EP0624183A1 - Compositions modifiees de resine epoxy, compositions de revetement a brillance reduite - Google Patents
Compositions modifiees de resine epoxy, compositions de revetement a brillance reduiteInfo
- Publication number
- EP0624183A1 EP0624183A1 EP93904648A EP93904648A EP0624183A1 EP 0624183 A1 EP0624183 A1 EP 0624183A1 EP 93904648 A EP93904648 A EP 93904648A EP 93904648 A EP93904648 A EP 93904648A EP 0624183 A1 EP0624183 A1 EP 0624183A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- epoxy resin
- amount
- composition
- employed
- 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- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
Definitions
- the present invention concerns modified epoxy resin compositions, curable compositions thereof and reduced gloss coating compositions.
- Epoxy resin based powder coatings generally have a high gloss. In some applications, it is desirable to have coatings with reduced gloss. It is important that formulations which provide coatings with reduced gloss also provide coatings with a stable level of gloss over a period of time that the coating formulation might need to be stored.
- One aspect of the present invention pertains to an improvement in a modified epoxy resin composition
- a modified epoxy resin composition comprising
- Another aspect of the present invention pertains to an improvement in a compositi suitable as a curing agent for epoxy resins which comprises
- Another aspect of the present invention pertains to an improvement in a curable composition
- a curable composition comprising
- component (B ) at least one polymer prepared from one or more ethylenically unsaturated monomers wherein at least one of such monomers contains a carboxylic acid group;
- component (D) at least one curing agent for component (A) which is different from either component (B) or t prereaction product of components (B) and (C); wherein said improvement resides in incorporating into said composition;
- a further aspect of the present invention pertains to an improvement in a powder coating composition which contains substantial quantities of pigment(s) or filler(s) comprising (A) at least one epoxy resin containing an average of more than one vicinal epoxy group per molecule and at least one aromatic ring in its backbone; ( B ) at least one polymer prepared from one or more ethylenically unsaturated monomers wher at least one of such monomers contains a carboxylic acid group;
- component (D) at least one curing agent for component (A) which is different from either component (B) o prereaction product of components (B) and (C); and (E) at least one or more additional component(s) including pigment, filler, flow control agent, leveling aid or other additive; wherein said improvement resides in incorporating into said composition;
- a further aspect of the present invention pertains to an improvement in a powd coating composition which is essentially free of pigments) and filler(s) comprising
- a further aspect of the present invention pertains to the product resulting from curing the aforementioned curable composition.
- a further aspect of the present invention pertains to articles which have been coated with the aforementioned coating composition.
- the present invention may suitably comprise, consist of, or consist essentially o aforementioned components.
- the invention illustratively disclosed herein suitably may be practiced in the absence of any component which is not specifically disclosed or enumerated herein and any of th compounds may contain or be free of any substituent not specifically named herein.
- the term "essentially free of pigment(s) and /or filler(s)" means that the composition is entirely free of or contains only inconsequential quantities of pigmentfe) and/or nTler(s), usually zero or less than 3, preferably less than 2, more preferably less than 1 percent b weight based upon total composition weight.
- compositions contains more than inconsequential quantities of pigmentCs) and/or filler s), usuall least 3 percent by weight based upon total composition weight.
- compositions of the present invention all of the components can be simultaneously blended or mixed together by any suitable means.
- compositions of the present invention can be prepared by blending any one of the components: epoxy resin, carboxyl-containing polymer or stabilizer with preblend of the remaining two components.
- compositions of the present invention can be prepared by blending the epoxy resin with a prereaction product of the carboxyl-containing polymer and the stabilizer.
- the blending can be accomplished by any suitable means such as dry blending, m extrusion, 2-roll mill or other means of melt compounding, or any combination thereof.
- the temperature should at a temperature such that no reaction takes place between the epoxy groups of the epoxy resin a the carboxyl groups of carboxyl-containing polymer.
- the melt extrusion blending is conducted at a temperature of from 30°C to 120°C, more preferably from 40°C to 100°C, most preferably from 50°C to 70°C.
- the blending is conducted for a time sufficient to cause the resultant blend to be substantially homogeneous.
- substantially homogeneous it is meant a fine, uniform suspension with no individual particles large enough to seen.
- the preferred method of blending the carboxyl-containing polymer or the ionom form of the carboxyl-containing polymer, the reaction product of the carboxyl-containing polym with the stabilizer is to blend the carboxyl-containing polymer or the ionomer form of the carboxyl-containing polymer with the epoxy resin in a separate step to form an epoxy resin mod with the carboxyl-containing polymer.
- the advantage of blending in this manner is that the carboxyl-containing polymer is more uniformly dispersed in the epoxy resin than if it is blended directly into a powder coating formulation. Also, it is preferable to blend the epoxy resin and t carboxyl-containing polymer or the ionomer form of the carboxyl-containing polymer at conditio which do not result in reaction between the epoxy groups and the acid groups. Such conditions ar preferably at a temperature of from 30°C to 120°C, more preferably from 40°C to 100°C, most preferably from 50°C to 70°C.
- compositions of the present invention it is preferable to employ the ionomer form of the carboxyl-containing polymer. This is accomplished by prereacting the carboxyl-contining polymer with the stabilizer compound.
- the stabilizer, component (C) is employed in an amount sufficient to provide a ratio o equivalents of metal per carboxyl equivalent of at least 0.04:1, preferably from 0.08:1 to 6:1, mor preferably from 0.15:1 to 1:1.
- the stabilizer, component (3) is employed in an amount sufficient to provide a rati equivalents of metal per carboxyl equivalent of at least 0.04:1, preferably from 0.08:1 to 6:1, mor preferably from 0.15:1 to 1:1.
- the stabilizer, component (C) is employed in an amount sufficient to provide a ratio of equivalents of metal per carboxyl equivalent of at least 0.04:1, preferably from 0.08:1 to 6:1, more preferably from 0.15:1 to 1:1.
- the stabilizer, component (C) is employed in an amount sufficient to provide a ratio of equivalents of metal per carboxyl equivalent of at least 05:1, preferably from 0.6:1 to 6:1, more preferably from 0.7:1 to 1:1.
- the epoxy resin component (A) is employed in an amount of from 66 to 99, preferably from 80 to 96, more preferably from 80 to 92 percent by weight based upon the combined weight of epoxy resin (A) and carboxyl-containing polymer (B).
- the carboxyl-containing polymer component (B) is employed in an amount of from 1 to 33, preferably from 4 to 20, more preferably from 8 to 20 percent by weight based upon the combined weight of epoxy resin component (A) and carboxyl-containing polymer component (B).
- the amount of the other curing agent, component (D) depends upon the particular curing agent being employed. Usually the other curing agent is employed in amounts which provide a ratio of equivalents of this curing agent, component (D), plus the polymer containing carboxylic acid groups or ionomers thereof, component (B), per epoxide equivalent contained in component (A) of from 0.8:1 to 3:1, preferably from 0.9:1 to 2.5:1, more preferably from 1:1 to 2:1.
- the carboxyl-containing polymer, component (1) is employed in an amount of from 1 to 99, preferably from 3 to 96, more preferably from 25 to 90 percent by weight based upon the combined weight of components (1) and (2).
- the other or different curing agent, component (2) is employed in an amount of from 99 to 1, preferably from 97 to 4, more preferably from 75 to 10 percent by weight based upon the combined weight of components (1) and (2).
- a promoter or catalyst component in the curing agent compositions of the present invention, can, if it is desirable to employ such promoter or catalyst, be employed in an amount of from 0.01 to 2, preferably from 0.1 to 1-5, more preferably from 0.2 to 0.8 percent by weight based upon the combined weight of all of the curing agents, the stabilizer component and the promoter or catalyst.
- the curing agent compositions of the present invention can be prepared by simple blending or melt extruding all of the components.
- the curable compositions can be prepared by blending, mixing, melt extruding or a combination thereof all of the components thereof.
- the preparation of the curing agent compositions are usually prepared at temperatures of from 20°C to 200°C, preferably from 50°C to 150°C, more preferably from 70°C to 130°C for a time sufficient to produce a homogeneous product, usually within a time of from 15 seconds to 2 hours, depending upon how the components are blended together. If an extruder is employed in the preparation of the composition, shorter times of from 15 seconds up to 2 minutes is suitably employed. If a batch reactor or blender is employed, longer times are employed to prepare the composition such as from 5 minutes up to 2 hours.
- the byproduct(s) from the reaction between the carboxyl-containing polymer component and the stabilizer component prior to or after blending with the epoxy resin component.
- they can be readily removed by subjecting the composition to a vacuum and if desired heating while subjecting the composition to a vacuum at a temperature which is not detrimental to the composition, usually from room or ambient temperature to a temperature not above 120°C, preferably not above 100°C, more preferably not above 70°C.
- the pressure can be from zero to 760, preferably from zero to 200, more preferably from zero to 60 mm Hg absolute.
- Suitable epoxy resins which can be employed herein as component (A) include, for example, any epoxy resin which contains at least one aromatic ring in its backbone.
- Particularly suitable epoxy resins include, for example, the glycidyl ethers of: dihydric phenols, bisphenols, phenol- or substituted phenol-aldehyde novolac resins, adducts of dihydric phenols or bisphenols with an alkylene oxide having from 2 to 4 carbon atoms per molecule, phenol or substituted phenol-unsaturated hydrocarbon resins, or any combination of any two or more of such compounds; wherein said epoxy resin contains an average of more than one glycidyl ether group per molecule.
- These compounds can also contain substituent groups such as saturated aliphatic hydrocarbon, unsaturated aliphatic hydrocarbon, halogens including chlorine, bromine, fluorine, iodine, nitro, or nitrile.
- the hydrocarbon substituent groups can also be substituted with such halogens including chlorine, bromine, fluorine, iodine, nitro, or nitrile.
- these compounds can be specifically free of any one or more of such substituent groups and likewise the substituted hydrocarbons can be specifically free of any one or more of such substituent groups.
- such compounds and substituted hydrocarbons can contain any substituent group not specifically enumerated herein.
- the compounds and substituted hydrocarbons can be free of any substituent group not specifically enumerated herein.
- the preferred epoxy resins include, for example, the glycidyl ethers of: resorcinol, catechol, hydroquinone, bisphenol A (4,4'-isopropylidenediphenol), bisphenol F (2,2'- methylenediphenol), bisphenol K (4,4'-dihydroxydiphenyl ketone), bisphenol S (4,4'- sulfonyldiphenol), fluorene, phenol-formaldehyde novolac resins, cresol-formaldehyde novolac resins, phenol-dicyclopentadiene resins, phenol-higher oligomers of dicyclopentadiene resins, cresol-dicyclopentadiene resins, cresol-higher oligomers of dicyclopentadiene resins; adducts of: either resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol K, bisphenol S, or fluorene with
- the epoxy resins of the present invention preferably have equivalent weights of from 200 to 2000, more preferably from 500 to 955, most preferably from 575 to 820.
- the equivalent weight being calculated on the basis of there being no substituent groups on the aromatic rings of th epoxy resin even if they in fact do contain substituent groups.
- component (B) or (1) indude for example, those copolymers or interpolymers of one or mor alpha-olefins having from 2 to 10 carbon atoms and one or more ethylenically unsaturated carboxylic adds or half esters of dibasic ethylenically unsaturated carboxylic adds.
- alpha-olefins for example, ethylene, propylene, butene, pentene, hexene, heptene, ortene, nonene, decene or any combination of any two or more alpha-olefins.
- Ethylene is preferred.
- Particularly suitable ethylenically unsaturated carboxylic adds indude for example, acrylic, methacrylic, maleic, fumaric, itaconic. Preferred are acrylic add and methacryli add with acrylic add being most preferred.
- Particularly suitable half esters include the Ci to Cio, preferably to Q;, more preferably C1-C4 hydrocarbon half esters of maleic, fumaric or itaconic adds. More particularly suitable are the methyl, ethyl, propyl, butyl, pentyl and hexyl half esters of such adds.
- Suitable stabilizers which can be employed herein include, for example, Group IA, IIA, IIB, IIIA, VIB or VIII of the periodic table of the elements metal salts of an organic carboxylic add; zinc carbonate, zinc oxide, sodium carbonate or potassium carbonate; or any combination of any such stabilizers.
- Particularly suitable stabilizers include, for example, zinc oxide, sodium carbonate, zinc carbonate, potassium carbonate, or sodium, lithium, potassium, zinc, calcium, magnesium, nickel, aluminum or chromium salt of a saturated or unsaturated aliphatic or cycloaliphatic or aromatic organic carboxylic add having from 1 to 30, preferably from 1 to 18, more preferably from 1 to 2 carbon atoms per molecule, or a combination of any two or more of such compounds.
- carboxylic add salts indude, for example zinc carbonate, zinc acetate, zinc propionate, zinc stearate, sodium acetate, calrium propionate, or any combination of any two or more of such compounds.
- Suitable curing agents which can be employed herein in addition to the polymers containing a carboxylic add group or an ionomer thereof in the curing agent compositions or the curable compositions or powder coating compositions indude, for example, guanidines, biguanides, aliphatic amines, aromatic amines, compounds containing an average of more than one phenolic hydroxyl group per molecule, aliphatic, cydoaliphatic or aromatic di- or poly-carboxylic adds or anhydrides, or any combination of two or more of such curing agents.
- curing agents which can be employed herein as component (D) or (2) indude, for example, dicyandiamide, o-tolubiguanide, add functional polyesters, compounds containing more than one phenolic group per molecule, or any combination of any two or more of such curing agents.
- the preferred curing agent is dicyandiamide.
- the actual amount of curing agent employed depends upon the particular curing agent being employed. Usually the curing agent is employed in amounts which provide a ratio of equivalents of this curing agent plus the polymer containing carboxylic add groups or ionomers thereof per epoxide equivalent of from 0.8:1 to 3:1, preferably from 0.9:1 to 2.5:1, more preferably from 1:1 to 2:1.
- Suitable promoters or catalysts for promoting the.reaction between the curing agent components) with the epoxy resin, indude for example, primary, secondary or tertiary aliphatic or cydoaliphatic or aromatic amines, Lewis adds, Lewis bases, or any combination of any two or more of such promoters or catalysts.
- promoters or catalysts include, for example, imidazoles, substituted imidazoles, imidazoles adducted with an epoxide-containing compound such as mono-, di-or polygly ⁇ dyl ether compounds, substituted imidazoles adducted with an epoxide-containing compound such as mono-, di- or polygly ⁇ dyl ether compounds, or any combination of any two or more of such promoters or catalysts.
- the preferred promoters or catalysts are 2-methyl imidazole, 2-methyl imidazole adducted with a diglyddyl ether of bisphenol A, or any combination of any two or more of such promoters or catalysts-
- the amount of promoter will depend upon the particular promoter and curing agent being employed. Usually, the amount of promoter employed is from 0.01 to 2, preferably from 0.1 to 1.5, more preferably from 0.2 to 0.8 percent by weight based upon the combined weight of all of the curing agents, the stabilizer component and the promoter or catalyst.
- Suitable fillers which can be employed herein indude for example, mineral fillers such as, for example, inorganic oxides, carbonates, sulfates or silicates of a metal of Groups IA, IIA, IDA, HB, VIB, or VIE of the periodic table of the elements, or any combination of any two or more of such fillers.
- mineral fillers such as, for example, inorganic oxides, carbonates, sulfates or silicates of a metal of Groups IA, IIA, IDA, HB, VIB, or VIE of the periodic table of the elements, or any combination of any two or more of such fillers.
- the preferred fillers are titanium oxide, caldum carbonate, barium sulfate, magnesium silicate strontium silicate, or any combination of any two or more of such fillers.
- Suitable pigments which can be employed herein indude, for example, any inorganic or organic pigment which will provide the composition with the desired color or any combination of any two or more of such pigments.
- Suitable flow modifiers or flow control agents which can be employed herein indude, for example, acrylate copolymers, silicones, fluorocarbons, or any combination of any two or more of such flow modifiers or flow control agents.
- the preferred modifiers or flow control agents are acrylate copolymers.
- Suitable leveling agents which can be employed herein indude for example, benzoin.
- the optional fillers, pigments, flow modifiers or flow control agents, leveling agents, which can be employed herein are employed in functional amounts, i.e. those amounts which provide the coating with the desired properties which the particular additive imparts to the coating. These amounts will vary with the particular epoxy resin, curing agent and additive employed.
- the filler(s) is (are) usually employed in amounts of from zero to 60, preferably from zero to 50, more preferably from 2 to 35 percent by weight based upon the total weight of the composition.
- the pigment(s) is (are) usually employed in amounts of from zero to 50, preferably from zero to 40, more preferably from 2 to 35 percent by weight based upon the total weight of the composition.
- the flow modifier(s) or flow control agent(s) is (are) usually employed in amounts of from zero to 5, preferably from zero to 3, more preferably from zero to 2 percent by weight based upon the total weight of the composition.
- the leveling agent(s) is (are) employed in amounts of from zero to 2, preferably from zero to 15, more preferably from zero to 0.5 percent by weight based upon the total weight of the composition.
- Flow Modifier A is ModerezTM MFP commerdally available from Synthron Chemicals.
- BS-1 is barium sulfate commercially available from Mountain Minerals as Sparwite
- BS-2 is barium sulfate commerdally available from Pfizer as Barytes #1.
- Pigment A is carbon black commercially available from Columbia Chemicals as
- a modified epoxy resin is prepared by extruder melt mixing at a temperature of 90°C-110°C Carrwxyl-Cbnteining Polymer A and Epoxy Resin A at a weight ratio of 0.087:1 in a Z0 100-mm Baker-Perkins twin-screw extruder. The product is extruded as a thin sheet onto a chilled belt and then crushed.
- a powder coating formulation is prepared by melt mixing 2,000 g of the modified
- a dry blend of these components prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 90°C, and the screw at 70°C and 200 rpm.
- the extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150 mesh brass sieves (105-micron
- a portion of the powder is coated within two days following the melt-mbdng. A portion of the powder is coated after aging for 43 days at ambient temperature. The powder is sprayed with a Gema Type 710 electrostatic spray gun, 60 kv applied, onto grounded cold rolled steel panels. The powder coated pands are baked for 15 minutes at 180°C and air cooled.
- a powder coating formulation is prepared by melt mixing 2,000 g of the modified epoxy resin from Comparative Experiment A-l, 80 g of Curing Agent B, 26 g of How Modifier A, and 80 g of CaPr2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment A-2. 0 EXAMPLE 2
- a powder coating formulation is prepared by melt mixing 2000 g of the modified epoxy resin from Comparative Experiment A-l, 80 g of Curing Agent B, 26 g of How Modifier A, and 240 g of CaPr2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment A-2.
- a modified epoxy resin is prepared by melt mixing 2,000 g of Carboxyl-Containing Polymer A and 8,000 g of Epoxy Resin B.
- a dry blend of these components prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 80°C, and the screw at 70°C and 200 rpm.
- the modified epoxy resin extrudate is pressed with chilled rollers to a thin sheet, air cooled, and crushed.
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin from 1 above, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, and 10.06 g of How Modifier A.
- a dry blend of these components prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 90°C, and the screw at 70°C and 200 rpm.
- the extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150 mesh brass sieves C105-micron opening).
- a portion of the powder is coated within two days following the melt mixing. Another portion of the powder is coated after aging for 23 hours at 36°G
- the powder is electrostatically sprayed with a Gema gun onto grounded cold rolled steel pands. The powder coated pands are baked for 15 minutes at 180°C and
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin from Comparative Experiment B-l, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, 10.06 g of How Modifier A, and 12 g of CaPr2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment B-2.
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin from Comparative Experiment B-l, 600 g of additional Epoxy Resin B, 48 g of Curing
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin from Comparative Experiment B-l, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, 10.06 g of How Modifier A, and 48 g of CaPr2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment B-2.
- COMPARATIVE EXPERIMENT D Preparation of an Epoxy resin modified with 20% by weight of a Carboxyl-Containing Polymer.
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin described in 1 above, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, 245 g of
- a dry blend prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 90°C, and the screw at 70°C and 200 rpm
- the extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150-mesh brass sieves.
- a portion of the powder is coated within one day following the mdt mixing.
- a portion of the powder is coated after aging for 20 hours at 40°C
- the powder is electrostatically sprayed with a Gema gun onto grounded cold rolled steel panels.
- the powder coated pands are baked for 15 minutes at 180°C and air cooled.
- a powder coating formulation is prepared by mdt mixing 600 g of the modified epoxy resin from Comparative Experiment D-1, 600 g of additional Epoxy Resin B, 48 g of Curing
- Agent A 247 g of BS-2 filler, 23.19 g of Pigment A, and 15.46 g of How Modifier A, and 12 g of CaPr2 stabilizer.
- the composition is prepared and tested in the same way and at the same time as Comparative F-xperiment D-2.
- a powder coating formulation is prepared by mdt mixing 600 g of the modified epoxy resin from Comparative Experiment D-1, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, 250 g of BS-2 filler, 23.41 g of Pigment A, and 15.61 g of How Modifier A, and 24 g of CaPr2 stabilizer.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment D-2.
- a powder coating formulation is prepared by melt mixing 600 g of the modified epoxy resin from Comparative Experiment D-1, 600 g of additional Epoxy Resin B, 48 g of Curing Agent A, 254 g of BS-2 filler, 23.85 g of Pigment A, and 15.90 g of How Modifier A, and 48 g of CaPr2 stabilizer.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment D-2.
- a modified epoxy resin is prepared by melt mixing 1,800 g of Carboxyl-Containing
- the modified epoxy resin extrudate is pressed with chilled rollers to a thin sheet, air cooled, and crushed.
- a powder coating formulation is prepared by melt mixing 1,200 g of the modified epoxy resin prepared in 1 above, 600 g of additional Epoxy Resin B, 72 g of Curing Agent A, and 18.9 g of How Modifier A.
- a dry blend prepared by shaking the components together in a plastic bag, is mdt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 90°C, and the screw at 70°C and 200 rpm. The extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150 mesh brass sieves. A portion of the powder is coated within two days following the melt mixing.
- a portion of the powder is coated after aging for 24 hours at 40°C.
- a portion of the powder is coated after aging for 27 days at ambient temperature.
- the powder is electrostatically sprayed with a Gema gun onto grounded cold rolled steel panels.
- the powder coated panels are baked for 15 minutes at 180°C and air cooled.
- EXAMPLE 8 A powder coating formulation is prepared by melt mixing 1,200 g of the modified epoxy resin from Comparative Experiment E-l, 600 g of additional Epoxy Resin B, 72 g of Curing Agent A, 19.2 g of How Modifier A, and 312 g of CaPr2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment E-2.
- a powder coating formulation is prepared by melt mixing 1,200 g of the modified epoxy resin from Comparative Experiment E-l, 600 g of additional Epoxy Resin B, 72 g of Qiring Agent A, 193 g of How Modifier A, and 37.2 g of ZnAc2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment E-2.
- a powder coating formulation is prepared by melt mixing 1,200 g of the modified epoxy resin from Comparative Experiment E-l, 600 g of additional Epoxy Resin B, 72 g of Curing Agent A, 20.0 g of How Modifier A, and 105.6 g of ZnS_2 stabilizer. The composition is prepared and tested in the same way and at the same time as Comparative Experiment E-2.
- a modified epoxy resin is prepared by melt mixing 900 g of Carboxyl-Containing
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin prepared in 1 above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- a dry blend prepared by shaking the components together in a plastic bag, is mdt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 80°C, and the screw at 70°C and 200 rpm. The extrudate is pressed with chilled rollers to a thin sheet air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150-mesh brass sieves.
- a portion of the powder is coated within one day following the mdt mixing. Another portion of the powder is coated after aging for 24 hours at 40°G Another portion of the powder is coated after aging for 33 days at ambient temperature.
- the powder is sprayed with a Wagner GlOO EPB dectrostatic spray gun onto grounded cold rolled sted panels. The powder coated panels are baked for 15 minutes at 180°C and air cooled.
- EXAMPLE 11 A Preparation of prereaction product of Carboxyl-Containing Polymer and metal salt.
- a prereaction product (ionomer) of Carboxyl-Containing Polymer A is prepared by mdt mixing 11.7 g/min of CaPi2 stabilizer and 270 g/rnin of C-arboxyl-Cbntaining Polymer A in a Werner and Pfldderer CWP) 30-mm twin-screw extruder.
- the barrel temperatures are: zone 1 at 52°C and zones 2 - 5 at 113°C - 121 °C
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 in C6 5 mm) pdlets.
- a modified epoxy resin is prepared by melt mixing 900 g of the caldum ionomer of Carboxyl-Containing Polymer A prepared in A above and 5,100 g of Epoxy Resin B.
- the composition is prepared in the same way as the modified resin from Comparative Experiment F-l.
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment F-2.
- a prereaction product Cionomer) of Carboxyl-Containing Polymer A is prepared by mdt mixing 13.2 g/min of ZnAc2 stabilizer and 270 g/min of C-arboxyl-C-Dntaining Polymer A in a Werner and Pfleiderer CWP) 30-mm twin-screw extruder.
- the barrel temperatures are: zone 1 at 52°C and zones 2 - 5 at 113°C - 121°C.
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 in C635 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 900 g of the zinc ionomer of
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A. The composition is prepared and tested in the same way and at the same time as Comparative Experiment F-2.
- a modified epoxy resin is prepared by melt mixing 600 g of Carboxyl-Containing Polymer A and 3,400 g of Epoxy Resin B.
- a dry blend prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 80°C, and the screw at 70°C and 200 rpm.
- the modified epoxy resin extrudate is pressed with chilled rollers to a thin sheet, air cooled, and crushed.
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin prepared in 1 above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- a dry blend prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 80°C, and the screw at 70°C and 200 rpm. The extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150-mesh brass sieves.
- a portion of the powder is coated within one day following the mdt mixing.
- a portion of the powder is coated after aging for 24 hours at 40°C.
- the powder is electrostatically sprayed with a Wagner gun onto grounded cold rolled steel pands.
- the powder coated panels are baked for 15 minutes at 180°C and air cooled.
- a prereaction product Cionomer) of Carboxyl-Containing Polymer A is prepared by mdt mixing 8.8 g/min of ZnAc2 stabilizer and 355 g/min of Carboxyl-Containing Polymer A in a WP 30-mm twin-screw extruder.
- the barrel temperatures are zone 1 at 53°C and zones 2 - 5 at 109 - 117°C.
- the product is extruded through a 3-strand die, water cooled, and chopped to 1 /4 in C635 mm) pellets.
- a modified epoxy resin is prepared by mdt mixing 600 g of the zinc ionomer of C-arboxyl-Containing Polymer A prepared in A above and 3,400 g of Epoxy Resin B.
- the composition is prepared in the same way as the modified resin from Comparative Experiment G-l.
- a powder coating formulation is prepared by mdt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- the composition is prepared and tested in the same way and at the same time as
- a prereaction product Cionomer) of Carboxyl-Containing Polymer A is prepared by mdt mixing 17.1 g/min of ZnAc2 stabilizer and 355 g/min of Carboxyl-Containing Polymer A in a WP 30-mm twin-screw extruder.
- the barrel temperatures are: zone 1 at 51°C and zones 2 - 5 at 105 - 116°C.
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 in C6-35 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 600 g of the zinc ionomer of Carboxyl-Containing Polymer A and 3,400 g of Epoxy Resin B.
- the composition is prepared in the same way as the modified resin from Comparative Experiment G-1.
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment G-2.
- a powder coating formulation is prepared by mdt mixing 1500 g of the modified epoxy resin from Comparative Experiment G-1, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, 19.1 g of How Modifier A, and 11.25 g of ZnAc2 stabilizer.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment G-2.
- COMPARATIVE EXPERIMENT H Preparation of an Epoxy resin modified with 15% by weight of a Carboxyl-Containing Polymer.
- a modified epoxy resin is prepared by extruder melt mixing at a temperature of 90°C-110°C and Epoxy Resin B at a weight ratio of 0.85:1 in a 100 mm Baker-Perkins twin-screw extruder. The product is extruded as a thin sheet onto a chilled bdt and then crushed.
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from 1 above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- a dry blend prepared by shaking the components together in a plastic bag, is mdt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 70°C, zone 2 at 80°C, and the screw at 70°C and 200 rpm. The extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150-mesh brass sieves.
- a portion of the powder is coated within one day following the mdt mixing. Another portion of the powder is coated after aging for 24 hours at 40°C The powder is dectrostatically sprayed with a Wagner gun onto grounded cold rolled steel panels. The powder coated pands are baked for 15 minutes at 180°C and air cooled.
- a prereaction product Cionomer) of C_-rboxyl-Containing Polymer A is prepared by mdt mixing 225 g/min of NaAc stabilizer and 355 g/min of C---rrx)xyl ntaining Polymer A in a WP 30-mm twin-screw extruder.
- the barrel temperatures are zone 1 at50°C and zones 2 - 5 at 104°C - 107°C
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 in (6.35 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 600 g of the zinc ionomer of
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A. The composition is prepared and tested in the same way and at the same time as Comparative Experiment H-2.
- a prereaction product Cionomer) of Carboxyl-Containing Polymer A is prepared by melt mixing 473 g/min of ZnAc2 stabilizer and 355 g/min of Carboxyl-Containing Polymer A in a
- WP 30-mm twin-screw extruder The barrel temperatures are zone 1 at 48°C and zones 2 - 5 at 105 - 113°C
- the product is extruded through a 3-strand die, water cooled, and chopped to 1 /4 in C635 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 600 g of the zinc ionomer of Carboxyl-Containing Polymer A and 3400 g of Epoxy Resin B.
- the composition is prepared in the same way as the modified resin from Comparative Experiment G-1.
- a powder coating formulation is prepared by mdt mixing 1500 g of the modified epoxy resin from B above, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment H-2.
- a powder coating formulation is prepared by melt mixing 1500 g of the modified epoxy resin from Comparative Experiment G-1, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, 19.1 g of How Modifier A, and 11.25 g of ZnAc2 stabilizer.
- the composition is prepared and tested in the same way and at the same time as Comparative Experiment H-2.
- a prereaction product (ionomer) of Carboxyl-Containing Polymer A is prepared by melt mixing 48.2 g/min of ZnSt2 stabilizer and 355 g/min of Carboxyl-Containing Polymer A in a WP 30-mm twin-screw extruder.
- the barrel temperatures are zone 1 at 56°C and zones 2 - 5 at 128°C - 139°C.
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 in (6.35 mm) pellets.
- a modified epoxy resin is prepared by mdt mixing 600 g of the zinc ionomer of
- a powder coating formulation is prepared by mdt mixing 1500 g of the modified epoxy resin, 60 g of Curing Agent A, 300 g of BS-1 filler, 28.6 g of Pigment A, and 19.1 g of How Modifier A. The composition is prepared and tested in the same way and at the same time as Comparative Experiment H-2.
- a prereaction product (ionomer) of Carboxyl-Containing Polymer A is prepared by mdt mixing a dry-blended mixture of approximately 4,000 g of a 0.0488:1 wdght ratio of ZnAc2 stabilizer and the ion product Cionomer) of Carboxyl-Containing Polymer A in a WP 30-mm twin screw extruder.
- the barrd temperatures are: zone l at44°C and zones 2-5 at 103°C-111°C
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 inch C635 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 450 g of the zinc ionomer of
- a powder coating formulation is prepared by melt mixing 1570 g of modified epoxy resin from B above, 62.9 g of Curing Agent A, 315 g of BS-1 filler, 30 g of Pigment A, and 20 g of How Modifier A.
- a dry blend prepared by shaking the components together in a plastic bag, is melt mixed in a Buss Condux PLK 46 extruder having two zones with zone 1 at 50°C, zone 2 at 80°C, and the screw at 50°C and 200 rpm. The extrudate is pressed with chilled rollers to a thin sheet, air cooled, ground to a fine powder with a Brinkmann ZM-1 grinder and sieved through 150 mesh brass sieves. A portion of the powder is coated within one day following the melt mixing. Another portion of the powder is coated after aging for 24 hours at 40°C The powder is electrostatically sprayed with a Wagner gun onto cold rolled sted panels. The powder coated panels are baked for 15 minutes at 180°C and air cooled.
- a prereaction product Cionomer of Carboxyl-Containing Polymer A is prepared by melt mixing a dry-blended mixture of 120.6 g of ZnCCt ⁇ stabilizer and 4324 g of Carboxyl-Containing Polymer A in a WP 30-mm twin screw extruder.
- the barrd temperatures are: zone 1 at 46°C and zones 2-5 at 105°C - 111°G
- the product is extruded through a 3-strand die, water cooled, and chopped to 1/4 inch C635 mm) pellets.
- a modified epoxy resin is prepared by melt mixing 450 g of the zinc ionomer of Carboxyl-Containing Polymer A prepared in A above and 2550 g of Epoxy Resin B. The composition is prepared in the same manner as in Example 20-B.
- a powder coating formulation is prepared by melt mixing 1570 g of modified epoxy resin from B above, 62.9 g of Curing Agent A, 315 g of BS-1 filler, 30 g of Pigment A, and 20 g of How Modifier A.
- the composition is prepared in the same manner as in Example 20-C
- Table I provides a summary description of the examples and comparative experiments grouped in sets of concurrently obtained examples and comparative experiments.
- CaPr2 caldum propionate, ZnAc2, zinc acetate; NaAc, sodium acetate; ZnSt2 , zinc stearate.
- Epoxy Resin A is not an example of the present invention. Epoxy Resin A.
- C-arboxyl-containing copolymer A Epoxy Resin B.
- CaPr2 Caldum propionate
- ZnAc2 zinc acetate
- NaAc sodium acetate
- Epoxy Resin B Carixjxyl-containing copolymer A.
- CaP ⁇ 2 Caldum propionate
- ZnAc2 zinc acetate
- NaAc sodium acetate
- ZnC ⁇ 3 zinc carbonate.
- Table V provides a summary of the coating thickness, coating gloss values, and the relative change in the gloss values comparing the coating from the aged powder to the coating from the fresh powder.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
On augmente la stabilité à la conservation de compositions de résine époxy contenant des polymères contenant un carboxyle en tant qu'additif de diminution de brillance au moyen de l'apport d'une quantité stabilisante d'au moins un composé stabilisateur qui est: (a) au moins un sel métallique d'un acide carboxylique organique, ce sel appartenant au groupe IA, IIA, IIB, IIIA, VIB ou VIII du tableau périodique des éléments; (b) au moins un composé parmi le carbonate de zinc, l'oxyde de zinc, le carbonate de sodium ou le carbonate de potassium; ou (c) toute combinaison de (a) et de (b). Ces compositions sont particulièrement efficaces dans des applications de revêtement en poudre.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82778192A | 1992-01-29 | 1992-01-29 | |
US827781 | 1992-01-29 | ||
PCT/US1993/000702 WO1993015158A1 (fr) | 1992-01-29 | 1993-01-27 | Compositions modifiees de resine epoxy, compositions de revetement a brillance reduite |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0624183A1 true EP0624183A1 (fr) | 1994-11-17 |
Family
ID=25250149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93904648A Withdrawn EP0624183A1 (fr) | 1992-01-29 | 1993-01-27 | Compositions modifiees de resine epoxy, compositions de revetement a brillance reduite |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0624183A1 (fr) |
JP (1) | JPH07503279A (fr) |
KR (1) | KR950700374A (fr) |
CN (1) | CN1074919A (fr) |
AU (1) | AU3593893A (fr) |
BR (1) | BR9305888A (fr) |
CA (1) | CA2128414A1 (fr) |
MX (1) | MX9300478A (fr) |
NO (1) | NO942815L (fr) |
TW (1) | TW252124B (fr) |
WO (1) | WO1993015158A1 (fr) |
ZA (1) | ZA93616B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009031278A1 (de) | 2009-06-30 | 2011-01-05 | REMIS Gesellschaft für Entwicklung und Vertrieb von technischen Elementen mit beschränkter Haftung | Lebensmittel-Kühltruhe und Abdeckung hierfür |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4400929A1 (de) * | 1994-01-14 | 1995-07-20 | Huels Chemische Werke Ag | Verfahren zur Herstellung von matten Epoxidharzbeschichtungen |
EP1102797B1 (fr) | 1998-07-27 | 2006-03-22 | E.I. Du Pont De Nemours And Company | Resines copolymeres neutralisees de metaux melanges utilisees pour appliquer une poudre de revetement sur des objets metalliques |
US6882058B2 (en) | 2002-11-05 | 2005-04-19 | Henkel Corporation | Organic acid containing compositions and methods for use thereof |
JP2006182963A (ja) * | 2004-12-28 | 2006-07-13 | Honda Motor Co Ltd | 塗料組成物及び自動車車体構成部材 |
US20110257299A1 (en) * | 2009-01-06 | 2011-10-20 | Dow Global Technologies Llc | Metal stabilizers for epoxy resins |
EP2385974A4 (fr) * | 2009-01-06 | 2012-12-05 | Dow Global Technologies Llc | Stabilisants métalliques pour résines époxydes et procédé de dispersion |
DE112018004743T5 (de) | 2017-09-05 | 2020-06-18 | Fujifilm Corporation | Härtbare zusammensetzung, gehärtetes produkt und linseneinheit |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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NL126705C (fr) * | 1964-07-31 | Carnaud & Forges | ||
US4419495A (en) * | 1981-09-21 | 1983-12-06 | The Dow Chemical Company | Epoxy resin powder coatings having low gloss |
-
1993
- 1993-01-27 CA CA002128414A patent/CA2128414A1/fr not_active Abandoned
- 1993-01-27 EP EP93904648A patent/EP0624183A1/fr not_active Withdrawn
- 1993-01-27 JP JP5513394A patent/JPH07503279A/ja active Pending
- 1993-01-27 BR BR9305888A patent/BR9305888A/pt not_active Application Discontinuation
- 1993-01-27 AU AU35938/93A patent/AU3593893A/en not_active Abandoned
- 1993-01-27 WO PCT/US1993/000702 patent/WO1993015158A1/fr not_active Application Discontinuation
- 1993-01-27 KR KR1019940702624A patent/KR950700374A/ko not_active Application Discontinuation
- 1993-01-28 CN CN93100906A patent/CN1074919A/zh not_active Withdrawn
- 1993-01-28 ZA ZA93616A patent/ZA93616B/xx unknown
- 1993-01-28 TW TW082100498A patent/TW252124B/zh active
- 1993-01-28 MX MX9300478A patent/MX9300478A/es unknown
-
1994
- 1994-07-28 NO NO942815A patent/NO942815L/no unknown
Non-Patent Citations (1)
Title |
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See references of WO9315158A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009031278A1 (de) | 2009-06-30 | 2011-01-05 | REMIS Gesellschaft für Entwicklung und Vertrieb von technischen Elementen mit beschränkter Haftung | Lebensmittel-Kühltruhe und Abdeckung hierfür |
DE102009031278B4 (de) * | 2009-06-30 | 2017-10-05 | REMIS Gesellschaft für Entwicklung und Vertrieb von technischen Elementen mit beschränkter Haftung | Lebensmittel-Kühltruhe und Abdeckung hierfür |
Also Published As
Publication number | Publication date |
---|---|
ZA93616B (en) | 1994-07-28 |
TW252124B (fr) | 1995-07-21 |
JPH07503279A (ja) | 1995-04-06 |
NO942815L (no) | 1994-09-21 |
BR9305888A (pt) | 1997-08-19 |
CA2128414A1 (fr) | 1993-08-05 |
KR950700374A (ko) | 1995-01-16 |
MX9300478A (es) | 1993-07-01 |
NO942815D0 (no) | 1994-07-28 |
AU3593893A (en) | 1993-09-01 |
CN1074919A (zh) | 1993-08-04 |
WO1993015158A1 (fr) | 1993-08-05 |
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