CA2270731A1 - Novel epoxy-amine coating compositions - Google Patents
Novel epoxy-amine coating compositions Download PDFInfo
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- CA2270731A1 CA2270731A1 CA002270731A CA2270731A CA2270731A1 CA 2270731 A1 CA2270731 A1 CA 2270731A1 CA 002270731 A CA002270731 A CA 002270731A CA 2270731 A CA2270731 A CA 2270731A CA 2270731 A1 CA2270731 A1 CA 2270731A1
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B20/00—Signal processing not specific to the method of recording or reproducing; Circuits therefor
- G11B20/10—Digital recording or reproducing
- G11B20/10527—Audio or video recording; Data buffering arrangements
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/14—Digital output to display device ; Cooperation and interconnection of the display device with other functional units
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/16—Sound input; Sound output
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B19/00—Driving, starting, stopping record carriers not specifically of filamentary or web form, or of supports therefor; Control thereof; Control of operating function ; Driving both disc and head
- G11B19/02—Control of operating function, e.g. switching from recording to reproducing
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B20/00—Signal processing not specific to the method of recording or reproducing; Circuits therefor
- G11B20/10—Digital recording or reproducing
- G11B20/10009—Improvement or modification of read or write signals
- G11B20/10018—Improvement or modification of read or write signals analog processing for digital recording or reproduction
- G11B20/10027—Improvement or modification of read or write signals analog processing for digital recording or reproduction adjusting the signal strength during recording or reproduction, e.g. variable gain amplifiers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B33/00—Constructional parts, details or accessories not provided for in the other groups of this subclass
- G11B33/12—Disposition of constructional parts in the apparatus, e.g. of power supply, of modules
- G11B33/121—Disposition of constructional parts in the apparatus, e.g. of power supply, of modules the apparatus comprising a single recording/reproducing device
- G11B33/122—Arrangements for providing electrical connections, e.g. connectors, cables, switches
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
- A45C2011/001—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00 for portable audio devices, e.g. headphones or MP3-players
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- Epoxy Resins (AREA)
Abstract
Accordingly, the invention described herein relates to a low VOC epoxy based coating utilizing the following essential components:
An epoxy functional resin component where the average epoxide functionality is > 1.
2. An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is >1. This includes polyamidoamines, polyamines, ketimines and aldimines.
3. An acetoacetonate functional oligomer where the molecular weight is <
1000 and the acetoacetonate functionality is >1.
4. Optionally other components that typically constitute a complete coatings system such as pigments, catalysts, additives, plasticizers, etc.
This is typically a three-package system however, with modification, it can become a two-package system.
An epoxy functional resin component where the average epoxide functionality is > 1.
2. An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is >1. This includes polyamidoamines, polyamines, ketimines and aldimines.
3. An acetoacetonate functional oligomer where the molecular weight is <
1000 and the acetoacetonate functionality is >1.
4. Optionally other components that typically constitute a complete coatings system such as pigments, catalysts, additives, plasticizers, etc.
This is typically a three-package system however, with modification, it can become a two-package system.
Description
NOVEL EPOXY - AMINE COATING COMPOSTTIONS
BACKGROUND OF THE INVENTION
to In the current environment of regulations intended to reduce the amount of volatile organic compounds (or VOC) that are released into the atmosphere on application of coatings, it is very difficult to formulate coating compositions that meet the regulatory limits without some kind of crosslinking mechanism that takes place after application. In order to achieve a suitable spray application viscosity (20-30 seconds #4 Ford cup @20°C) as VOC
regulations have 15 mandated higher application non-volatiles it has been necessary to use resins with lower molecular weights and generally lower Tg. Both of these changes generally have the effect of lengthening the dry time of the applied coating since the number of crosslink reactions required to achieve a "dry to handle" condition increases significantly. Epoxy/amine coatings systems are well known in the art as a class of coatings that is useful as a primer. A low VOC
epoxy/amine system may be 2o achieved through the use of low molecular weight epoxy resins and optionally the use of low molecular weight polyamines, polyketimines or polyaldimines. Health concerns are raised when considering the use of a low molecular weight epoxy resin, which may, depending on the application, preclude its use. The present invention effectively reduces the VOC of epoxy/amine coating systems without resorting to use of low molecular weight epoxides.
25 This invention also describes a method to reduce the volatile organic content (VOC) of a paint composition by increasing the solids of a paint composition without adversely affecting the sprayable viscosity of the paint and also without significantly decreasing the durability or performance of the final paint film so produced.
SUMMARY OF THE INVENTION
Accordingly, the invention described herein relates to a low VOC epoxy based coating utilizing the following essential components:
1. An epoxy functional resin component where the average epoxide functionality is >1.
BACKGROUND OF THE INVENTION
to In the current environment of regulations intended to reduce the amount of volatile organic compounds (or VOC) that are released into the atmosphere on application of coatings, it is very difficult to formulate coating compositions that meet the regulatory limits without some kind of crosslinking mechanism that takes place after application. In order to achieve a suitable spray application viscosity (20-30 seconds #4 Ford cup @20°C) as VOC
regulations have 15 mandated higher application non-volatiles it has been necessary to use resins with lower molecular weights and generally lower Tg. Both of these changes generally have the effect of lengthening the dry time of the applied coating since the number of crosslink reactions required to achieve a "dry to handle" condition increases significantly. Epoxy/amine coatings systems are well known in the art as a class of coatings that is useful as a primer. A low VOC
epoxy/amine system may be 2o achieved through the use of low molecular weight epoxy resins and optionally the use of low molecular weight polyamines, polyketimines or polyaldimines. Health concerns are raised when considering the use of a low molecular weight epoxy resin, which may, depending on the application, preclude its use. The present invention effectively reduces the VOC of epoxy/amine coating systems without resorting to use of low molecular weight epoxides.
25 This invention also describes a method to reduce the volatile organic content (VOC) of a paint composition by increasing the solids of a paint composition without adversely affecting the sprayable viscosity of the paint and also without significantly decreasing the durability or performance of the final paint film so produced.
SUMMARY OF THE INVENTION
Accordingly, the invention described herein relates to a low VOC epoxy based coating utilizing the following essential components:
1. An epoxy functional resin component where the average epoxide functionality is >1.
2. An aliphatic amine or aliphatic blocked amine fianctional component where the 1o amine functionality is >1. This includes polyamidoamines, polyamines, ketimines and aldimines.
3. An acetoacetonate functional oligomer where the molecular weight is < 1000 and the acetoacetonate functionality is > 1.
4. Optionally other components that typically constitute a complete coatings system such as pigments, catalysts, additives, plasticizers, etc.
This is typically a three-package system however, with modification, it can become a two-package 2o system.
The low molecular weight polyacetoacetonate component can be prepared by various methods, the preferred method being transesterification of a polyol, such as ethylene glycol or preferably glycerine, with t-butylacetoacetonate, and then distilling offt-butanol as a by-product.
DETAILED DESCRIPTION
Accordingly, the invention described herein relates to a low VOC epoxy based coating utilizing the following essential components:
An epoxy functional resin component where the average epoxide functionality is >1.
2. An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is > 1. This includes polyamidoamines, polyamines, ketimines and aldimines.
An acetoacetonate functional oligomer where the molecular weight is < 1000 and the acetoacetonate functionality is > I.
4. Optionally other components that typically constitute a complete coatings system such as pigments, catalysts, additives, plasticizers, etc.
This is typically a three-package system however, with modification, it can become a two-package system.
The low molecular weight polyacetoacetonate component can be prepared by various methods, the preferred method being transesterification of a polyol, such as ethylene glycol or preferably glycerine, with t-butylacetoacetonate, and then distilling off t-butanol as a by-product.
Finding utility in the instant coatings are flow and rheology modifying agents which 2o include but are not limited to synthetic amorphous hydrophobic silica such as Degussa Aerosil 8972, synthetic amorphous hydrophilic silica Degussa Aerosil 200, organo clays, polyethylene wax dispersions, polypropylene wax dispersions, polyamid wax dispersions, ethylene vinyl acetate wax dispersions. Agents such as Byk Anti-terra 202, Byk Anti-terra 204, Byk Anti-terra V, Byk W-960, Byk R-405, Byk-P104, Byk P-104s; Troy Chemical Troythix Antisag 4, Troy Chemical Troythix Antisettle; Raybo Chemical Raybo 6, Raybo Chemical Raybo 94, and Tego Chemie ZFS
460.
Also finding utility are pigment wetting and dispersing aids which include but are not limited to ICI Solsperse hyperdispersants such as Solsperse 5000, Solsperse 12000, Solsperse 22000 and Solsperse 24000; Troy Chemical Troysol CDI, Troy Chemical Troysol CD2 and Troy Chemical Troysol 98C; Daniel Products DispersAyd 9100; Raybo Chemical Raybo 63; Byk Anti-terra U, Byk Anti terra 202, Byk W-960, Byk p 104 Disperbyk 160, Disperbyk 162, Disperbyk 163; Nuodex Nuosperse 657; Nuodex Nuosperse 700. Also finding utility in these coatings are ultraviolet light absorbers and stabilizers which include but are not limited to Sandoz Chemicals Sanduvor 3206, Sanduvor VSU, Sanduvor 3050; Ciba Geigy Corp. Tinuvin 123, Tinuvin 292, Tinuvin 328, Tinuvin 440, Tinuvin 900, Tinuvin 1130.
Also finding utility in these coatings are various types pigments common to the art which include but are not limited to titanium dioxide, graphite, carbon black, zinc oxide, cadmium Io sulfide, chromium oxide, zinc sulfide, zinc chromate, strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silico chromate, chromium oxide, zinc sulfide, yellow nickel titanium, yellow chromium titanium, red iron oxide, transparent red iron oxide, yellow iron oxides, transparent yellow oxide, black iron oxide, naphthol reds and browns, anthraquinones, dioxazine violet, isoindoline yellows, arylide yellow and oranges, ultramarine blue, phthalocyanine complexes, amaranth, quinacridones, halogenated thioindigo pigments, extender pigments such as magnesium silicate, aluminum silicate, calcium silicate, calcium carbonate, fumed silica, barium sulfate.
The coating composition can be applied using conventional spray equipment or high volume pressure spray equipment resulting in a high quality finish. Other modes of application are 2o roller coating, brushing, sprinkling, flow coating, dipping, electrostatic spraying, or electrophoresis. Exemplary metal substrates include such things as steel, aluminum, copper, zinc, magnesium and alloys thereof. Exemplary non-metallic substrates include such things as the rigid and non-rigid plastics common to the art. The components of the compositions can be varied to and non-rigid plastics common to the art. The components of the compositions can be varied to suit the temperature tolerance of the substrate material. For example, the components can be constituted for ambient or room temperature drying (e.g. less than 100°F), force drying or low temperature baking (e.g. 100°F. - 180°F.), or high temperature baking (e.g. over 180°F.). The coatings may be formulated to meet the requirements of the equipment intended for use during application.
The pigments can be introduced by first forming a mill base with the resin utilized in the composition or with other compatible polymers by conventional techniques, such as sand-to grinding, ball-milling attritor grinding, two roll milling and the like, to disperse the pigments. The mill base is then blended with other film forming constituents as shown in the examples which follow:
Coating compositions described by the present invention find utility in applications of ambient or room temperature drying (e.g. less than 100°F), force drying or low temperature baking (e.g. 100° F. - 180° F.), or high temperature baking (e.g. over 180° F.). The coating cure process for the present invention may also be accelerated by the utilization of radiant heating or Infra red emitting devices known to the art.
The following examples are intended to illustrate the invention. All quantities are shown on a weight bases unless otherwise indicated.
Example 1 Preparation of Acetoacetate-Functional Oligomer GDAA) from Eth~rlene Glycol A 2-liter, 3-necked flask was fitted with a heating mantle, stirrer, thermocouple, NZ inlet, distillation head with thermometer, condenser and receiver. The flask was charged with 173.9 gams of ethylene glycol and 930.2 gams of tert-butyl acetoacetate. It was heated slowly to 140°C under a N2 gas purge. When the temperature reached about 140°C, distillation of byproduct t-butanol was initiated at a head temperature of about 90°C.
The reaction temperature was slowly increased in stages to 180°C, at which point 98% of the calculated amount of t-butanol byproduct had been removed. Yield of ethylene glycol diacetoacetate (EGDAA) was 680 grams. The product was a light-colored liquid with 18 cps Brookfield viscosity and having molecular weight of 230 and an acetoacetate equivalent weight of 115.1.
Example 2 Preparation of Acetoacetate-Functional Oligomer from Glycerol (GTAA~
Into a 2-liter, 3-necked flask set up as described in Example lwas charged 138.1 gams of glycerol and 759.4 gams of t-butylacetoac;etate. Under a nitrogen flow the flask was heated in stages to 175° C. Distillation of byproduct t-butanol began at a head temperature of 95°C and was completed when about 97% of the theoretical amount of t-butanol was collected. Yield of approximately 98% pure glycerol triacetoacetate (GTAA) was 537 gams. The product was a light-colored mobile liquid with a viscosity of 85 - 90 cps (Brookfield), a molecular weight of approximately 344 and an acetoacetate equivalent weight of 114.8.
2o Low molecular weight acetoacetyl derivatives of pentaerythritol, trimethylol propane, Tone~
301 and several other low molecular weight polyols were made by similar procedures. All were low-viscosity light-colored liquids with molecular weights below 1000 and are suitable for use in low VOC coatings of the type described herein.
Example 3 Low VOC Coatings from Epoxy Resins, Low Molecular Weight Acetoacetates.
Aldimines and Other Ingredients Primer coating compositions were formulated from a resin base, DE15, which is a standard BASF
epoxy-resin primer base that also contains pigment and other additives in addition to the epoxy resin; AEP (aminoethylpiperazine), which is a standard epoxy curing agent (the control used PA16, a polyamidoamine curing agent) ; and PR70, which is a standard BASF
toluene/butyl acetate reducer. The experimental coatings were modified with varying amounts of low molecular weight acetoacetate reactive diluents and an aldehyde blocked amine (aldimine) curing 2 0 agent for the acetoacetate. In the experimental resins some of the PR70 reducer was replaced by methyl ethyl ketone, which stabilizes the aldimine hardener. The table below shows a representative sample of such coatings compared with an epoxy primer control that does not incorporate the acetoacetate-blocked amine reactive reducer modifcation. The table also shows VOC results and other important system properties.
Ingredient Coating A Exper. Coating Exper. Coating Exper. Coating (grams) (control) B C D
DE15 252.0 252.0 252.0 252.0 GTAA 0 36.0 22.5 27.0 EGDAA 0 0 10.0 11.4 3 0 PR70 33.0 18.0 18.0 15.0 MEK* 0 19.5 19.5 19.5 PA16 hardener 67.0 0 0 0 AEP 0 4.5 4.8 4.8 CE4072 Aldimine 0 44.8 17.5 23.6 *Methyl ethyl ketone Properties:
Visc. (#4Cup) 17.5 sec 18 sec l9.Ssec 19.5sec Wt.(lb. per gal.) 11.1 11.1 11.6 11.6 VOC(Ib. per gal) 4.7 3.1 3.48 3.24 Pot life for the control and the experimental coatings was at least one hour for each one. All coatings were drawn down over bare steel plates or sprayed on to these plates and compared for dust-free and tack-free times. The control and experimental compositions were dust-free in less than 30 minutes and tack-free in less than two hours. As primers, all systems could be overcoated with white basecoats in 30 minutes and demonstrated enough holdout of the basecoat to prevent any dieback of the white basecoats.
2o Note that all the experimental primer coatings have at least a 25% lower volatile organic content (VOC) than the control, while retaining adequate performance as a primer coating..
The low molecular weight (< 1000) of these acetoacetates results in the low viscosity properties that allow for incorporation as reactive diluents or reducers. Higher molecular weight 2s acetoacetate-functional compounds would not have given the low viscosities that would permit practical use as modifiers for epoxy coating systems.
s
This is typically a three-package system however, with modification, it can become a two-package 2o system.
The low molecular weight polyacetoacetonate component can be prepared by various methods, the preferred method being transesterification of a polyol, such as ethylene glycol or preferably glycerine, with t-butylacetoacetonate, and then distilling offt-butanol as a by-product.
DETAILED DESCRIPTION
Accordingly, the invention described herein relates to a low VOC epoxy based coating utilizing the following essential components:
An epoxy functional resin component where the average epoxide functionality is >1.
2. An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is > 1. This includes polyamidoamines, polyamines, ketimines and aldimines.
An acetoacetonate functional oligomer where the molecular weight is < 1000 and the acetoacetonate functionality is > I.
4. Optionally other components that typically constitute a complete coatings system such as pigments, catalysts, additives, plasticizers, etc.
This is typically a three-package system however, with modification, it can become a two-package system.
The low molecular weight polyacetoacetonate component can be prepared by various methods, the preferred method being transesterification of a polyol, such as ethylene glycol or preferably glycerine, with t-butylacetoacetonate, and then distilling off t-butanol as a by-product.
Finding utility in the instant coatings are flow and rheology modifying agents which 2o include but are not limited to synthetic amorphous hydrophobic silica such as Degussa Aerosil 8972, synthetic amorphous hydrophilic silica Degussa Aerosil 200, organo clays, polyethylene wax dispersions, polypropylene wax dispersions, polyamid wax dispersions, ethylene vinyl acetate wax dispersions. Agents such as Byk Anti-terra 202, Byk Anti-terra 204, Byk Anti-terra V, Byk W-960, Byk R-405, Byk-P104, Byk P-104s; Troy Chemical Troythix Antisag 4, Troy Chemical Troythix Antisettle; Raybo Chemical Raybo 6, Raybo Chemical Raybo 94, and Tego Chemie ZFS
460.
Also finding utility are pigment wetting and dispersing aids which include but are not limited to ICI Solsperse hyperdispersants such as Solsperse 5000, Solsperse 12000, Solsperse 22000 and Solsperse 24000; Troy Chemical Troysol CDI, Troy Chemical Troysol CD2 and Troy Chemical Troysol 98C; Daniel Products DispersAyd 9100; Raybo Chemical Raybo 63; Byk Anti-terra U, Byk Anti terra 202, Byk W-960, Byk p 104 Disperbyk 160, Disperbyk 162, Disperbyk 163; Nuodex Nuosperse 657; Nuodex Nuosperse 700. Also finding utility in these coatings are ultraviolet light absorbers and stabilizers which include but are not limited to Sandoz Chemicals Sanduvor 3206, Sanduvor VSU, Sanduvor 3050; Ciba Geigy Corp. Tinuvin 123, Tinuvin 292, Tinuvin 328, Tinuvin 440, Tinuvin 900, Tinuvin 1130.
Also finding utility in these coatings are various types pigments common to the art which include but are not limited to titanium dioxide, graphite, carbon black, zinc oxide, cadmium Io sulfide, chromium oxide, zinc sulfide, zinc chromate, strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silico chromate, chromium oxide, zinc sulfide, yellow nickel titanium, yellow chromium titanium, red iron oxide, transparent red iron oxide, yellow iron oxides, transparent yellow oxide, black iron oxide, naphthol reds and browns, anthraquinones, dioxazine violet, isoindoline yellows, arylide yellow and oranges, ultramarine blue, phthalocyanine complexes, amaranth, quinacridones, halogenated thioindigo pigments, extender pigments such as magnesium silicate, aluminum silicate, calcium silicate, calcium carbonate, fumed silica, barium sulfate.
The coating composition can be applied using conventional spray equipment or high volume pressure spray equipment resulting in a high quality finish. Other modes of application are 2o roller coating, brushing, sprinkling, flow coating, dipping, electrostatic spraying, or electrophoresis. Exemplary metal substrates include such things as steel, aluminum, copper, zinc, magnesium and alloys thereof. Exemplary non-metallic substrates include such things as the rigid and non-rigid plastics common to the art. The components of the compositions can be varied to and non-rigid plastics common to the art. The components of the compositions can be varied to suit the temperature tolerance of the substrate material. For example, the components can be constituted for ambient or room temperature drying (e.g. less than 100°F), force drying or low temperature baking (e.g. 100°F. - 180°F.), or high temperature baking (e.g. over 180°F.). The coatings may be formulated to meet the requirements of the equipment intended for use during application.
The pigments can be introduced by first forming a mill base with the resin utilized in the composition or with other compatible polymers by conventional techniques, such as sand-to grinding, ball-milling attritor grinding, two roll milling and the like, to disperse the pigments. The mill base is then blended with other film forming constituents as shown in the examples which follow:
Coating compositions described by the present invention find utility in applications of ambient or room temperature drying (e.g. less than 100°F), force drying or low temperature baking (e.g. 100° F. - 180° F.), or high temperature baking (e.g. over 180° F.). The coating cure process for the present invention may also be accelerated by the utilization of radiant heating or Infra red emitting devices known to the art.
The following examples are intended to illustrate the invention. All quantities are shown on a weight bases unless otherwise indicated.
Example 1 Preparation of Acetoacetate-Functional Oligomer GDAA) from Eth~rlene Glycol A 2-liter, 3-necked flask was fitted with a heating mantle, stirrer, thermocouple, NZ inlet, distillation head with thermometer, condenser and receiver. The flask was charged with 173.9 gams of ethylene glycol and 930.2 gams of tert-butyl acetoacetate. It was heated slowly to 140°C under a N2 gas purge. When the temperature reached about 140°C, distillation of byproduct t-butanol was initiated at a head temperature of about 90°C.
The reaction temperature was slowly increased in stages to 180°C, at which point 98% of the calculated amount of t-butanol byproduct had been removed. Yield of ethylene glycol diacetoacetate (EGDAA) was 680 grams. The product was a light-colored liquid with 18 cps Brookfield viscosity and having molecular weight of 230 and an acetoacetate equivalent weight of 115.1.
Example 2 Preparation of Acetoacetate-Functional Oligomer from Glycerol (GTAA~
Into a 2-liter, 3-necked flask set up as described in Example lwas charged 138.1 gams of glycerol and 759.4 gams of t-butylacetoac;etate. Under a nitrogen flow the flask was heated in stages to 175° C. Distillation of byproduct t-butanol began at a head temperature of 95°C and was completed when about 97% of the theoretical amount of t-butanol was collected. Yield of approximately 98% pure glycerol triacetoacetate (GTAA) was 537 gams. The product was a light-colored mobile liquid with a viscosity of 85 - 90 cps (Brookfield), a molecular weight of approximately 344 and an acetoacetate equivalent weight of 114.8.
2o Low molecular weight acetoacetyl derivatives of pentaerythritol, trimethylol propane, Tone~
301 and several other low molecular weight polyols were made by similar procedures. All were low-viscosity light-colored liquids with molecular weights below 1000 and are suitable for use in low VOC coatings of the type described herein.
Example 3 Low VOC Coatings from Epoxy Resins, Low Molecular Weight Acetoacetates.
Aldimines and Other Ingredients Primer coating compositions were formulated from a resin base, DE15, which is a standard BASF
epoxy-resin primer base that also contains pigment and other additives in addition to the epoxy resin; AEP (aminoethylpiperazine), which is a standard epoxy curing agent (the control used PA16, a polyamidoamine curing agent) ; and PR70, which is a standard BASF
toluene/butyl acetate reducer. The experimental coatings were modified with varying amounts of low molecular weight acetoacetate reactive diluents and an aldehyde blocked amine (aldimine) curing 2 0 agent for the acetoacetate. In the experimental resins some of the PR70 reducer was replaced by methyl ethyl ketone, which stabilizes the aldimine hardener. The table below shows a representative sample of such coatings compared with an epoxy primer control that does not incorporate the acetoacetate-blocked amine reactive reducer modifcation. The table also shows VOC results and other important system properties.
Ingredient Coating A Exper. Coating Exper. Coating Exper. Coating (grams) (control) B C D
DE15 252.0 252.0 252.0 252.0 GTAA 0 36.0 22.5 27.0 EGDAA 0 0 10.0 11.4 3 0 PR70 33.0 18.0 18.0 15.0 MEK* 0 19.5 19.5 19.5 PA16 hardener 67.0 0 0 0 AEP 0 4.5 4.8 4.8 CE4072 Aldimine 0 44.8 17.5 23.6 *Methyl ethyl ketone Properties:
Visc. (#4Cup) 17.5 sec 18 sec l9.Ssec 19.5sec Wt.(lb. per gal.) 11.1 11.1 11.6 11.6 VOC(Ib. per gal) 4.7 3.1 3.48 3.24 Pot life for the control and the experimental coatings was at least one hour for each one. All coatings were drawn down over bare steel plates or sprayed on to these plates and compared for dust-free and tack-free times. The control and experimental compositions were dust-free in less than 30 minutes and tack-free in less than two hours. As primers, all systems could be overcoated with white basecoats in 30 minutes and demonstrated enough holdout of the basecoat to prevent any dieback of the white basecoats.
2o Note that all the experimental primer coatings have at least a 25% lower volatile organic content (VOC) than the control, while retaining adequate performance as a primer coating..
The low molecular weight (< 1000) of these acetoacetates results in the low viscosity properties that allow for incorporation as reactive diluents or reducers. Higher molecular weight 2s acetoacetate-functional compounds would not have given the low viscosities that would permit practical use as modifiers for epoxy coating systems.
s
Claims (6)
1. A low VOC coating composition comprising:
(a) An epoxy functional resin component where the average epoxide functionality is >1., (b) An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is > 1, and (c) An acetoacetonate functional oligomer where the molecular weight is < 1000 and the acetoacetonate functionality is > 1.
(a) An epoxy functional resin component where the average epoxide functionality is >1., (b) An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is > 1, and (c) An acetoacetonate functional oligomer where the molecular weight is < 1000 and the acetoacetonate functionality is > 1.
2. The coating composition of claim 1 wherein the amine component is selected from the group consisting of polyamidoamine, polyamine, ketimine and aldimine.
3. The coating composition of claim 1 that additionally contains a pigment.
4. The coating composition of claim 1 that additionally contains a catalyst.
5. The coating composition of claim 1 that additionally contains a plasticizer.
6. A low VOC coating composition comprising:
(a) An epoxy functional resin component whre the average epoxide functionality is >1, (b) An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is >1. This includes polyamidoamines, polyamines, ketimines and aldimines.
(c) An acetoacetonate functional oligomer where the molecular weight is <1000 and the acetoacetonate functionality is > 1 and (d) Optionally other components that typically constitute a compete coatings system.
(a) An epoxy functional resin component whre the average epoxide functionality is >1, (b) An aliphatic amine or aliphatic blocked amine functional component where the amine functionality is >1. This includes polyamidoamines, polyamines, ketimines and aldimines.
(c) An acetoacetonate functional oligomer where the molecular weight is <1000 and the acetoacetonate functionality is > 1 and (d) Optionally other components that typically constitute a compete coatings system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9233898A | 1998-06-05 | 1998-06-05 | |
| US09/092,338 | 1998-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2270731A1 true CA2270731A1 (en) | 1999-12-05 |
Family
ID=22232753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002270731A Abandoned CA2270731A1 (en) | 1998-06-05 | 1999-04-29 | Novel epoxy-amine coating compositions |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2000038543A (en) |
| KR (1) | KR20000005709A (en) |
| CN (1) | CN1238362A (en) |
| AU (1) | AU2695299A (en) |
| BR (1) | BR9901662A (en) |
| CA (1) | CA2270731A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303171C (en) * | 2002-04-29 | 2007-03-07 | 三菱瓦斯化学株式会社 | Composition for coating with gas shielding characteristic, said coating using the composition and coating film |
| CN114127043A (en) * | 2019-07-17 | 2022-03-01 | 阿尔萨达股份公司 | Process for the preparation of decolorized acetoacetylated glycols |
-
1999
- 1999-04-29 CA CA002270731A patent/CA2270731A1/en not_active Abandoned
- 1999-05-05 AU AU26952/99A patent/AU2695299A/en not_active Abandoned
- 1999-05-25 KR KR1019990018809A patent/KR20000005709A/en not_active Application Discontinuation
- 1999-05-25 JP JP11145423A patent/JP2000038543A/en active Pending
- 1999-05-27 BR BR9901662-1A patent/BR9901662A/en not_active Application Discontinuation
- 1999-05-28 CN CN99106944A patent/CN1238362A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000005709A (en) | 2000-01-25 |
| CN1238362A (en) | 1999-12-15 |
| AU2695299A (en) | 1999-12-16 |
| BR9901662A (en) | 1999-12-28 |
| JP2000038543A (en) | 2000-02-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |