WO2010097196A1 - Procédé de préparation de revêtements de polyuréthanne du type aqueux, durcissables à basses températures - Google Patents

Procédé de préparation de revêtements de polyuréthanne du type aqueux, durcissables à basses températures Download PDF

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Publication number
WO2010097196A1
WO2010097196A1 PCT/EP2010/001108 EP2010001108W WO2010097196A1 WO 2010097196 A1 WO2010097196 A1 WO 2010097196A1 EP 2010001108 W EP2010001108 W EP 2010001108W WO 2010097196 A1 WO2010097196 A1 WO 2010097196A1
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WO
WIPO (PCT)
Prior art keywords
composition
polyol
coat
acid
clear
Prior art date
Application number
PCT/EP2010/001108
Other languages
English (en)
Inventor
Denis Heymans
Cedric Le Fevere De Ten Hove
Christophe Steinbrecher
Original Assignee
Hexion Specialty Chemicals Research Belgium S.A.
Hexion Specialty Chemicals 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
Priority claimed from EP09002570A external-priority patent/EP2221332A1/fr
Application filed by Hexion Specialty Chemicals Research Belgium S.A., Hexion Specialty Chemicals Inc. filed Critical Hexion Specialty Chemicals Research Belgium S.A.
Publication of WO2010097196A1 publication Critical patent/WO2010097196A1/fr

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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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6258—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids the acid groups being esterified with polyhydroxy compounds or epoxy compounds during or after polymerization
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the invention relates to a process to prepare at ambient temperature a curable waterborne polyurethane coating by which the isocyanate and the polyols are mixed thoroughly before their emulsification in water.
  • polyisocyanates are rendered hydrophilic with polyethylene oxide or other hydrophilic groups as sulfonate.
  • hydrophobic polyisocyanates can be blended with hydrophilic polyisocyanate up to a any ratios.
  • the formulation of the clear-coat is summarized in Table 2 below.
  • First step is the addition of methoxypropanol acetate (MPA) to the polyol (A).
  • MPA methoxypropanol acetate
  • DMEA, DBTDL and BYK 011 (B) are added successively to Component A at low shear rate.
  • the hardener (C) is then added and the final step is the addition of demineralized water (D) to obtain the emulsion and a viscosity of 6OcP.
  • the emulsion obtained had a viscosity of 6OcP at 23 0 C and an average particle size of 2 microns. It was bar-coated on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash- off at 23°C(air drying) then in an oven at 60 0 C for 30 minutes, the cured panels are stored at 23°C for 7 days. The characterization results are given in Table 5.
  • the dosing equipment was rinsed with 14 g butylglycol, which was subsequently added to the reactor content.
  • the reactor charge was held at 140°C for 15 minutes.
  • a solution of 1 g Trigonox 42 S in 4 g of butylglycol was then added in two equal portions with a time interval of 15 minutes. After the mixture was held at 14O 0 C for another 30 minutes, the reactor content was cooled down to room temperature.
  • the emulsion obtained has a viscosity of 6OcP at 23°C and an average particle size of 550nm. It was then applied on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash-off (air drying) then in an oven at 60°C for 30 minutes, the cured panels are stored at 23 0 C for 7 days. The characterization results are given in Table 8 below.
  • This section describes the preparation of a clear-coat similar to the one described in clear-coat Example 2 but where the emulsion occurs before the addition of the hardener.
  • a reaction vessel equipped with an anchor stirrer, a condenser, a thermocouple, and a nitrogen inlet device was charged with 25 g Cardura 1OP and 2.5 g of methylproxitol acetate, and heated to 157°C under a nitrogen flow of 20 liters per hour. Then a mixture of 10.5 g acrylic acid, 28 g hydroxylethyl methacryiate, 4 g styrene, 33 g n-butylacrylate, 4 g ditert-amyl peroxide and 7.5 g methylproxitol acetate was added continuously to the reactor for a dosing time of 360 minutes. During the addition, the temperature of the reactor content was maintained at 157 0 C. After completion of the monomer addition, 1 g of ditert-amyl peroxide is added for a dosing time of 60 minutes at 157 0 C. The reactor content was then cooled down to room temperature.
  • the polyacrylate polyol had an acid value of 22 mg KOH/g on solids, a weight average molecular weight of 4000 and a number average molecular weight of 2000.
  • the calculated Tg was O 0 C.
  • the solids content of the solution was 90 % by weight.
  • the emulsion obtained has a viscosity of 6OcP at 23 0 C and an average particle size of 160nm. It was then sprayed on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash-off at 23 0 C (air drying) then in an oven at 6O 0 C for 30 minutes, the cured panels were stored at 23 0 C for 7 days. The characterization results are given in Table 15 below.
  • the formulation of the clear-coat is summarized in Table 16 below.
  • A is made by the successive addition of MPA, DME ⁇ A, and BYK 011 to the polyol at low shear rate.
  • the hardener (B) is then added and the final step is the addition of demineralized water (C) to obtain the emulsion with a viscosity of HBOcP.
  • the emulsion obtained has a viscosity of 56cP at 23°C and an average particle size of 185nm. It was then applied on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash-off at 23 0 C (air drying) then in an oven at 6O 0 C for 30 minutes, the cured panels were stored at 23 0 C for 7 days. The characterization results are given in Table 17 below.
  • the formulation of the clear-coat is summarized in Table 18 below.
  • A is made by the successive addition of MPA, DMEA, demineralized water and BYK 011 to the polyol at low shear rate.
  • the hardener (B) is then added and the final step is the addition of demineralized water (C) to obtain the emulsion with a viscosity of ⁇ 60cP.
  • the emulsion obtained had a viscosity of 69cP at 23°C and an average particle size of 0.9 microns. It was applied on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash-off (air drying) then in an oven at 6O 0 C for 30 minutes, the cured panels are stored at 23 0 C for 7 days. The characterization results are given in Table 21. icrons
  • a reaction vessel equipped with an anchor stirrer, a condenser, a thermocouple, and a nitrogen inlet device was charged with 25 g Cardura 10P and 2.5 g of methylproxitol acetate, and heated to 157 0 C under a nitrogen flow of 20 liters per hour. Then a mixture of 10.2 g acrylic acid, 18 g hydroxylethyl methacrylate, 30 g styrene, 19.8 g methylmethacrylate, 4 g ditert-amyl peroxide and 7.5 g methylproxitol acetate was added continuously to the reactor for a dosing time of 360 minutes. During the addition, the temperature of the reactor content was maintained at 157 0 C. After completion of the monomer addition, 1 g of ditert-amyl peroxide is added for a dosing time of 60 minutes at 157°C. The reactor content was then cooled down to room temperature.
  • the formulation of the clear-coat is summarized in Table 23 below.
  • A is made by the successive addition of MPA, DMEA, and BYK 011 to the polyol at low shear rate.
  • the hardener (B) is then added and the final step is the addition of demineralized water (C) to obtain the emulsion and a viscosity of 6OcP.
  • Table 23 Clear-coat example 4 formulation
  • the emulsion obtained has a viscosity of 6OcP at 23 0 C and an average particle size of 2500nm. It was then applied on Q panels and on Leneta sheets. The coatings were cured for first 15 minutes flash-off at 23 0 C (air drying) then in an oven at 60 0 C for 30 minutes, the cured panels are stored at 23 0 C for 7 days.
  • the characterization results are given in Table 24 below.
  • Table 28 Clear-coat 2 example 5 formulation
  • the emulsion obtained has a viscosity of 7OcP at 23 0 C and an average particle size of 420 nm. It was then applied on Q panels and on Leneta sheets. The coatings were cured for first 10 minutes flash-off (air drying) then in an oven at 60°C for 30 minutes, the cured panels are stored at 23 0 C for 7 days. The characterization results are given in Table 29 below.
  • the emulsion obtained has a viscosity of 8OcP at 23 0 C and an average particle size of 198 nm. It was then applied on Q panels and on Leneta sheets. The coatings were cured for first 10 minutes flash-off (air drying) then in an oven at 6O 0 C for 30 minutes, the cured panels are stored at 23 0 C for 7 days. The characterization results are given in Table 31 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne un procédé de préparation de revêtements de polyuréthanne du type aqueux, durcissables à température ambiante. Dans le procédé selon l'invention, l'isocyanate et les polyols sont intimement mélangés avant émulsification dans l'eau, par mélange à bas cisaillement à température ambiante. Les résines polyols utilisables pour la présente invention sont les résines polyacrylate ayant un indice d'hydroxyle de 60 à 18 mg de KOH/g de fractions solides, un indice d'acide de 10 à 30 mg de KOH/g de fractions solides, et une température de transition vitreuse calculée de -40 °C à +65 °C.
PCT/EP2010/001108 2009-02-24 2010-02-22 Procédé de préparation de revêtements de polyuréthanne du type aqueux, durcissables à basses températures WO2010097196A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP09002570A EP2221332A1 (fr) 2009-02-24 2009-02-24 Procédé pour préparer des revêtements de polyuréthane à l'eau durcissable à faible température
EP09002570.1 2009-02-24
EP09007727.2 2009-06-11
EP09007727 2009-06-11
EP09075477 2009-10-26
EP09075477.1 2009-10-26

Publications (1)

Publication Number Publication Date
WO2010097196A1 true WO2010097196A1 (fr) 2010-09-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107646041A (zh) * 2015-05-22 2018-01-30 巴斯夫涂料有限公司 制备多层涂层的方法
CN112368314A (zh) * 2018-07-10 2021-02-12 帝斯曼知识产权资产管理有限公司 可辐射固化水性聚氨酯分散体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670600A (en) * 1993-07-03 1997-09-23 Basf Lacke + Farben, Ag Aqueous two-component polyurethane coating composition, process for its preparation, and its use in processes for the production of a multicoat finish
US5852120A (en) * 1992-07-15 1998-12-22 Herberts Gmbh Aqueous, heat curable coating compound, its preparation and its use
WO2006039430A1 (fr) 2004-09-29 2006-04-13 E.I. Dupont De Nemours And Company Compositions de revetement et procede de production de revetements multicouches
EP1671990A2 (fr) 2004-12-10 2006-06-21 E.I.Du pont de nemours and company Compositions de revêtement aqueux
US20060216525A1 (en) 2005-03-24 2006-09-28 Josef Huybrechts Aqueous coating compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852120A (en) * 1992-07-15 1998-12-22 Herberts Gmbh Aqueous, heat curable coating compound, its preparation and its use
US5670600A (en) * 1993-07-03 1997-09-23 Basf Lacke + Farben, Ag Aqueous two-component polyurethane coating composition, process for its preparation, and its use in processes for the production of a multicoat finish
WO2006039430A1 (fr) 2004-09-29 2006-04-13 E.I. Dupont De Nemours And Company Compositions de revetement et procede de production de revetements multicouches
EP1671990A2 (fr) 2004-12-10 2006-06-21 E.I.Du pont de nemours and company Compositions de revêtement aqueux
US20060216525A1 (en) 2005-03-24 2006-09-28 Josef Huybrechts Aqueous coating compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107646041A (zh) * 2015-05-22 2018-01-30 巴斯夫涂料有限公司 制备多层涂层的方法
CN107646041B (zh) * 2015-05-22 2020-05-12 巴斯夫涂料有限公司 制备多层涂层的方法
CN112368314A (zh) * 2018-07-10 2021-02-12 帝斯曼知识产权资产管理有限公司 可辐射固化水性聚氨酯分散体

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