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WO1993020121A1 - Nouvel agent de reticulation utilise dans des laques en poudre d'urethane a base acrylique - Google Patents

Nouvel agent de reticulation utilise dans des laques en poudre d'urethane a base acrylique Download PDF

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Publication number
WO1993020121A1
WO1993020121A1 PCT/US1993/000542 US9300542W WO9320121A1 WO 1993020121 A1 WO1993020121 A1 WO 1993020121A1 US 9300542 W US9300542 W US 9300542W WO 9320121 A1 WO9320121 A1 WO 9320121A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
crosslinker
acrylic
blocking agent
hydroxyl
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.)
Ceased
Application number
PCT/US1993/000542
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English (en)
Inventor
Melvin Kaplan
Rose Maria Trapasso
Stephen Craig Lapin
Frank Courtney Briden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of WO1993020121A1 publication Critical patent/WO1993020121A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the invention relates to novel crosslin ers which may be used to produce acrylic-based urethane powder coatings having improved flexibility and impact resistance. These coatings may be used in a variety of automotive, decorative and protective industrial and household applications including coatings for bathroom fixtures, furniture builders' hardware and cast aluminum wheels.
  • acrylic-based urethane powder coatings are superior to polyester or epoxy-based urethane coatings in a number of areas including clarity, durability, resistance to UV degradation and chemical and solvent resistance, their use has been limited by their brittleness. Impact resistance and flexibility are key concerns in many applications including automotive trim and outdoor furniture applications.
  • crosslinkers do not improve the limited flexibility and impact resistance of the acrylic-based systems.
  • the crosslinkers that have traditionally been employed in acrylic-based powder coating applications either do not contain a polyol component or contain a low molecular weight polyol which when blended with the acrylic resin increase its hardness and ultimately makes the resulting coating somewhat brittle.
  • novel crosslinkers of the invention eliminate this brittleness problem and thus, for the first time, open the door to a range of applications in which acrylic-based urethane powder coatings have traditionally been excluded.
  • acrylic-based urethane powder coating shall refer to any urethane powder coating in which the resin component of the coating composition comprises an acrylic resin.
  • a typical acrylic-based urethane powder coating contains an acrylic resin, a crosslinker, fillers or pigments and other additives like surfactants and flow modifiers.
  • the polyol portion of the crosslinker when present in the crosslinker, has included such low molecular weight polyols like 1,4- hexanediol, trimethylolpropane, 1,4- cyclohexanedimethanol, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, dipropylene glycol and trimethylolethane.
  • polyols like 1,4- hexanediol, trimethylolpropane, 1,4- cyclohexanedimethanol, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, dipropylene glycol and trimethylolethan
  • a crosslinker composition comprising a polyol, polyisocyanate and blocking agent wherein the blocking agent is other than a 1,2-polyol or a monoethylenically unsaturated blocking agent
  • the improvement comprises utilizing as said polyol an organic polyol or mixture of polyols wherein each polyol has at least two hydroxyl groups, an equivalent weight greater than 250 to about 2500, an acid number of less than about 20 and functional groups solely selected from the group consisting of ester, other than lactones, ether, acrylic, carboxyl and hydroxyl wherein when an acrylic polyol is used, said acrylic polyol is used in combination with a polyol having a functionality solely selected from the group consisting of ester, other than lactones, ethers, carboxyl and hydroxyl which produces a crosslinker composition having less than about 1% by weight unblocked isocyanate, at least about 4% by weight available isocyanate after deblocking and a softening point of from about 75
  • the crosslinker has from at least 4 to about 12 weight percent available isocyanate after deblocking and a softening point of from about 85 to about 120°C.
  • the crosslinker has from about 6 to about 11 weight percent available isocyanate after deblocking and a softening point of from about 105 to about 120°C.
  • the crosslinker has from about 7 to about 9 weight percent available isocyanate after deblocking.
  • the invention comprises an organic polyol or mixture of polyols wherein each polyol has an equivalent weight greater than 250 to about 2500, at least 2 hydroxyl groups per polyol, an acid number of less than about 20 and functional groups solely selected from the group consisting of ester, other than lactones, ether, acrylic, carboxyl and hydroxyl wherein when an acrylic polyol is used, said acrylic polyol is used in combination with a polyol having a functionality solely selected from the group consisting of ester, other than lactones, ethers, carboxyl and hydroxyl.
  • the blocking agent is a ketoxime, lactam or blend thereof.
  • the organic polyol of the invention is selected from the group consisting of: Cargill 30-3000, FORMREZ «8009-146, F0RMREZ»55-225, RUCOTE «lll, RUCOTE «112, Cargill 30- 3016, Joncryl SCX-800 B and mixtures thereof.
  • the organic polyol is prereacted with the isocyanate component of the crosslinker to form an NCO terminated prepolymer.
  • the organic polyol has an average hydroxyl functionality of at least 2 to about 4.
  • hydroxyl number (for the organic polyols) was determined in accordance with ASTH D 4274-83.
  • Acid number (for the organic polyols) was determined in accordance with ASTM D 4662- 87.
  • Cargill 30-3000 and Cargill 30-3016 may be purchased from Cargill Inc. of Minneapolis, Minnesota.
  • F0RMREZ «8009-146 may be purchased from Witco Corporation, Organics Division of Melrose Park, Illinois.
  • RUC0TE»111 and 112 may be purchased from Ruco Polymer Corporation of Hicksville, New York and Joncryl SCX-800 B may be purchased from S.C. Johnson & Son, Inc. of Racine, Wisconsin. Based on the instant disclosure, other suitable organic polyols will readily occur to those skilled in the art.
  • polyester polyols useful in the invention may be obtained by the conventional condensation of a polybasic acid such as isophthalic acid with a polyol such as neopentyl glycol and/or 1,6- hexanediol or the like with an excess of hydroxyls.
  • a polybasic acid such as isophthalic acid
  • a polyol such as neopentyl glycol and/or 1,6- hexanediol or the like
  • acrylic polyols useful in the invention may be obtained by copolymerizing a hydroxyl containing acrylic monomer such as hydroxy ethyl methacrylate with an acrylic monomer such as methyl methacrylate and styrene.
  • Other suitable polyether polyols may be prepared by the condensation reaction of a polyol with propylene and/or ethylene oxide.
  • organic aliphatic or aromatic polyisocyanates or blends thereof may be used in practicing the invention. They include isophorone diisocyanate, 4,4'-methylene bis-(cyclohexyl isocyanate) , toluene diisocyanate, hexamethylene diisocyanate, cyclohexylene-l,3-diisocyanate, m- phenylene diisocyanate, p-phenylene diisocyanate, 4,4'- diphenyl diisocyanate, 1,5-napthalene diisocyanate, toluene trisisocyanate, 1,4-xylene diisocyanate and 4,4 * -diphenyl methyl diisocyanate.
  • Isophorone diisocyanate, toluene diisocyanate, l,3-bis-(l- isocyanato-1-methylethyl)-benzene, bis-(4-isocyanato cyclohexyl)methane are preferred. These materials are all commercially available. Isophorone diisocyanate is available, for example, through H ⁇ ls America Inc. Bis- (4-isocyanato cyclohexyl) methane, may be purchased, for example, through Miles Inc. of Pittsburgh, Pennsylvania under the name Desmodur W 1 .
  • l,3-bis-(l- isocyanato-1-methylethyl)-benzene may be purchased, for example, through American Cyanamid Company and toluene diisocyanate is available, for example, through Miles Inc. as Mondur TD-80 2 .
  • any of the blocking agents known in the art to be useful in acrylic-based powder coating applications other than 1,2-polyols including, for example, ethylene glycol, 1,2-propylene glycol, 1,2-butane diol and hydrolyzed butyl glycidyl ether
  • ethylenically unsaturated blocking agents including, for example, butylaminoethyl methacrylate, methacrylamide, allyl alcohol and 4-(4-hydroxybutyl)-2-vinyl-l,3-dioxolane
  • Desmodur W is a liquid cycloaliphatic diisocyanate which is used in the manufacture of high performance specialty polymers such as light fast and color stable urethane coatings. It has the following typical properties:
  • Mondur TD-80 is an aromatic diisocyanate. Specifically it is a mixture of 2,4 and 2,6 toluene diisocyanate isomers in the ratio of 80% and 20% respectively. Mondur TD-80 has the following typical properties:
  • lactams like e-caprolactam and mixtures thereof are commercially available and may be purchased, for example, through Allied-Signal Inc. of Morristown, New Jersey. Alternately, acetone oxime and other keto imes may be synthesized in accordance with U.S. Patent 4,323,706 to Bonfield et al.
  • the crosslinker compositions of the invention may also contain an organometallic catalyst or a blend thereof.
  • organometallic catalyst Of those known in the art, dibutyl tin dilaurate is preferred.
  • the proportions in which the organic polyol, polyisocyanate and blocking agent components of the crosslinker composition of the invention can be combined are well known to those skilled in the art.
  • the composition is formulated such that the equivalents ratio of NCO groups to hydroxyl groups and blocking agents is about 0.85:1 to about 1:1.3.
  • the equivalents ratio of NCO groups to hydroxyl groups and blocking agents is about 0.85:1 to about 1:1.3.
  • to form a composition in which substantially all of the groups react about a 1:1 to about a 1:1.03 ratio is used.
  • Percent NCO by weight before deblocking was determined using ASTM D1638. Percent NCO by weight after deblocking (or % NCO blocked) was determined using the following formula:
  • Acrylic-based urethane powder coatings were prepared using the crosslinkers of the Examples. Various physical properties of these coatings were measured.
  • Average dry film thickness was determined using Model # 256FN from Elcometer of Birmingham, Michigan. Gloss was determined at two different angles, i.e., 60 s and 20° using a glossmeter. Model # 4411, from K. Chemie of Chicago, Illinois. Film hardness was determined using the procedure and equipment described in ASTM D3363-74 (reapproved 1989) . Cross-hatch adhesion was determined using the procedure and equipment described in ASTM D3359-90. Reverse and direct impact were determined using the apparatus and procedure described in ASTM D2794-90 using a 5/8 inch dia eter die/head. Conical mandrel was determined using the procedure and equipment described in ASTM D522-88.
  • Solvent rub reported in certain Examples was determined in accordance with the procedure recommended by the Powder Coating Institute for solvent cure test 1988. Distinctness of image was determined using a distinctness of image meter from the Paul N. Gardner Company of Pompano Beach, Florida. Various coatings were visually rated within a series. "A” represents coatings which were uniform and smooth. “B” represents coatings which were not as uniform or smooth as the "A” coatings.
  • IPDI isophorone diisocyanate 3
  • the isophorone diisocyanate (3-isocyanatomethyl- 3 , 5 , 5-trimethylcyclohexyl isocyanate) used herein was manufactured by H ⁇ ls America , Inc . It has the following typical properties :
  • FORMREZ® 55-225 is Witco • s trademark for its poly(neopentyl adipate) . It has the following properties: OH # 25.3 % H 2 0 0.017
  • Cargill 30-3000 is manufactured by Cargill, Inc. of Minneapolis, Minnesota. It is a functional polyester resin having the following properties:
  • FORMREZ® 8009-146 is a linear adipate/isophthalate polyester resin otherwise known as poly 1,6- hexane/neopentyl adipate/isophthalate. It typically has the following properties:
  • the effluent from the extruder was passed through rollers into a sheet.
  • the resulting extrudate was broken up into small flat chips which were cooled with liquid nitrogen and ground into a powder. Subsequent sizing through a 40 mesh screen yielded a fine powder.
  • the resulting composition was electrostatically sprayed onto metal sample panels. The panels were then baked for 25 minutes at 190°C.
  • the resulting panel coatings were 1-2 mil
  • Degussa Special Black 4A pigment was the black pigment used in the coating formulation described herein.
  • Benzoin is an additive to reduce surface imperfections. It may be purchased, for example, from Aldrich Chemical Company of Milwaukee, Wisconsin. It has the following typical properties:
  • MODAFLOW® is a registered trademark of Monsanto Company.
  • MODAFLOW® Powder III is a resin modifier developed to reduce surface imperfections in industrial powder coatings. It has the following typical properties:
  • RUCOTE® is a registered trademark of Ruco Polymer Corporation of Hicksville, New York.
  • RUCOTE® 111 is a polyester resin useful in powder coatings. It has the following typical properties:
  • the resulting crosslinker had the following properties:
  • crosslinkers prepared in Examples 4 and 5 above were formulated with Joncryl SCX-800B into an acrylic- based urethane powder coating at an NCO:OH ratio of 1:1 in accordance with the procedure outlined below:
  • TMXDI® (META) aliphatic isocyanate or meta- Tetra ethylxylene diisocyanate is commercially available from American Cyanamid. It has the following typical properties:
  • RUCOTE® is a registered trademark of Ruco Polymer Corporation of Hicksville, New York.
  • RUCOTE® 112 is a polyester resin useful in powder coatings. It has the following typical properties: Color (Gardner-Holt/50%in M-PYROL (GAF) ⁇ 2 Viscosity (ICI Cone and Plate @ 200°C) , poise 40-55 Hydroxyl # 28-35
  • H ⁇ ls B 1530 crosslinker was the control.
  • H ⁇ ls B 1530 is a standard crosslinker used to make acrylic-based urethane powder coatings. Applicants believe that this crosslinker does not contain a polyol. It has the following typical properties:
  • Joncryl . SCX-800B, black pigment, benzoin, MODAFLOW® Powder III and crosslinker were premixed using a Vita-Mix blender Model 3600 from Vita-Mix Corporation of Cleveland, Ohio at high speed before melt mixing. Samples of the dry powder blend were then processed on a Brabender two-roll mill Type PM-3000, No. 128 B from c.w. Brabender Instruments, Inc. of E. Hackensack, New Jersey with the hot roll at 130°C and the cold roll chilled with tap water. The melt was processed for a total of 3 minutes at 130 rpm with sample rotation at 1 minute intervals.
  • the resulting product was then ground using a Brinkman ultra centrifugal mill, Model ZM-l from Brinkman Instruments of Westbury, New " York at 20,000 rp through a 0.5 screen. Samples were sieved through a 140 mesh vibratory sieve prior to electrostatic spray application over grounded steel panels pretreated with zinc phosphate. The coated panels were then baked at 190°C for 25 minutes to form hard glossy coatings.
  • the resulting coatings had the following properties:
  • the resulting crosslinker had the following properties:
  • the resulting crosslinker had the following properties:
  • the cured crosslinker prepared in Example 7 was formulated with SCX-802 into an acrylic-based urethane powder coating at an NCO:OH ratio of 1:1 in accordance with the procedure outlined on pages 18-19 above.
  • SCX-802 is manufactured by S.C. Johnson & Son Inc. of Racine, Wisconsin. It has the following typical properties:
  • ** H ⁇ LS B 1530 was the control. See page 25 for control formulation.
  • the resulting coating had the following properties:
  • the cured crosslinkers prepared in Examples 6 and 7 were formulated with Joncryl 587 at an NCO:OH ratio of 1:1 in accordance with the procedure outlined on pages 18 and 19 above.
  • Joncryl 587 is an acrylic polyol designed for use in high performance isocyanate-crosslinked urethane coatings. It has the following typical properties:
  • Non-volatile content 100% Color, Gardner-Holt ⁇ l Equivalent Wt. 600 OH ⁇ (calc.) 94 Density,lb/gal. 9.7
  • the resulting coatings had the following properties:
  • crosslinkers prepared in Examples 8-10 above were formulated into an acrylic-based urethane powder coating. Specifically, the cured crosslinker prepared in Example was formulated with Joncryl SCX-802 at an NCO:OH ratio of 1:1 in accordance with the procedure outlined on pages 18 and 19 above.
  • the resulting coatings had the following properties:
  • the cured crosslinkers prepared in Examples 9 and 10 were formulated with SCX-802 into an acrylic based urethane powder coating at a NCO:OH ratio of 1:1 in accordance with the procedure outlined on pages 18 and 19 above.
  • H ⁇ Ti- ⁇ -5TO ⁇ c"rosslinker was th ⁇ -ontrol ⁇ ee page 25 for control formulation.
  • the resulting coatings had the following properties:
  • Huls B 1530 crosslinker was the control, See page 26 for control comparative data.
  • crosslinker prepared in Example 11 above was formulated with Joncryl SCX-802 into an acrylic-based urethane powder coating at an NCO:OH ratio of 1:1 in accordance with the procedure outlined on pages 18 and 19 above.
  • the resulting coating had the following properties:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention se rapporte à de nouveaux agents de réticulation qui peuvent être utilisés pour produire des laques en poudre d'uréthane à base acrylique présentant une flexibilité et une résistance au choc améliorées. Ces laques peuvent être utilisées dans différents domaines d'application industriels et domestiques, à des fins de décoration et de protection ainsi qu'en ce qui concerne les automobiles, y compris comme laques pour les accessoires de salles de bains, pour du matériel pour fabricants de mobilier et pour des roues coulées en aluminium.
PCT/US1993/000542 1992-03-31 1993-01-21 Nouvel agent de reticulation utilise dans des laques en poudre d'urethane a base acrylique Ceased WO1993020121A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86091392A 1992-03-31 1992-03-31
US860,913 1992-03-31

Publications (1)

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WO1993020121A1 true WO1993020121A1 (fr) 1993-10-14

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2205322A (en) * 1987-05-29 1988-12-07 Takeda Chemical Industries Ltd Thermosetting resin compositions and precoated metal
EP0324370A1 (fr) * 1988-01-12 1989-07-19 Mobay Corporation Compositions aqueuses pour utilisation lors de la préparation de polyuréthanes réticulés
WO1990007531A1 (fr) * 1988-12-27 1990-07-12 Cargill, Incorporated Isocyanate bloque et son procede de fabrication
EP0403779A2 (fr) * 1989-06-19 1990-12-27 Cytec Technology Corp. Compositions de revêtement pulvérulentes durcissables contenant des isocyanates bloqués par caprolactame
WO1991015532A1 (fr) * 1990-04-09 1991-10-17 Eastman Kodak Company Compositions de poudres pour revetement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2205322A (en) * 1987-05-29 1988-12-07 Takeda Chemical Industries Ltd Thermosetting resin compositions and precoated metal
EP0324370A1 (fr) * 1988-01-12 1989-07-19 Mobay Corporation Compositions aqueuses pour utilisation lors de la préparation de polyuréthanes réticulés
WO1990007531A1 (fr) * 1988-12-27 1990-07-12 Cargill, Incorporated Isocyanate bloque et son procede de fabrication
EP0403779A2 (fr) * 1989-06-19 1990-12-27 Cytec Technology Corp. Compositions de revêtement pulvérulentes durcissables contenant des isocyanates bloqués par caprolactame
WO1991015532A1 (fr) * 1990-04-09 1991-10-17 Eastman Kodak Company Compositions de poudres pour revetement

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