Coating #2 is described by the supplier as a cationic W sealer. Coating #3 is described by the supplier as a polyester W filler. Coating #4 is described by the supplier as a polyester/epoxy W
filler. Coating #5 is described by the supplier as an epoxy W primer.
The W coated Masonite substrates were then coated with the waterbased formulation #1-#13. Examples #1- #13 were each drawn down at a 175mm (microns) wet film over the coated boards which were prepared as described above. The wet coatings were allowed to dry for 30 minutes at 25~C. The boards were then placed in CA 0222~027 1997-12-18-an oven at 50~C for 30 minutes. After waiting at least 24 hours the adhesion wasrated using a Gardner cross hatch adhesion tester (PA-2054 blade) and following ASTM test method D-3359. The coating was scored with the adhesion tester, and ScotchTU MagiclM Tape (#810) was applied to the scored area. The tape was removed as given by ASTM test method D-3359. The adhesion rating for each of the examples over the W coated and cured boards is given in Table II.
Table II
W Coat Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. E~. Ex. Ex.
#1 #2 # #4 #5 #6#7 #8 #9 #10 #11 #12 #13 : ~ 3 ~ r ~ r ___ ___ ___ __- --- 2 5 4 ~_ _ _ ~ indicates complete removal of the coating; 5 indicates no coating was removed; 2, 3, and 4 all represent an intermediate level of adhesion The results clearly show that Examples 2-11, and Example 13 which are in accordance with the invention all display improved adhesion relative to the two comparative examples, Example #1 and Example #12, which do not contain the invention.
The above results are not predictable from the prior art. As will be demonstrated below, coatings which may adhere well and so be suitable for coating one particular thermoplastic substrate may not adhere well to another thermoplastic substrate. It is therefore not possible to predict that a composition which adheres well to and so is suitable for coating a low crosslinked thermoplastic material would adhere well to and so be suitable for coating a highly crosslinked thermoset material such as a W
coating. The examples below also indicate the contrary, that a composition whichadheres well to a highly crosslinked thermoset substrate may not adhere well to a thermoplastic substrate.
Examples 1, 3, 8, and 9 above were drawn down over the following thermoplastic materials:
1) Plexiglas~ - a polymethyl methacrylate supplied by Atohaas North America, 100Independence Mall West, Philadelphia PA.
CA 0222~027 1997-12-18 2) GE Noryl~ PX844 - a blend polymer of high impact poly~lyLel~e and polyphenylene oxide supplied by Standard Plaque Inc. 17271 Francis St. Melvindale, M~ 48122.
3) GE Lexan~ ML4291-7502 - a polycarbonate supplied by Standard Plaque Inc.
17271 Francis St. Melvindale, MI 48122 4) GE Cycolac AR-3501 - an ABS plastic supplied by Standard Plaque Inc. 17271 Francis St. Melvindale, MI 48122 Examples #1, 3, 8, and 9 above were each drawn down at a 175mm (microns) wet film thickness over all four plastic materials. The wet coatings were allowed to dry for 30 minutes at 25~C. The boards were then placed in an oven at 50~C for 30 rninutes. After waiting at least 24 hours the adhesion was rated using a Gardnercross hatch adhesion tester (PA-2054 blade) and following ASI~M test method D-3359. The coating was scored with the adhesion tester, and ScotchlM Magic~ Tape (#810) was applied to the scored area. The tape was removed as given by ASTM test method D-3359. The adhesion rating for the examples over the plastic is given inTable III.
Table III
Plastic Ex. #1 Ex. #3 Ex. #8 Ex. #9 #1 5 5 5 5 #2 0 0 0 5 #3 5 5 5 5 #4 5 5 5 5 The results clearly show that even a non-carbonyl functional polymer displays adhesion to the following thermoplastic plastics: polymethyl methacrylate, polycarbonate, and ABS, and so the carbonyl functional containing polymers required in invention are not needed to obtain adhesion. When compared to the data for W-cured materials, this data underscores the fact that adhesion is not predictable and is much more difficult to obtain to highly crosslinked thermosetmaterials such as W-cured coatings. In contrast only one of the examples containing carbonyl functional polymer displays adhesion to the high impact ~ 17 poly~lylene/polyphylene oxide blended thermoplastic. In essence what is found isthat carbonyl functional polymers are not required to get adhesion to thermoplastics such as PMMA, PC, and ABS, and that carbonyl functional polymers do not appear to provide adhesion to PPO/HIPS thermplastics. The highly crosslinked W~ured m~tPriAl.~-employed in the present invention are a unique dass of materials which offer a unique set of problems not seen for standard thermoplastics.
100g Polymer B 100g Polymer C
2.88g Diethyleneglycol monobutyl ether 2.88g Diethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 24.2g water 18.8g water Example #5: Example #6:
100g Polymer D 100g Polymer E
2.88g Diethyleneglycol monobutyl ether 2.88g Diethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 8.62g Ethyleneglycol monobutyl ether 22.4 g water 17.6g water Exampfe #7 Example #8 100g Polymer F 100g Polymer G
2.55g Diethyleneglycol monobutyl ether 2.03g Diethyleneglycol monobutyl ether 7.64g Ethyleneglycol monobutyl ether 6.07g Ethyleneglycol monobutyl ether 16.4g water 15.2g water 1.55g AcrysolrM RM-8W
CA 0222~027 1997-12- 18 ~ 13 Example #9: Example 10:
100g Polymer H 10g Example 1 2.55g Diethyleneglycol monobutyl ether 10.2g Example 3 7.64g Ethyleneglycol monobutyl ether 10.1g water Example 11: Example #12:
10g Example 1 25g Example #1 5.1g Example 3 8.8g Pigment Grind A
Example #13: Pigment Grind A:
25g Exarnple #3 855.4g water 8.5g Pigment Grind A 140.4g TamollM 731 23.8g Triton~ CF-10 11.8g TegolM Foamex 800 2688g Ti-PurerM R-700 Diethyleneglycol monobutyl ether is supplied by Union Carbide, Chemicals and Plastics Company Inc., 39 Old Ridgebury Rd., Danbury CT 06817-0001 Ethyleneglycol monobutyl ether is supplied by Union Carbide, Chemicals and Plastics Company Inc., 39 Old Ridgebury Rd., Danbury CT 06817-0001 AcrysolrM RM-8W is supplied by Rohm and Haas Company, Independence Mall West, Philadelphia PA 19105 TamolrM 731 is supplied by Rohm and Haas Company, Independence Mall West, Philadelphia PA 19105 TritonrM CF-10 is supplied by Union Carbide, Indutrial Chemicals Division, 39 Old Ridgebury Rd., Danbury CT 06817-0001 TegoTM Foamex 800 is supplied by Goldschrnidt Chemical Corp. P.O. Box 1299, 914 Randolph Rd., Hopewell, VA 23860 Ti-Pure~ R-700 is supplied by Dupont Company, Chemi~Al~ and Pigments Division, Wilmington, DE 19898.
CA 0222~027 1997-12-18-Preparation of substrates Five different W curable materials were used to coat the substrate and they are listed below along with the supplier. A #12 wire wound rod was used to apply a 37.5 rnm (microns) wet filrn thickness over a Masonite type hardboard-substrate.The first coat was allowed to dry 10 minutes then irradiated with 2 W lamps ~
200watts/2.5 cm using a W processor from AETEK, Van Dyke Rd Plainfield Illinois 60544. The W line speed was 12 m per minute. The coating was then sanded with 240 grit sand paper. A second coat was applied as above and allowed to dry 10 minutes then irradiated with 2 W lamps lal 200watts/2.5 cm at a line speed of 12 m per minute.
Coating #1: CDG #W-102 is supplied by the Coating Development Group, P.O. Box 14817, Philadelphia PA 19134 Coating #2: CDG #WM0010 is supplied by the Coating Development Group, P.O.
Box 14817, Philadelphia PA 19134 Coating#3: W sealer/filler #107R000 is supplied by Forest Paint Company, 1011 McKinley Ave, Eugene Oregon 97402 Coating#4: Magic Light Clear Sealer #107R014 - is supplied by Forest Paint Company, 1011 McKinley Ave, Eugene Oregon 97402 Coating#5: Off White W Primer #99-4647-07 - is supplied by Forest Paint Company,1011 McKinley Ave, Eugene Oregon 97402 Coating #1 is described by the supplier as a urethane acrylic. Coating #2 is described by the supplier as a cationic W sealer. Coating #3 is described by the supplier as a polyester W filler. Coating #4 is described by the supplier as a polyester/epoxy W
filler. Coating #5 is described by the supplier as an epoxy W primer.
The W coated Masonite substrates were then coated with the waterbased formulation #1-#13. Examples #1- #13 were each drawn down at a 175mm (microns) wet film over the coated boards which were prepared as described above. The wet coatings were allowed to dry for 30 minutes at 25~C. The boards were then placed in CA 0222~027 1997-12-18-an oven at 50~C for 30 minutes. After waiting at least 24 hours the adhesion wasrated using a Gardner cross hatch adhesion tester (PA-2054 blade) and following ASTM test method D-3359. The coating was scored with the adhesion tester, and ScotchTU MagiclM Tape (#810) was applied to the scored area. The tape was removed as given by ASTM test method D-3359. The adhesion rating for each of the examples over the W coated and cured boards is given in Table II.
Table II
W Coat Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. E~. Ex. Ex.
#1 #2 # #4 #5 #6#7 #8 #9 #10 #11 #12 #13 : ~ 3 ~ r ~ r ___ ___ ___ __- --- 2 5 4 ~_ _ _ ~ indicates complete removal of the coating; 5 indicates no coating was removed; 2, 3, and 4 all represent an intermediate level of adhesion The results clearly show that Examples 2-11, and Example 13 which are in accordance with the invention all display improved adhesion relative to the two comparative examples, Example #1 and Example #12, which do not contain the invention.
The above results are not predictable from the prior art. As will be demonstrated below, coatings which may adhere well and so be suitable for coating one particular thermoplastic substrate may not adhere well to another thermoplastic substrate. It is therefore not possible to predict that a composition which adheres well to and so is suitable for coating a low crosslinked thermoplastic material would adhere well to and so be suitable for coating a highly crosslinked thermoset material such as a W
coating. The examples below also indicate the contrary, that a composition whichadheres well to a highly crosslinked thermoset substrate may not adhere well to a thermoplastic substrate.
Examples 1, 3, 8, and 9 above were drawn down over the following thermoplastic materials:
1) Plexiglas~ - a polymethyl methacrylate supplied by Atohaas North America, 100Independence Mall West, Philadelphia PA.
CA 0222~027 1997-12-18 2) GE Noryl~ PX844 - a blend polymer of high impact poly~lyLel~e and polyphenylene oxide supplied by Standard Plaque Inc. 17271 Francis St. Melvindale, M~ 48122.
3) GE Lexan~ ML4291-7502 - a polycarbonate supplied by Standard Plaque Inc.
17271 Francis St. Melvindale, MI 48122 4) GE Cycolac AR-3501 - an ABS plastic supplied by Standard Plaque Inc. 17271 Francis St. Melvindale, MI 48122 Examples #1, 3, 8, and 9 above were each drawn down at a 175mm (microns) wet film thickness over all four plastic materials. The wet coatings were allowed to dry for 30 minutes at 25~C. The boards were then placed in an oven at 50~C for 30 rninutes. After waiting at least 24 hours the adhesion was rated using a Gardnercross hatch adhesion tester (PA-2054 blade) and following ASI~M test method D-3359. The coating was scored with the adhesion tester, and ScotchlM Magic~ Tape (#810) was applied to the scored area. The tape was removed as given by ASTM test method D-3359. The adhesion rating for the examples over the plastic is given inTable III.
Table III
Plastic Ex. #1 Ex. #3 Ex. #8 Ex. #9 #1 5 5 5 5 #2 0 0 0 5 #3 5 5 5 5 #4 5 5 5 5 The results clearly show that even a non-carbonyl functional polymer displays adhesion to the following thermoplastic plastics: polymethyl methacrylate, polycarbonate, and ABS, and so the carbonyl functional containing polymers required in invention are not needed to obtain adhesion. When compared to the data for W-cured materials, this data underscores the fact that adhesion is not predictable and is much more difficult to obtain to highly crosslinked thermosetmaterials such as W-cured coatings. In contrast only one of the examples containing carbonyl functional polymer displays adhesion to the high impact ~ 17 poly~lylene/polyphylene oxide blended thermoplastic. In essence what is found isthat carbonyl functional polymers are not required to get adhesion to thermoplastics such as PMMA, PC, and ABS, and that carbonyl functional polymers do not appear to provide adhesion to PPO/HIPS thermplastics. The highly crosslinked W~ured m~tPriAl.~-employed in the present invention are a unique dass of materials which offer a unique set of problems not seen for standard thermoplastics.
Claims (10)
1. A method comprising tandem coating a substrate with (i) a highly crosslinked coating formed from a UV curable composition, and (ii) a cured coating formed from an aqueous composition comprising a polymer comprising, as polymerised units, 0.1 to 100%, preferably 1 to 50% and even more preferably 5 to 20%, by weight of thepolymer of at least one monomer capable of contributing pendant carbonyl functional groups to the polymer.
2. A method as claimed in claim 1, wherein the substrate is coated first with the highly crosslinked coating (i) followed by the cured coating (ii).
3. A method as claimed in claim 1, wherein the substrate is coated first with the cured coating (ii) followed by the highly crosslinked coating (i).
4. A method as claimed in any one of the preceding claims, wherein the coating (ii) is formed from an aqueous composition comprising a polymer comprising, as polymerised units, one or more monomers selected from the group consisting of ethyleneurido-containing monomers, cyanoacetoxy-containing monomers, acetoacetoxy-containing monomers, acrolein, methacrolein, vinyl (C1-C20)alkyl ketones and keto-containing amides such as diacetone acrylamide.
5. A method as claimed in claim 5, wherein the the aqueous composition comprises a polymer comprising from 0.1 to 100%, more preferably 1 to 50%, and most preferably 5 to 20% by weight polymerised units of one or more acetoacetyl functional monomers having the structure:
wherein R1 is either H, alkyl having 1 to 10 carbon atoms or phenyl;
A is either:
or wherein R2 is either H, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, halo, CO2CH3, or CN, R3 is eitherH, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl or halo, R4 is either alkylene or substituted alkylene having 1 to 10 carbon atoms or phenylene, or substituted phenylene, R5 is either alkylene or substituted alkylene having 1 to 10 carbon atoms;
a, m, n and q are independently either 0 or 1, X and Y are independently either -NH- or -O-;
B is either A, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, or heterocyclic.
wherein R1 is either H, alkyl having 1 to 10 carbon atoms or phenyl;
A is either:
or wherein R2 is either H, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, halo, CO2CH3, or CN, R3 is eitherH, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl or halo, R4 is either alkylene or substituted alkylene having 1 to 10 carbon atoms or phenylene, or substituted phenylene, R5 is either alkylene or substituted alkylene having 1 to 10 carbon atoms;
a, m, n and q are independently either 0 or 1, X and Y are independently either -NH- or -O-;
B is either A, alkyl having 1 to 10 carbon atoms or phenyl, substituted phenyl, or heterocyclic.
6. A method as claimed in claim 5, wherein the monomers are acetoacetoxyethylmethacrylate (AAEM), acetoacetoxyethylacrylate (AAEA), acetoacetoxypropylmathacrylate, allylacetoacetate, acetacetoxybutylmethacrylate,2,3-di(acetoacetoxy)propyl methacrylate, vinyl acetoacetate, or combinations thereof.
7. A method as claimed in any one of the preceding claims, wherein the polymer used in coating (ii) is a copolymer comprising carbony functionality wherein thecopolymer comprises, as polymerised units, from 0 to 99.9%, preferably 50 to 99%, more preferably 80 to 95%, by weight of one or more copolymerisable monomers.
Preferably, the copolymerisable monomers are selected from the group consisting of substituted and unsubstituted, saturated and monoethylenically unsaturated carboxylic acid ester monomers, such as methyl(meth) acrylate, ethyl(meth) acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, isodecyl(meth)acrylate, oleyl(meth)acrylate, palmityl(meth)acrylate, steryl(meth)acrylate, methyl itaconate, methylfumarate, butyl fumarate, glycidyl methacrylate, dicyclopentadienyl(meth)acrylate, isocyanoatoethylmethacrylate hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, N,N'-dimethylamino(meth)acrylate and vinyl acetate;subsituted and unsubstituted carboxylic acid monomers and anhydrides thereof, such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydide; substituted and unsubstituted (meth)acrylamide monomers;
styrene and substituted styrene monomers; other substituted or unsubstituted vinyl monomers such as vinyl chloride, vinylidene chloride and N-vinylpyrrolidone; other substituted and unsubstituted alkylene monomers such as ethylene, propylene, butylene, and isopropylene; and acrylonitrile and methacrylonitrile.
Preferably, the copolymerisable monomers are selected from the group consisting of substituted and unsubstituted, saturated and monoethylenically unsaturated carboxylic acid ester monomers, such as methyl(meth) acrylate, ethyl(meth) acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, isodecyl(meth)acrylate, oleyl(meth)acrylate, palmityl(meth)acrylate, steryl(meth)acrylate, methyl itaconate, methylfumarate, butyl fumarate, glycidyl methacrylate, dicyclopentadienyl(meth)acrylate, isocyanoatoethylmethacrylate hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, N,N'-dimethylamino(meth)acrylate and vinyl acetate;subsituted and unsubstituted carboxylic acid monomers and anhydrides thereof, such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydide; substituted and unsubstituted (meth)acrylamide monomers;
styrene and substituted styrene monomers; other substituted or unsubstituted vinyl monomers such as vinyl chloride, vinylidene chloride and N-vinylpyrrolidone; other substituted and unsubstituted alkylene monomers such as ethylene, propylene, butylene, and isopropylene; and acrylonitrile and methacrylonitrile.
8. A method as claimed in any one of the preceding claims, wherein the polymer used in coating (ii) comprises, as polymerised units, 0.1 to 25% by weight substituted and unsubstituted polyfunctional ethylenically unsaturated monomers such as allylmethacrylate, diallylphthalate, 1,4-butyleneglycol di(meth)acrylate, 1,6-hexanediol diacrylate and divinylbenzene.
9. A method as claimed in any one of the preceding claims, wherein the polymer used in coating (ii) comprises acid functional pendant moiety sufficient to provide the polymer with an acid number of from 1 to 325, preferably from 3 to 130.
10. A method as claimed in any one of the preceding claims, wherein the polymer used in coating (ii) has a glass transition temperature of from -40 °C to 120°C, and/or a GPC weight average molecular weight of 500 to 5,000,000, and/or an average particle size from 20 to 1000 nm, more preferably 30 to 500 nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3348196P | 1996-12-19 | 1996-12-19 | |
| US60/033,481 | 1996-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2225027A1 true CA2225027A1 (en) | 1998-06-19 |
Family
ID=21870662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002225027A Abandoned CA2225027A1 (en) | 1996-12-19 | 1997-12-18 | Coating substrates |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5932350A (en) |
| EP (1) | EP0849004B1 (en) |
| JP (1) | JPH10192781A (en) |
| AU (1) | AU721046B2 (en) |
| BR (1) | BR9705821A (en) |
| CA (1) | CA2225027A1 (en) |
| DE (1) | DE69735524T2 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6417267B1 (en) * | 1996-05-28 | 2002-07-09 | Eastman Chemical Company | Adhesive compositions containing stable amino-containing polymer latex blends |
| US6197844B1 (en) * | 1996-09-13 | 2001-03-06 | 3M Innovative Properties Company | Floor finish compositions |
| EP1032474B1 (en) * | 1997-11-20 | 2001-10-17 | E.I. Dupont De Nemours And Company | Method for multi-layered repair coating of substrates |
| WO1999026728A2 (en) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Method for multi-layered coating of substrates |
| US6534130B1 (en) * | 1997-11-20 | 2003-03-18 | E. I. Du Pont De Nemours And Company | Method for multi-layered coating of substrates |
| MXPA02001970A (en) * | 1999-08-25 | 2002-10-31 | Ecolab Inc | Method for removing an ultraviolet light cured floor finish, removable ultraviolet light curable floor finish and strippable finished floor. |
| US6500877B1 (en) | 1999-11-05 | 2002-12-31 | Krohn Industries, Inc. | UV curable paint compositions and method of making and applying same |
| US6544942B1 (en) * | 2000-04-28 | 2003-04-08 | Ecolab Inc. | Phase-separating solvent composition |
| AU5377801A (en) * | 2000-04-28 | 2001-11-12 | Ecolab Inc | Strippable laminate finish |
| AU2001253777B2 (en) | 2000-04-28 | 2005-05-19 | Ecolab Inc. | Antimicrobial composition |
| US6887933B2 (en) * | 2000-09-25 | 2005-05-03 | Rohm And Haas Company | Aqueous acrylic emulsion polymer composition |
| AU2002301310B2 (en) | 2001-10-17 | 2007-12-20 | Rohm And Haas Company | Polymer composition |
| DE10322767A1 (en) * | 2003-05-19 | 2004-12-16 | Thomas Kerle | Process for the production of technical inlays |
| US20050249929A1 (en) * | 2004-05-05 | 2005-11-10 | Reichwein David P | Digitally printed surface covering |
| US20050282029A1 (en) * | 2004-06-18 | 2005-12-22 | 3M Innovative Properties Company | Polymerizable composition and articles therefrom |
| US7150770B2 (en) * | 2004-06-18 | 2006-12-19 | 3M Innovative Properties Company | Coated abrasive article with tie layer, and method of making and using the same |
| US7150771B2 (en) * | 2004-06-18 | 2006-12-19 | 3M Innovative Properties Company | Coated abrasive article with composite tie layer, and method of making and using the same |
| US7435453B2 (en) * | 2004-08-04 | 2008-10-14 | Valspar Sourcing, Inc. | Method of finishing veneer surface of veneered wood product by application and curing of UV-curable coating layers having cationically and free-radically polymerizable moieties |
| US7344575B2 (en) * | 2005-06-27 | 2008-03-18 | 3M Innovative Properties Company | Composition, treated backing, and abrasive articles containing the same |
| US7344574B2 (en) * | 2005-06-27 | 2008-03-18 | 3M Innovative Properties Company | Coated abrasive article, and method of making and using the same |
| DE102006039941A1 (en) * | 2006-08-25 | 2008-02-28 | Wacker Chemie Ag | Process for the treatment of cellulosic fibers or fabrics containing cellulosic fibers |
| JP4519184B2 (en) * | 2008-07-08 | 2010-08-04 | 欧文印刷株式会社 | Writing paper and method for manufacturing writing paper |
| US9029451B2 (en) | 2010-12-15 | 2015-05-12 | Eastman Chemical Company | Waterborne coating compositions that include 2,2,4-trimethyl-3-oxopentanoate esters as reactive coalescents |
| US8809447B2 (en) | 2010-12-15 | 2014-08-19 | Eastman Chemical Company | Acetoacetate-functional monomers and their uses in coating compositions |
| US8809446B2 (en) | 2010-12-15 | 2014-08-19 | Eastman Chemical Company | Substituted 3-oxopentanoates and their uses in coating compositions |
| EP2945994B1 (en) | 2013-01-18 | 2018-07-11 | Basf Se | Acrylic dispersion-based coating compositions |
| WO2016030538A1 (en) * | 2014-08-29 | 2016-03-03 | Van Wijhe Beheer B.V. | Multilayer radiation-curable coating for indoor and outdoor application |
| CN111570229A (en) * | 2020-05-26 | 2020-08-25 | 梦天家居集团股份有限公司 | Roller coating process for UV roller color primer and water-based white finish |
| CN112298121A (en) * | 2020-10-26 | 2021-02-02 | 黄冈格罗夫氢能汽车有限公司 | Method for repairing hydrogen energy automobile parts by using UV (ultraviolet) type resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4099973A (en) * | 1973-10-24 | 1978-07-11 | Hitachi, Ltd. | Photo-sensitive bis-azide containing composition |
| US4035274A (en) * | 1976-05-24 | 1977-07-12 | Scm Corporation | Dual cure cathodic electrocoating |
| US4291087A (en) * | 1979-06-12 | 1981-09-22 | Rohm And Haas Company | Non-woven fabrics bonded by radiation-curable, hazard-free binders |
| US4781987A (en) * | 1987-03-06 | 1988-11-01 | Armstrong World Industries, Inc. | Stain and scratch resistant resilient surface coverings |
| US5227423A (en) * | 1989-08-29 | 1993-07-13 | Rohm And Haas Company | Paints and binders for use therein |
| US5213901A (en) * | 1989-08-29 | 1993-05-25 | Rohm And Haas Company | Coated articles |
| EP0493317B2 (en) * | 1990-12-18 | 2001-01-10 | Ciba SC Holding AG | Radiosensitive composition on basis of water as solvent |
| DE4117487A1 (en) * | 1991-05-28 | 1992-12-03 | Wacker Chemie Gmbh | AMINOOXY CROSSLINKER CONTAINING AQUEOUS DISPERSIONS OF COPOLYMERISATES CONTAINING CARBONYL GROUPS |
| GB2262055A (en) * | 1991-11-28 | 1993-06-09 | Tudor Hart George Henry | Distressed paint finishes |
| CA2082614A1 (en) * | 1992-04-24 | 1993-10-25 | Paul J. Shustack | Organic solvent and water resistant, thermally, oxidatively and hydrolytically stable radiation-curable coatings for optical fibers, optical fibers coated therewith and processes for making same |
| JP3075549B2 (en) * | 1993-09-30 | 2000-08-14 | 日本カーバイド工業株式会社 | Composition for aqueous coating of acetoacetyl group-containing copolymer |
| DE4343885A1 (en) * | 1993-12-22 | 1995-06-29 | Hoechst Ag | Aqueous, radiation-curable binder dispersions |
| DE4344391A1 (en) * | 1993-12-24 | 1995-06-29 | Roehm Gmbh | polymer dispersions |
| US5534310A (en) * | 1994-08-17 | 1996-07-09 | Rohm And Haas Company | Method of improving adhesive of durable coatings on weathered substrates |
-
1997
- 1997-11-20 AU AU45306/97A patent/AU721046B2/en not_active Ceased
- 1997-11-24 BR BR9705821A patent/BR9705821A/en not_active Application Discontinuation
- 1997-12-04 EP EP97309800A patent/EP0849004B1/en not_active Expired - Lifetime
- 1997-12-04 DE DE69735524T patent/DE69735524T2/en not_active Expired - Fee Related
- 1997-12-05 US US08/985,665 patent/US5932350A/en not_active Expired - Fee Related
- 1997-12-18 CA CA002225027A patent/CA2225027A1/en not_active Abandoned
- 1997-12-19 JP JP9364409A patent/JPH10192781A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| MX9708947A (en) | 1998-09-30 |
| US5932350A (en) | 1999-08-03 |
| BR9705821A (en) | 1999-06-01 |
| EP0849004A2 (en) | 1998-06-24 |
| DE69735524D1 (en) | 2006-05-11 |
| AU4530697A (en) | 1998-06-25 |
| EP0849004B1 (en) | 2006-03-22 |
| JPH10192781A (en) | 1998-07-28 |
| DE69735524T2 (en) | 2006-11-16 |
| AU721046B2 (en) | 2000-06-22 |
| EP0849004A3 (en) | 2002-10-16 |
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