WO1999060046A1 - Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings - Google Patents
Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings Download PDFInfo
- Publication number
- WO1999060046A1 WO1999060046A1 PCT/US1998/027921 US9827921W WO9960046A1 WO 1999060046 A1 WO1999060046 A1 WO 1999060046A1 US 9827921 W US9827921 W US 9827921W WO 9960046 A1 WO9960046 A1 WO 9960046A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- functionality
- carboxylic acid
- acid
- glycol
- polyester
- 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
Links
Classifications
-
- 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
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- 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
Definitions
- This invention concerns the use of trimellitic anhydride (TMA) and/or dimethylolpropionic acid (DMPA) in concert with polyols and chain extending diacids and glycols at temperatures at or below 180°C to produce acid-functional polyesters with high hydroxyl functionality for waterbome applications (Table 1 and Table 4) .
- TMA and/or DMPA provide chain-extension and pendant acid groups while polyols provide branching to the polyester. This allows for formulation of highly branched polyesters with reduced propensity for gelation during polymerization.
- These polyesters are suitable for use with crosslinkers that are capable of reacting with hydroxyls such as isocyanates and melamines .
- HHTA hexahydro- trimellitic anhydride
- TMA trimethylolpropane
- glycerol trimethylolethane
- di-trimethylolpropane pentaerythritol
- Glycols and diacids that are hydrophobic and non-polar provide TMA and/or DMPA containing polyesters with excellent hydrolytic stability (Table 3) .
- hydrophobic, non-polar monomers include, but are not limited to, dodecanedioic acid (DDDA) , 1 , 4-cyclohexanedicarboxylic acid (1,4-CHDA), 1, 3-cyclohexanedicarboxylic acid (1,3-CHDA), hexahydrophthalic anhydride (HHPA) , tetrahydrophthalic anhydride (THPA) , 3-hydroxy-2 , 2-dimethylpropyl 3-hydroxy-2 , 2-dimethylpropanoate (HPHP) , 2-butyl-2-ethyl-l, 3-propanediol (BEPD) , 2,2,4- trimethyl-l,3-pentanediol ( TMPD glycol) , 2 , 2-diethyl-l , 3- propane
- Stage 2 maximum reaction temperature is 180°C.
- polyester resins were dispersed in water (Table 6) and tested for hydrolysis resistance at 52°C. Acid number and pH drift were measured every two weeks .
- the resins were tested in coating formulations (Table 7) .
- the coatings were stored at 50°C and samples taken at two and six weeks of aging. Various cure-film tests were performed.
- the resins have acceptable storage stability in water as well as acceptable film properties before and after aging.
- Resins of the invention are useful in coatings exposed to natural weather conditions.
- the resins may also be used in zero to low VOC systems when combined with a neutralizing agent such as ammonia.
- Resins of the invention may also be formulated over a wide range of viscosity profiles.
- Resins of the invention may also be blended with water-reducible resins known in the art, such as acrylic resins, to
- Glycol variable TMPD glycol, BEPD, or CHDM Table 2 Camile System Startup & Shutdown Conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention describes a gel resistant, hydrolytically stable polyseter resin with high hydroxyl functionality and carboxylic acid functionality. A waterborne coating composition based on such resins is also described. A method of preparing such waterborne coating compositions is described as well.
Description
Gel Resistant, Hydrolytically Stable Polyester Resins with High Hydroxyl Functionality and Carboxylic Acid Functionality for Isocyanate Crosslinkable, Waterbome Coatings
This invention concerns the use of trimellitic anhydride (TMA) and/or dimethylolpropionic acid (DMPA) in concert with polyols and chain extending diacids and glycols at temperatures at or below 180°C to produce acid-functional polyesters with high hydroxyl functionality for waterbome applications (Table 1 and Table 4) . TMA and/or DMPA provide chain-extension and pendant acid groups while polyols provide branching to the polyester. This allows for formulation of highly branched polyesters with reduced propensity for gelation during polymerization. These polyesters are suitable for use with crosslinkers that are capable of reacting with hydroxyls such as isocyanates and melamines . Using temperatures at or below 180°C without catalysts, TMA esterifies at only two of the possible three sites; likewise, DMPA will only esterify at its hydroxyls. In this manner TMA and/or DMPA function as chain-extenders rather than as chain-branchers . Since the pendant acid group from the TMA and/or DMPA moiety is unreactive due to steric shielding, the effective reactive acid functionality on the polyester is reduced thus reducing the likelihood of gelation in the reactor. The remaining, sterically hindered acid group can be neutralized later to provide water dispersibility to the polymer without using organic cosolvents (Table 2) . It is also possible to use hexahydro- trimellitic anhydride (HHTA) in the place of TMA.
As the pendant acid groups from the TMA (or HHTA) and/or DMPA moieties are essentially unreactive at these low temperatures, high levels of polyol can be incorporated into the polyester to provide high hydroxyl functionality. For crosslinkers that react only with hydroxyl groups such as isocyanates, high levels of branching may be necessary to provide sufficient hydroxyl functionality for good cure. Examples of polyols useful for branching include, but are not limited to, trimethylolpropane (TMP) , trimethylolethane, glycerol, di-trimethylolpropane, and pentaerythritol .
Glycols and diacids that are hydrophobic and non-polar provide TMA and/or DMPA containing polyesters with excellent hydrolytic stability (Table 3) . Examples of hydrophobic, non-polar monomers include, but are not limited to, dodecanedioic acid (DDDA) , 1 , 4-cyclohexanedicarboxylic acid (1,4-CHDA), 1, 3-cyclohexanedicarboxylic acid (1,3-CHDA), hexahydrophthalic anhydride (HHPA) , tetrahydrophthalic anhydride (THPA) , 3-hydroxy-2 , 2-dimethylpropyl 3-hydroxy-2 , 2-dimethylpropanoate (HPHP) , 2-butyl-2-ethyl-l, 3-propanediol (BEPD) , 2,2,4- trimethyl-l,3-pentanediol ( TMPD glycol) , 2 , 2-diethyl-l , 3- propanediol (DEPD) , and 1 , 4-cyclohexanedimethanol (CHDM) .
These resin design parameters coupled with quality resin intermediates result in excellent film properties (Table 3) . CHDM, for example, provides fast cure with its unhindered primary hydroxyls. Distinctness of image (DOI), gloss, pencil hardness, and solvent resistance (MEK double-rubs) all show excellent results.
Table 1 Resin Formulation
[OH] / [COOH] = 1.28912
Final acid value = 60
Polyols Mole % Polyacids Mole %
CHDM 39.990 1,4-CHDA 53.744
Glycol variable* 39.990 TMA 46.256
TMP 20.020
Stage 1 Stage 2
Glycol variable CHDM
TMP TMA
1,4-CHDA
Take the first stage to 90% of theoretical distillate,
React the second stage to an acid number of 60. Stage 2 maximum reaction temperature is 180°C.
*Glycol variable = TMPD glycol, BEPD, or CHDM
Table 2
Coating Formulation
Isocyanate crosslinker Bayer's Bayhydur Product
NCO : OH 2.0:1.0
Neutralizing amine 2 -dimethylaminoethanol
Solvent distilled water
Cosolvent none
Table 3
Coating Storage Stability TMA-based resins before and after aging at 50°C for two weeks
Glycol Variable BEPD CHDM TMPD® glycol
Tπitial Final Initial Final Initial Final
Dry Time (hr) 3.3 3.5 2.9 2.2 3.3 3.0
MEK Double-rubs 100+ 100+ 100+ 100+ 100+ 100+
Pencil Hardness H 3H 2H 2H 2H 2H
Gloss
60° 100 95 100 100 100 100
20° 90 72 90 90 90 90
DOI 88 80 80 77 80 83
Purpose: To make a hydrolytically-stable, waterbome polyester resin to compliment other waterbome isocyanate crosslinkers . Prior experiments with commercial acrylics gave poor film properties while commercial polyesters had poor hydrolytic stability.
Procedure: 1,4-CHDA (1 , 4-cyclohexanedicarboxylic acid), CHDM (1, -cyclohexanedimethanol) , TMA (trimellitic anhydride) , and TMP
(trimethylolpropane) were used in each resin formulation. Fifty percent of the CHDM in the original formula was replaced with either TMPD glycol (2 , 2 , 4-trimethyl-l , 3-pentanediol) or BEPD (2-butyl-2-ethyl-l, 3-propanediol) (Tables
1 to 5) .
The polyester resins were dispersed in water (Table 6) and tested for hydrolysis resistance at 52°C. Acid number and pH drift were measured every two weeks .
The resins were tested in coating formulations (Table 7) . The coatings were stored at 50°C and samples taken at two and six weeks of aging. Various cure-film tests were performed.
Results: Acid number and pH drift results are given in Table 8. The resins dropped only ten percent
in acid equivalent weight every two weeks. This should correspond to a ten percent drop per year at ~23°C.
Coating results were satisfactory with aged samples exhibiting no significant property changes at two weeks and small changes at six weeks (Table 9) . All resins gave similar coating properties.
10
The resins have acceptable storage stability in water as well as acceptable film properties before and after aging.
15 Resins of the invention are useful in coatings exposed to natural weather conditions. The resins may also be used in zero to low VOC systems when combined with a neutralizing agent such as ammonia. Coating compositions based on
20 or containing the resins of the invention may also be formulated over a wide range of viscosity profiles. Resins of the invention may also be blended with water-reducible resins known in the art, such as acrylic resins, to
25 form resin blends or coating compositions.
Table 1 Resin Formulation R value = [OH] / [COOH] = 1.28912
Final acid value = 60 Hydroxyl number = 176
Polyols Mole % Polyacids Mole %
CHDM 39.990 1,4-CHDA 53.744
Glycol variable* 39.990 TMA 46.256
TMP 20.020
Stage 1 Stage 2
Glycol variable CHDM
TMP TMA
1,4-CHDA
Glycol variable = TMPD glycol, BEPD, or CHDM
Table 2 Camile System Startup & Shutdown Conditions
Hot oil bath temperature (°C) 103
Meltdown Ramp Rate (C°/min) 1
Meltdown Temperature (°C) 150
Final Resin Cool down Temperature (°C) 150
Final Cool down Stirring Rate (RPM) 150
Table 3 Camile System Process Parameters
Reactant
1st Ramp 2nd Ramp Addition
Stage Description Rate Stage Rate Stage Stage
Ramp Starting Temperature (°C) 140 180 150
Ramp Rate (C°/min) 1 0.25 0.25
Max. Ramp Temp. (°C) 180 210 175
Cook Time at Max. Temp, (min) 15 180 See Table 4
Overnight Hold Temp. (°C) N/A 150 N/A
Table 4 Second Stage Cook Time
Cook Time at Max. Glycol Variable Temperature (min)
BEPD 63.6
CHDM 54.9
TMPD glycol 121.2
Table 5
Analytical Results for the Resins
Glycol No.
Variable Repeat No. Ic , (°C) M_ (g/mol) M,„ (g/mol) Acid No. OH No.
BEPD 1 21 1510 6182 59 169
10 BEPD 2 21 1529 6392 59 169
BEPD 3 20 1538 6610 58 170
I ro
CHDM 1 32 1503 6411 58 173
CHDM 2 36 1650 8278 56 170
15 CHDM 3 37 1551 6771 57 173
TMPD glycol 1 34 1832 17472 59 140
TMPD glycol 2 35 1931 26261 58 131
TMPD glycol 3 34 1946 23982 58 131
20
Table 6 Resin Aqueous Dispersion Formulation
Component t . Percent
Polyester 35, .0
2-Dimethylaminoethanol (DMEA)* 3, .2
Distilled water* 67, .8
*DMEA added according to acid number for 100% neutralization.
Water added to achieve 35% solids.
Table 7 Coating Formulation
Isocyanate crosslinker* Bayer ' s Bayhydur Product NCO : OH 2.0:1.0
Neutralizing amine 2-dimethylaminoethanol
Solvent distilled water
Cosolvent none
*Isocyanate crosslinker added just prior to spray application.
Table 8
Resin Dispersion Acid Number and pH Drift*
Glycol Acid No. Acid No. Acid No. pH pH pH Variable Repeat No . Initial 2 Weeks 4 Weeks Initial 2 Weeks 4 Weeks
BEPD 1 60.4 67.7 75.4 7.90 6.67 6.24
10 BEPD 2 59.4 67.1 75.3 7.97 6.75 6.21
BEPD 3 59.1 67.4 74.9 7.52 6.61 6.13
1 on
CHDM 1 56.2 62.6 69.5 8.09 6.84 6.28 1
CHDM 2 56.4 64.1 70.0 8.42 6.70 6.37
15 CHDM 3 57.3 64.4 71.0 8.10 6.76 6.32
TMPD glycol 1 60.5 67.6 74.8 7.49 6.66 6.39
TMPD glycol 2 58.7 65.0 71.9 8.03 6.81 6.38
TMPD glyc :ol 3 58.6 65.4 72.8 7.79 6.75 6.34
20
*Aging conducted at 52 °C.
Table 9 Coating Property Changes* BEPD CHDM TMPD glycol
2 6 2 6 2 6
Glycol Variable Initial Weeks Weeks Initial Weeks Weeks Initial Weeks Weeks
Dry Time (hr) 3.3 3.5 2.8 2.9 2.2 3.8 3.3 3.0 3.0
MEK Double-rubs 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+
Pencil Hardness H 3H HB 2H 2H HB 2H 2H HB
10 Gloss
60° 100 95 96 100 100 94 100 100 98
20° 90 72 80 90 90 84 90 90 86
DOI 88 80 92 80 77 92 80 83 87
15 *Spray applied to Bonderite-952 pretreated, cold-rolled steel panels for a 1.0 to 1.5 mil dry film thickness. Aging conduced at 50°C.
Claims
1. A gel resistant, hydrolytically stable polyester resin having high hydroxyl functionality and carboxylic acid functionality comprising the reaction product of: trimellitic anhydride or hexahydrotrimellitic anhydride and/or dimethylolpropionic acid; a polyol ; a diacid; and a glycol, wherein said trimellitic anhydride, hexahydrotrimellitic anhydride, and/or said dimethylolpropionic acid provide chain-extension and pendant acid groups to the polyester and said polyol provides branching to the polyester.
2. A waterbome coating composition comprising: a neutralized polyester resin of claim 1; a crosslinker, wherein said crosslinker is capable of reacting with hydroxyl groups; and water.
3. A waterbome coating composition of claim 2, wherein said cross-linker is an isocyanate or a melamine .
4. A method of preparing a waterbome coating composition of claim 2 comprising the steps of: neutralizing a polyester resin having carboxylic acid functionality comprising the reaction product of: trimellitic anhydride or hexahydrotrimellitic anhydride and/or dimethylolpropionic acid; a polyol ; a diacid; and a glycol, wherein said trimellitic anhydride, hexahydrotrimellitic anhydride and/or said dimethylolpropionic acid provide chain-extension and pendant acid groups to the polyester and said polyol provides branching to the polyester; dispersing the neutralized polyester resin in water; and adding a crosslinker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/027921 WO1999060046A1 (en) | 1998-12-30 | 1998-12-30 | Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/027921 WO1999060046A1 (en) | 1998-12-30 | 1998-12-30 | Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999060046A1 true WO1999060046A1 (en) | 1999-11-25 |
Family
ID=22268590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1998/027921 Ceased WO1999060046A1 (en) | 1998-12-30 | 1998-12-30 | Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1999060046A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1261650A4 (en) * | 2000-01-18 | 2003-04-02 | Accurez Corp | Water-reducible polyester resins and urethane coatings produced therefrom |
| US7199194B2 (en) * | 2002-02-20 | 2007-04-03 | E. I. Du Pont De Nemours And Company | Two component coating compositions containing highly branched copolyester polyol |
| CN110358047A (en) * | 2017-02-14 | 2019-10-22 | 广东博海化工科技有限公司 | A kind of environment-friendly type heatproof transfer coatings aqueous polyurethane coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116902A (en) * | 1977-10-05 | 1978-09-26 | International Minerals & Chemical Corp. | Polyurethane-modified alkyd resin |
| US4172822A (en) * | 1977-06-06 | 1979-10-30 | Herberts Gesellschaft Mit Beschrankter Haftung | Aqueous coating compositions containing polyester containing carboxyl groups |
| US5306567A (en) * | 1992-11-27 | 1994-04-26 | Eastman Kodak Company | Thermosetting coating compositions |
| EP0612779A2 (en) * | 1993-02-26 | 1994-08-31 | Hoechst Aktiengesellschaft | Acid modified polyesters and their use in stove enamels |
-
1998
- 1998-12-30 WO PCT/US1998/027921 patent/WO1999060046A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172822A (en) * | 1977-06-06 | 1979-10-30 | Herberts Gesellschaft Mit Beschrankter Haftung | Aqueous coating compositions containing polyester containing carboxyl groups |
| US4116902A (en) * | 1977-10-05 | 1978-09-26 | International Minerals & Chemical Corp. | Polyurethane-modified alkyd resin |
| US5306567A (en) * | 1992-11-27 | 1994-04-26 | Eastman Kodak Company | Thermosetting coating compositions |
| EP0612779A2 (en) * | 1993-02-26 | 1994-08-31 | Hoechst Aktiengesellschaft | Acid modified polyesters and their use in stove enamels |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1261650A4 (en) * | 2000-01-18 | 2003-04-02 | Accurez Corp | Water-reducible polyester resins and urethane coatings produced therefrom |
| US7199194B2 (en) * | 2002-02-20 | 2007-04-03 | E. I. Du Pont De Nemours And Company | Two component coating compositions containing highly branched copolyester polyol |
| CN110358047A (en) * | 2017-02-14 | 2019-10-22 | 广东博海化工科技有限公司 | A kind of environment-friendly type heatproof transfer coatings aqueous polyurethane coating and preparation method thereof |
| CN110358046A (en) * | 2017-02-14 | 2019-10-22 | 广东博海化工科技有限公司 | A kind of heatproof transfer coatings aqueous polyurethane emulsion of good film-forming property and preparation method thereof |
| CN110358048A (en) * | 2017-02-14 | 2019-10-22 | 广东博海化工科技有限公司 | A kind of preparation method of heatproof transfer coatings aqueous polyurethane emulsion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6992133B2 (en) | Low VOC, coating compositions having improved flexibility and impact resistance based upon nonlinear, low-molecular weight polyester polyol resins | |
| CN107531889B (en) | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol | |
| US5004779A (en) | Process for the preparation of aqueous, oxidatively drying alkyd resins and their use in or as aqueous lacquers and coating compounds | |
| CN102307959A (en) | Coating compositions containing tetramethyl cyclobutanediol | |
| JP2003531258A (en) | Branched hydroxyl-functional polyester resins and their use in aqueous crosslinkable binder compositions | |
| JPH08231695A (en) | Carbamate-functional polyester polymer or oligomer with pendent carbamate group | |
| CA2170209A1 (en) | Aqueous binders for coating compositions based on polyester polyurethanes | |
| WO2009121887A1 (en) | Aqueous autoxidisable polyester coating composition | |
| US6824834B2 (en) | Coating composition | |
| EP1453882A1 (en) | Copolyester resin for solventborne coating and coating composition comprising the same | |
| EP0769030A4 (en) | Compositions containing polyols, phenolic esters and isocyanates | |
| WO1999060046A1 (en) | Gel resistant, hydrolytically stable polyester resins with high hydroxyl functionality and carboxylic acid functionality for isocyanate cross-linkable, waterborne coatings | |
| EP0662983A1 (en) | Water-dispersible polyester resins and process for their preparation | |
| EP0771857B1 (en) | Coating composition comprising stabilized inorganic pigments | |
| EP0797611B1 (en) | Acid etch resistant automotive topcoat | |
| CA2455880A1 (en) | Coating agent, method of production and use thereof for generation of structured painted surfaces | |
| EP2456799B1 (en) | Water-borne binders for primer-surfacer coating compositions | |
| WO2002024823A2 (en) | Polyester triglycidyl isocyanurate resin powder coatings based on 1, 3-propanediol | |
| CA1269480A (en) | Resinous composition for a top coat | |
| EP0970995B1 (en) | Polyester resin composition, cured resin, and coating material | |
| CA2495694C (en) | Water-dilutable polyesters with a cyclic imide and isocyanurate structure | |
| CA2495700A1 (en) | Water-dilutable polyesters with a cyclic imide structure | |
| CA1261346A (en) | Linear, low-molecular-weight polyester-based polyols | |
| CA2200082A1 (en) | Polymeric vehicles which include a phenolic urethane reactive diluent | |
| WO1996035735A1 (en) | Alkoxylated dimethylolpropionic acid modifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |