WO2002053621A1 - Advanced resin derived from a low molecular weight glycidyl ether and a di-tertiary carboxylic acid and powder coating compositions comprising it - Google Patents
Advanced resin derived from a low molecular weight glycidyl ether and a di-tertiary carboxylic acid and powder coating compositions comprising it Download PDFInfo
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- WO2002053621A1 WO2002053621A1 PCT/EP2001/014706 EP0114706W WO02053621A1 WO 2002053621 A1 WO2002053621 A1 WO 2002053621A1 EP 0114706 W EP0114706 W EP 0114706W WO 02053621 A1 WO02053621 A1 WO 02053621A1
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- powder coating
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- 0 *C(*)(C(*)=O)N Chemical compound *C(*)(C(*)=O)N 0.000 description 3
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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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 invention relates to an advanced resin derived from a low molecular weight glycidyl ether and a di- tertiary carboxylic acid and to powder coating compositions comprising it.
- Diglycidyl esters of alpha, alpha' -di-branched dicarboxylic acids having both alpha carbon atoms with respect to the carbonyl groups substituted with alkyl, halogen or aryl groups have been described for use in ther osetting resin compositions in US patent No. 3,629,295. These diglycidyl esters were found to have improved hydrolytic stability and resistance to transesterification, presumably due to the presence of the sterically hindered ester linkages . According to said US patent curing of the diglycidyl esters can be performed using any type of ⁇ polyfunctional curing agent which is capable of adding to an epoxy compound such as primary or secondary amines and carboxylic acid anhydrides .
- European patent application publication No. 366205 also relates to diglycidyl esters of alpha, alpha' -di- branched dicarboxylic acids. It shows inter alia some favourable properties of castings (good hardness and clear coloured) and of a film (good adhesion to metal and high initial gloss) that were prepared from the diglycidyl ester of thiodipivalic acid using isophoronedia ine (IPD) or diphenyldiaminomethane (DDM) as curing agent.
- IPD isophoronedia ine
- DDM diphenyldiaminomethane
- powder coating compositions providing attractive coating film properties in combination with attractive processing properties.
- the invention relates to powder coating compositions, comprising: (i) an advanced resin product, obtainable by reacting (a) a diglycidyl ether of a bisphenol of the general formula I
- R_ symbols may be the same or different and each R]_ represents hydrogen or lower alkyl, having from 1 to 4 C atoms, and wherein n has a value in the range of from 0.1 to 2, said diglycidyl ether having an epoxide content in the range of from 5500 to 2000 mmol/kg and a hydroxyl content in the range of from 250 to 2500, with (b) an alpha, alpha' -di-branched dicarboxylic acid of the general formula II
- R 2 2 wherein the R 2 symbols may be the same or different and each R 2 represents a lower alkyl having from 1 to 3 carbon atoms, and preferably 1 or 2 carbon atoms, and wherein m is an integer in the range of from 0 to 8, and preferably from 2 to 6, the advanced resin having a number average molecular weight in the range of from 500 to 7000;. and
- the advancement reaction between components (a) and (b) to form the advanced resin product (i) is generally carried out at a temperature of between 60 °C and 160 °C and the molar ratio between components (a) and (b) is in the range of from 1.1 to 2.0 and preferably from 1.2 to 1.5.
- Preferred components (a) are commercially available diglycidyl ethers such as EPON 828, EPON 1001 or EPON 3003 or EPIKOTE 828, EPIKOTE 1001 or EPIKOTE 3003 type resins (EPON and EPIKOTE are trade marks) .
- starting components (a) also mixtures of glycidyl ether resins, derived from different types of bisphenol starting compounds (i.e. having different symbols R]_) , can be used.
- Preferred components (b) are ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acids containing from 8 to 18 carbon atoms in the acid residue and more preferably from 10 to 14 carbon atoms, while the symbols R either all represent methyl or three of them represent methyl and one presents ethyl, as specified in European patent application No. 00200357.2, filed 2 February 2000, which is included herein by reference.
- component (b) technical mixtures of ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic diacids can be used as component (b) , and in particular mixtures of from 10 to 14 carbon atoms in the residue wherein all R are methyl and wherein three R are methyl and one R is ethyl.
- a non- interfering solvent may be used in a small amount, which has to be evaporated later on and selected from aromatic hydrocarbons, ketones, alcohols and ethers.
- any suitable catalyst may be added to the reaction mixture, e.g. tertiary phosphines and amines, quaternary phosphonium or ammonium salts, and metal salts such as chromium salts.
- a preferred catalyst is triphenyl phosphine. It was surprisingly found that the combination of
- an advanced resin product of a low molecular weight diglycidyl ether of a bisphenol and alpha, alpha' -di- branched dicarboxylic acid, i.e. a linear advanced resin, carrying epoxy groups and hydroxyl groups along the chain, and a curing agent (ii) can provide such attractive properties.
- reaction components (b) are:
- Said preferred mixtures are further referred to herein as DTA (about 1 : 1 mixture) .
- thermosetting powder coating composition of the invention comprises a curing compound (ii) which cures via the finally present hydroxyl and/or epoxy groups of the advanced product (i) , in such a way that ether, amine, urethane or alpha-di-branched ester linkages are formed, but unbranched ester linkages are avoided.
- typical curing agents can be used melamine- formaldehyde resins, urea formaldehyde resins, glycoluryl resins, alcohol blocked isophorone diisocyanates ,
- the cure can be effected in one or more cycles at temperatures of from 80 to 200 °C and preferably from 140 to 170 °C for a period of from 5 to 30 minutes.
- the final powder coating compositions of the present invention can be prepared by mixing the components (i) and (ii) alone or together with usual modifiers such as extenders, fillers, pigments, dyestuffs, flow control agents, anti-caking agents and the like. Due to the ⁇ , ⁇ ' -di-branched ester structures, the resin compositions and powder coatings provide, when cured insoluble and infusible films and in particular having an improved flexibility.
- Another aspect of the present invention is formed by cured powder coating compositions on a substrate and more in particular by cured powder coating compositions on the surface of a shaped article .
- EPIKOTE 828 ECC 5321
- DTA a mixture predominantly comprising 2, 2, 6, 6-tetramethyl pimelic acid and 2, 2 , 5-trimethyl-5-ethyl adipic acid in a mutual molar ratio of 52:48
- EPC 5321 EPIKOTE 828
- DTA a mixture predominantly comprising 2, 2, 6, 6-tetramethyl pimelic acid and 2, 2 , 5-trimethyl-5-ethyl adipic acid in a mutual molar ratio of 52:48
- the mixture is heated up to 110 °C.
- a catalyst concentration of 0.1% (w/w) triphenylphosphine is then added to the mixture.
- the exotherm temperature is allowed to reach 183 °C before stabilizing at 170 °C for 10 minutes before dumping.
- the reaction time was 35 minutes. Intake was selected to get a type-3 like epoxy resin for powder applications (average EGC 1340 mmol/kg) .
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Abstract
Powder coating compositions, comprising: (i) an advanced resin product, obtainable by reacting (a) a diglycidyl ether of a bisphenol of formula (I) wherein the R1 symbols may be the same or different and each R1 represents hydrogen or lower alkyl, having from 1 to 4 C atoms, and wherein n has a value in the range of from 1.0 to 2, said diglycidyl ether having an epoxide content in the range of from 5500 to 2000 mmol/kg and a hydroxyl content in the range of from 250 to 2500, which (b) an alpha-alpha'-di-branched dicarboxylic acid of the formula (II) wherein the R2 symbols may be the same or different and each R2 represents a lower alkyl having from 1 to 3 carbon atoms, and preferably 1 or 2 carbon atoms, and wherein m is an integer in the range of from 0 to 8, the advanced resin having a number average molecular weight in the range of from 500 to 7000; and (ii) a curing compound selected from the group consisting of amino resins, blocked or unblocked (cyclo)aliphatic isocyanates alpha,alpha'-dibranced cyclic anhydrides, acid functional linear polyesters (cyclo)aliphatic polyamine amides; advanced resin product (i) itself, and cured coating compositions on a substrate.
Description
ADVANCED RESIN DERIVED FROM A LOW MOLECULAR WEIGHT GLYCIDYL ETHER AND A DI-TERTIARY CARBOXYLIC ACID AND POWDER COATING COMPOSITIONS COMPRISING IT
The invention relates to an advanced resin derived from a low molecular weight glycidyl ether and a di- tertiary carboxylic acid and to powder coating compositions comprising it. Diglycidyl esters of alpha, alpha' -di-branched dicarboxylic acids having both alpha carbon atoms with respect to the carbonyl groups substituted with alkyl, halogen or aryl groups have been described for use in ther osetting resin compositions in US patent No. 3,629,295. These diglycidyl esters were found to have improved hydrolytic stability and resistance to transesterification, presumably due to the presence of the sterically hindered ester linkages . According to said US patent curing of the diglycidyl esters can be performed using any type of^polyfunctional curing agent which is capable of adding to an epoxy compound such as primary or secondary amines and carboxylic acid anhydrides .
European patent application publication No. 366205 also relates to diglycidyl esters of alpha, alpha' -di- branched dicarboxylic acids. It shows inter alia some favourable properties of castings (good hardness and clear coloured) and of a film (good adhesion to metal and high initial gloss) that were prepared from the diglycidyl ester of thiodipivalic acid using isophoronedia ine (IPD) or diphenyldiaminomethane (DDM) as curing agent. However, in spite of the above mentioned advantageous properties inherent to the use of diglycidyl
esters of alpha, alpha' -di-branched dicarboxylic acids in the cured resin systems, these systems were found to suffer from a major deficiency i.e. insufficient weathering resistance, which in fact precludes their use in automotive topcoats and in other end uses requiring a high degree of outdoor durability. Moreover, said alpha, alpha' -di-branched dicarboxylic acids could not be applied in powder coatings .
Due to the ongoing pressure from health and environmental organizations there is still a strong need for improved powder coating compositions, which show an attractive combination of flexibility; measured as reverse impact strength and attractive reactivity i.e. significant curing below 180 °C and even at 70 °C and flow (lower viscosity) during curing.
Therefore it is an object of the present invention to find powder coating compositions providing attractive coating film properties in combination with attractive processing properties. As a result of extensive research and experimentation, powder coating compositions aimed at have now surprisingly been found.
Accordingly, the invention relates to powder coating compositions, comprising: (i) an advanced resin product, obtainable by reacting (a) a diglycidyl ether of a bisphenol of the general formula I
0 R2 R2 0
HO C ■C •(CH2) m C C OH
R2 2 wherein the R2 symbols may be the same or different and each R2 represents a lower alkyl having from 1 to 3 carbon atoms, and preferably 1 or 2 carbon atoms, and wherein m is an integer in the range of from 0 to 8, and preferably from 2 to 6, the advanced resin having a number average molecular weight in the range of from 500 to 7000;. and
(ii) a curing compound selected from the group consisting of amino resins, blocked or unblocked
(cyclo) liphatic isocyanates alpha, alpha' -dibranced cyclic anhydrides, acid functional polyesters,
(cyclo) aliphatic polyamine amides.
The advancement reaction between components (a) and (b) to form the advanced resin product (i) is generally carried out at a temperature of between 60 °C and 160 °C and the molar ratio between components (a) and (b) is in the range of from 1.1 to 2.0 and preferably from 1.2 to 1.5.
Preferred components (a) are commercially available diglycidyl ethers such as EPON 828, EPON 1001 or EPON 3003 or EPIKOTE 828, EPIKOTE 1001 or EPIKOTE 3003 type resins (EPON and EPIKOTE are trade marks) .
It will be appreciated that as starting components (a) also mixtures of glycidyl ether resins, derived from different types of bisphenol starting compounds (i.e. having different symbols R]_) , can be used. Preferred components (b) are α, α, α' , α' -branched aliphatic dicarboxylic acids containing from 8 to 18 carbon atoms in the acid residue and more preferably from 10 to 14 carbon atoms, while the symbols R either all represent methyl or three of them represent methyl and one presents ethyl, as specified in European patent application No. 00200357.2, filed 2 February 2000, which is included herein by reference.
It will be appreciated that technical mixtures of α,α, α' , α' -branched aliphatic diacids can be used as component (b) , and in particular mixtures of from 10 to 14 carbon atoms in the residue wherein all R are methyl and wherein three R are methyl and one R is ethyl.
It is preferred to react the components (a) and (b) in the absence of solvent. However, if necessary, a non- interfering solvent may be used in a small amount, which has to be evaporated later on and selected from aromatic hydrocarbons, ketones, alcohols and ethers.
No catalyst is needed for the advancement reaction of a great number of reactions of components (a) and (b) . However, if required in special cases any suitable
catalyst may be added to the reaction mixture, e.g. tertiary phosphines and amines, quaternary phosphonium or ammonium salts, and metal salts such as chromium salts. A preferred catalyst is triphenyl phosphine. It was surprisingly found that the combination of
(i) an advanced resin product of a low molecular weight diglycidyl ether of a bisphenol and alpha, alpha' -di- branched dicarboxylic acid, i.e. a linear advanced resin, carrying epoxy groups and hydroxyl groups along the chain, and a curing agent (ii) can provide such attractive properties.
Typical examples of reaction components (b) are
2, 2 , 6, 6-tetramethyl pimelic acid, 2, 2, 5-trimethyl-5-ethyl adipic acid, or mixtures thereof, in a mutual molar ratio in the range of from 10:1 to 1:10, and preferably in the range of from 2:1 to 1:2, and optionally mixed with minor proportions of higher and lower homologs . Said preferred mixtures are further referred to herein as DTA (about 1 : 1 mixture) . The thermosetting powder coating composition of the invention comprises a curing compound (ii) which cures via the finally present hydroxyl and/or epoxy groups of the advanced product (i) , in such a way that ether, amine, urethane or alpha-di-branched ester linkages are formed, but unbranched ester linkages are avoided. As typical curing agents can be used melamine- formaldehyde resins, urea formaldehyde resins, glycoluryl resins, alcohol blocked isophorone diisocyanates ,
3, 3, 4 , 4-tetramethyl succinic anhydride, isophorondiamine, VERSAMID 100 (a trademark for an aminoamide), hexamethoxymethyl melamine, N, N,N' , N' -tetramethyl-1, 6- diaminohexane and acid functional polyesters (e.g. CRYLCOAT polyesters) (CRYLCOAT is a trademark), of which the acid functional polyester is preferred.
Depending on the choice of the curing component (ii) , the cure can be effected in one or more cycles at temperatures of from 80 to 200 °C and preferably from 140 to 170 °C for a period of from 5 to 30 minutes. The final powder coating compositions of the present invention can be prepared by mixing the components (i) and (ii) alone or together with usual modifiers such as extenders, fillers, pigments, dyestuffs, flow control agents, anti-caking agents and the like. Due to the α, α' -di-branched ester structures, the resin compositions and powder coatings provide, when cured insoluble and infusible films and in particular having an improved flexibility.
It will be appreciated that another aspect of the present invention is formed by cured powder coating compositions on a substrate and more in particular by cured powder coating compositions on the surface of a shaped article .
The following examples are presented to illustrate certain specific embodiments, however without restricting the scope of the invention to these embodiments. Example 1 Synthesis of the resin:
1090.5 g of EPIKOTE 828 (EGC 5321) and 409.5 g of DTA (a mixture predominantly comprising 2, 2, 6, 6-tetramethyl pimelic acid and 2, 2 , 5-trimethyl-5-ethyl adipic acid in a mutual molar ratio of 52:48) are charged in a 2 1 glass reactor equipped with anchor stirrer, thermocouple and nitrogen inlet. The mixture is heated up to 110 °C. A catalyst concentration of 0.1% (w/w) triphenylphosphine is then added to the mixture. The exotherm temperature is allowed to reach 183 °C before stabilizing at 170 °C for 10 minutes before dumping. The reaction time was 35 minutes.
Intake was selected to get a type-3 like epoxy resin for powder applications (average EGC 1340 mmol/kg) .
Resin properties: white clear solid, measured EGC 1355 mmol/kg, measured residual acid 72 mmol/kg, melt viscosity 18 Poise @ 125 °C. Example 2
Powder formulations and coating properties
Extrusion Buss single screw extruder 100-105 °C No pigment/epoxy masterbatch was made Extruded twice
* CRYLCOAT CC430 ex. UCB
Claims
1. Powder coating compositions, comprising: (i) an advanced resin product, obtainable by reacting (a) a diglycidyl ether of a bisphenol of the general formula I
(ii) a curing compound selected from the group consisting of amino resins, blocked or unblocked
(cyclo) aliphatic isocyanates, alpha, alpha' -dibranced cyclic anhydrides, acid functional polyesters,
(cyclo) aliphatic polyamine amides.
2. Powder coating compositions according to claim 1, characterized in that the advanced resin product (i) is formed by a reaction between components (a) and (b) at a temperature of between 60 °C and 160 °C.
3. Powder coating compositions according to claims 1 and 2, characterized in that the molar ratio between components (a) and (b) is in the range of from 1.1 to 2.0.
4. Powder coating compositions according to claim 3, characterized in that the molar ratio between the components (a) and (b) is in the range of from 1.2 to 1.5.
5. Powder coating compositions according to claim 1, characterized in that component (b) is an α, , , ' α' -branched aliphatic dicarboxylic acids containing from 8 to 18 carbon atoms in the acid residue and preferably from 10 to 14 carbon atoms while the symbols R either all represent methyl or three of them represent methyl and one represents ethyl.
6. Powder coating compositions according to claim 5, characterized in that component (b) is composed of 2, 2, 6, 6-tetramethyl pimelic acid, 2 , 2 , 5-trimethyl-5-ethyl adipic acid or mixtures thereof in a mutual molar ratio in the range of from 2:1 to 1:2.
7. Powder coating compositions according to claim 1, characterized in that the curing agent is selected from acid functional polyesters.
8. Cured powder coating compositions on a substrate, characterized in that powder coating compositions according to claims 1-7 have been applied.
9. Advanced resin product, obtainable by reacting (a) a diglycidyl ether of a bisphenol of the general formula I
10. Advanced resin product according to claim 9, characterized in that the advanced resin product (i) is formed by a reaction between components (a) and (b) at a temperature of between 60 °C and 160 °C.
11. Advanced resin product according to claims 9 and 10, characterized in that the molar ratio between components (a) and (b) is in the range of from 1.1 to 2.0.
12. Advanced resin product according to claim 11, characterized in that the molar ratio between the components (a) and (b) is in the range of from 1.2 to 1.5.
13. Advanced resin product according to claim 9, characterized in that component (b) is an α, α, α, ' α' -branched aliphatic dicarboxylic acids containing from 8 to 18 carbon atoms in the acid residue and preferably from 10 to 14 carbon atoms while the symbols R either all represent methyl or three of them represent methyl and one represents ethyl.
14. Advanced resin product according to claim 13, characterized in that component (b) is composed of 2 , 2 , 6, 6-tetramethyl pimelic acid, 2, 2, 5-trimethyl-5-ethyl adipic acid or mixtures thereof in a mutual molar ratio in the range of from 10:1 to 1:10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01200034 | 2001-01-05 | ||
| EP01200034.5 | 2001-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002053621A1 true WO2002053621A1 (en) | 2002-07-11 |
Family
ID=8179726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2001/014706 WO2002053621A1 (en) | 2001-01-05 | 2001-12-07 | Advanced resin derived from a low molecular weight glycidyl ether and a di-tertiary carboxylic acid and powder coating compositions comprising it |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2002053621A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220162374A1 (en) * | 2019-03-27 | 2022-05-26 | Showa Denko Materials Co., Ltd. | Epoxy resin, epoxy resin composition, epoxy resin cured product and composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518408A2 (en) * | 1991-05-31 | 1992-12-16 | Shell Internationale Researchmaatschappij B.V. | Thermosetting resin composition |
| JPH08302242A (en) * | 1995-05-12 | 1996-11-19 | Dainippon Ink & Chem Inc | Powdery coating material composition |
-
2001
- 2001-12-07 WO PCT/EP2001/014706 patent/WO2002053621A1/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518408A2 (en) * | 1991-05-31 | 1992-12-16 | Shell Internationale Researchmaatschappij B.V. | Thermosetting resin composition |
| JPH08302242A (en) * | 1995-05-12 | 1996-11-19 | Dainippon Ink & Chem Inc | Powdery coating material composition |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 1997, no. 03 31 March 1997 (1997-03-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220162374A1 (en) * | 2019-03-27 | 2022-05-26 | Showa Denko Materials Co., Ltd. | Epoxy resin, epoxy resin composition, epoxy resin cured product and composite material |
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