CA1129587A - Saturated cross-linkable composition - Google Patents
Saturated cross-linkable compositionInfo
- Publication number
- CA1129587A CA1129587A CA322,917A CA322917A CA1129587A CA 1129587 A CA1129587 A CA 1129587A CA 322917 A CA322917 A CA 322917A CA 1129587 A CA1129587 A CA 1129587A
- Authority
- CA
- Canada
- Prior art keywords
- cross
- composition
- paint
- powdered
- composition according
- 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.)
- Expired
Links
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
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Abstract
A powdered saturated cross-linkable composition suitable for use as a bonding agent in a powdered paint mixture, said composition comprising at least one epoxy resin and a diarhydride cross-linking agent having at least one eater group function obtained by the reaction of trimellitic anhydride with a diol containing from 2 to 10 carbon atoms in a molar ratio of trimellitic anhydride to diol between 2:1 and 2:1.5. Paint compositions in powder form which include the cross-linkable compositions are also disclosed which give cured paint coatings having superior mechanical properties, such as resistance to impact and bending, and superior chemical properties, such as resistance to solvents.
Description
s~
The present invention relates to saturated cross-linkable composi-tions for paint in powder form, more particularly to compositions having an epoxy resin and a cross-linking agent having acid-anhydri~e groupsO
A Canadian Patent Application 242,409 in the Applicant's name, filed December 23rd, 1975, describes compositions containing a dianhydride having es~er group functions obtained by reacting trimellitic anhydride with a diol in a trimellitic anhydride:diol molecular ratio of less than two, preferably between 2:1 and 2:1,5, and the use thereof as cross-linkers in saturated cross-linkable compounds or compositions containirg a saturated polyester resin having mainly hydroxyl group functions.
The Applicant has now found that the anhydride cross-linking compounds having ester group functions may be used as epoxy-resin cross-linking agents. The present invention therefore relates to saturated cross-linkable compositions comprising at least one saturated epoxy resin and at least one cross-linking agent which is a compound containing a dianhydride having ester group functions. The invention also relates to paints in powder form comprising the said composition and their method of preparation.
According to the present invention, there is provided a powdered saturated cross-linkable composition suitable for use as a bonding agent in a powdered paint mixture, said composition comprising at least one epoxy resin and a dianhydride cross-linking agent having at least one ester group function obtained by the reaction of trimellitic anhydride with a diol con-taining from 2 to 10 carbon atoms in a molar ratio of trimellitic anhydride to diol bet~een 2:1 and 2:1.5.
The compositions according to the invention contain a saturated epoxy resin, which are known condensation products of a diphenol such as 2,2-;` ' , ~ ~
13~2~
:~ `
. .
.
(4-hydroxyphenyl)-propane and of an epihalohydrin such as epichlorhydrin, the molecular ratio of the epichlorhydrin or diphenol being generally between 1,2 and 1,5, and which are prepared by known methods. The epoxy resins used in the compositions according to the invention are solid masses, the melting ` points of which, as measured by the ball-and-ring method, are between 50 and 120C, preferably between 70 and 100Co The epoxy equivalent of the epoxy resins is between about 400 and 1500, preferably between 500 and 1000.
~; These epoxy resins are known in the art As non-restrictive examples, representative resins are epoxy resins having epoxy equivalents of between 850 and 950, as described by S.T. HARRIS -"The technology of powder coatings - PORTCULIIS PRESS, London - 1976 - pages 16 and 17"; and for example resins sold commercially by CIB~-GEIGY under the Trade Mark ARALDITE
7004, DER 664 U, Trade Mark, sold by DOW, and the resin sold by SHELL
CHEMICAL under the Trade Mark EPIKOTE 10040 The cross-linking agent according to the present invention is a compound having anhydride groups. It generally consists of a dianhydride compound having ester groups obtained by reacting trimellitic anhydride with a diol in a molecular ratio generally between 2:1 and 2:1,50 The diol used is preferably ethylene glycol. The cross-linking agent has a softening point of between 70 and 120C, preferably between 75 and 110C, an acid index in an aqueous medium preferably between 390 and 540~ and an acid index in an alcohol medium preferably between 250 and 320. The cross-linking agent is . . .
generally prepared by reacting trimellitic anhydride and diol at a temperature ``~ of between 180 and 250 C until no further water is released.
The compositions according to the invention are cross-linkable by poly-addition and poly-condensation at temperatures of between 140 and 200~, ' ;. ;
. . . . . ........................ .
" ,, ~ .. .. . .
1~1.2 ,'.
for periods of between S and 40 minutes.
In the case of paints in powder form in which the bonding agent ~ is a composition according to the invention, the epoxy resin and its cross-`~ linking agent are present, respectively, in quantities such that there exists substantially stoichiometric equilibrium between the reactive functions of the two constituents. Paint compositions in powder form contain, in addition to the above-mentioned bonding agents, film-forming or spreading agents in amounts of between 0,1 and 1.0% by weight of the composition such as acrylic polymers and additives known in the paint industry, such as pig-ments, dyestuffs and fillers.
The paints in powder form according to the invention are prepared merely by mixing the paint constituents in a certain order or certain combina-tions. For example, the resin and the cross-linking agent may first be mixed to form the bonding agent composition by melting at a temperature generally below 120 C, preferably below 100 C, for a short time, in an internal mixer, an extruder, or an apparatus of the Bliss type. This is followed by cooling, after which the bonding agent is crushed and the additives are incorporated in a dry-mixing operation. This is followed by further mi~ing by melting, as before. It is also possible to mix various constituents together before the final mixing by melting. It is generally preferable to mix all of the solid constituents together in the dry state, and then to homogenize them by melting the organic constituentsO The product thus obtained is crushed, grolmd and screened to a particle size which does not generally exceed 100 microns. The products thus obtained are generally applied by known methods such as that of the fluidized bed and electrostatic pulverization onto previously degreased heat-resistant materials such as metals or ceramics, after which cross-linking is carried out at temperatures .2~
..: `
of be~een 150 and 220C for between 5 and 40 minutes. The average thickness of the coating obtained upon the base is usually between 30 and 120 microns.
The compounds according to the invention make it possible to ob-tain coatings having superior or mechanical properties, such as resistance to impact and bending, and superior chemical properties, such as resistance to solvents.
Paints in powder form, in which the bonding agent is a constituent ~` according to the invention are used in automobiles, eonstruction, and agri-cultural machines as coatings for metallic surfacesO
The following examples are intended to be merely illustrative and ;~ non-restrictive the proportions being by weight unless otherwise indicated.
~PLE 1 The epoxy resin used in this example is ~raldite 7004, Trade Mark for epoxy resin sold by CIBA-GEIGY.
The cross-linking agent used is prepared by reacting 384 g (2 moles) of a trimellitic anhydride with 77,5 g (1,25 mole~ of ethylene glycol. The trimellitie anhydride is first plaeed in a reaetor swept with nitrogen which is heated to 230 C. The~ethylene glycol is then introduced progressively, the temperature in the reactor being maintained by external coolingO Two hours after the end of this addition, there is no further release of waterO
" The produet is then cast, cooled and ground and has the following charac-teristics: `
- acid index in an aqueous medium 463 - acid index in an alcohol medium 284 - melting point (ball-and-ring method) ~0C.
The paint powder composition is then prepared as follows:
- ~raldite resin lO0 parts - Cross-linking agent as prepared above 25 parts - . .
~L3.~ 7 ,, - TiO2 rutile ~- 50 parts - film-forming agent~ 2 parts me powdered components are thoroughly mixed and the mixture is extruded from a Buss mixer at a temperature of 100 C. ~he mixture is cooled, ; finely gro~md, and then screened through a 100 micron-mesh screen.
The paint powder mixture thus obtained is applied with an electro-static gun ~SAMES brand Trade Mark) to a steel plate which has been previous-ly degreased, the steel plate measuring 20 x 10 x 0,8 cmO This plate is then baked for 25 minutes at 200C.
~ 10 After cooling, the cured film of paint is checked for the follow-- ing properties:
- impact resistance : measured according to NFT 30039 - Ericson deep-drawing : " " " NFT 30019 ~ - ASTM bending : " " " ASTM D 522-60 - Persoz hardness (seconds): " " " NFT 30016 - MEK test a drop of methyl-ethyl ketone is : placed upon the coating, the spot is rubbed with a fingernail, and the time in minutes, required to remove .~ the coating, is noted.
:~ The res~ts are given in the table hereinbelowO
~A~PLE 2 The epoxy resin used in this example is the same as that used in . Example lo The cross-linking agent is prepared as in Example 1, but the trimellitic anhydride : ethylene glycol molecular ratio is as 2:1,50 The cross-linking agent thus obtained has the following characteristics:
:`
* titanium oxide rutile - Kronos CL 220 Trade;Mark sold by the Société
Industrielle du Titane Acronal 4F, Trade Mark sold by BASF.
. .
~ . . ~ ~, , . ' .
1~ 7 - acid index in an aqueous medium 390 - acid index in an alcohol medium 250 - melting point (ball-and-ring method)0 100 C
- As in Example 1~ painting is carried out with a powder mixture of the following composition:
- Araldite resin 7004100 parts - reticulant as prepared abovc 25 parts - TiO2 rutile* 50 parts - film-forming agent~ff~2 parts -~ titanium oxide rutile - Kronos CL 220, Trade Mark sold by the Société
Industrielle du Titane ~^-Acronal 4F, Trade Mark sold by BASF.
The paint powder mixture is applied to a steel plate as in Example 1. The characteristics of the coating are given in the table hereinbelow.
~''' .
,~ .
:' :
., - . ,.~. :, . .
~.2~7 :`
~ ll /l ': _ ..
N ~ o . ~ ~ C`l ~. S~ ~ jn ~ cil -. ~ _ -~ ~ H ~1: O ~1 `''~ ~i .____ .
' S: ~ 1~ ~) ,.' ~
_ ~_ _ ~ H o o ' ~1 ri ~
1~ ~ ~ ~
- . _ _ '',:
'
The present invention relates to saturated cross-linkable composi-tions for paint in powder form, more particularly to compositions having an epoxy resin and a cross-linking agent having acid-anhydri~e groupsO
A Canadian Patent Application 242,409 in the Applicant's name, filed December 23rd, 1975, describes compositions containing a dianhydride having es~er group functions obtained by reacting trimellitic anhydride with a diol in a trimellitic anhydride:diol molecular ratio of less than two, preferably between 2:1 and 2:1,5, and the use thereof as cross-linkers in saturated cross-linkable compounds or compositions containirg a saturated polyester resin having mainly hydroxyl group functions.
The Applicant has now found that the anhydride cross-linking compounds having ester group functions may be used as epoxy-resin cross-linking agents. The present invention therefore relates to saturated cross-linkable compositions comprising at least one saturated epoxy resin and at least one cross-linking agent which is a compound containing a dianhydride having ester group functions. The invention also relates to paints in powder form comprising the said composition and their method of preparation.
According to the present invention, there is provided a powdered saturated cross-linkable composition suitable for use as a bonding agent in a powdered paint mixture, said composition comprising at least one epoxy resin and a dianhydride cross-linking agent having at least one ester group function obtained by the reaction of trimellitic anhydride with a diol con-taining from 2 to 10 carbon atoms in a molar ratio of trimellitic anhydride to diol bet~een 2:1 and 2:1.5.
The compositions according to the invention contain a saturated epoxy resin, which are known condensation products of a diphenol such as 2,2-;` ' , ~ ~
13~2~
:~ `
. .
.
(4-hydroxyphenyl)-propane and of an epihalohydrin such as epichlorhydrin, the molecular ratio of the epichlorhydrin or diphenol being generally between 1,2 and 1,5, and which are prepared by known methods. The epoxy resins used in the compositions according to the invention are solid masses, the melting ` points of which, as measured by the ball-and-ring method, are between 50 and 120C, preferably between 70 and 100Co The epoxy equivalent of the epoxy resins is between about 400 and 1500, preferably between 500 and 1000.
~; These epoxy resins are known in the art As non-restrictive examples, representative resins are epoxy resins having epoxy equivalents of between 850 and 950, as described by S.T. HARRIS -"The technology of powder coatings - PORTCULIIS PRESS, London - 1976 - pages 16 and 17"; and for example resins sold commercially by CIB~-GEIGY under the Trade Mark ARALDITE
7004, DER 664 U, Trade Mark, sold by DOW, and the resin sold by SHELL
CHEMICAL under the Trade Mark EPIKOTE 10040 The cross-linking agent according to the present invention is a compound having anhydride groups. It generally consists of a dianhydride compound having ester groups obtained by reacting trimellitic anhydride with a diol in a molecular ratio generally between 2:1 and 2:1,50 The diol used is preferably ethylene glycol. The cross-linking agent has a softening point of between 70 and 120C, preferably between 75 and 110C, an acid index in an aqueous medium preferably between 390 and 540~ and an acid index in an alcohol medium preferably between 250 and 320. The cross-linking agent is . . .
generally prepared by reacting trimellitic anhydride and diol at a temperature ``~ of between 180 and 250 C until no further water is released.
The compositions according to the invention are cross-linkable by poly-addition and poly-condensation at temperatures of between 140 and 200~, ' ;. ;
. . . . . ........................ .
" ,, ~ .. .. . .
1~1.2 ,'.
for periods of between S and 40 minutes.
In the case of paints in powder form in which the bonding agent ~ is a composition according to the invention, the epoxy resin and its cross-`~ linking agent are present, respectively, in quantities such that there exists substantially stoichiometric equilibrium between the reactive functions of the two constituents. Paint compositions in powder form contain, in addition to the above-mentioned bonding agents, film-forming or spreading agents in amounts of between 0,1 and 1.0% by weight of the composition such as acrylic polymers and additives known in the paint industry, such as pig-ments, dyestuffs and fillers.
The paints in powder form according to the invention are prepared merely by mixing the paint constituents in a certain order or certain combina-tions. For example, the resin and the cross-linking agent may first be mixed to form the bonding agent composition by melting at a temperature generally below 120 C, preferably below 100 C, for a short time, in an internal mixer, an extruder, or an apparatus of the Bliss type. This is followed by cooling, after which the bonding agent is crushed and the additives are incorporated in a dry-mixing operation. This is followed by further mi~ing by melting, as before. It is also possible to mix various constituents together before the final mixing by melting. It is generally preferable to mix all of the solid constituents together in the dry state, and then to homogenize them by melting the organic constituentsO The product thus obtained is crushed, grolmd and screened to a particle size which does not generally exceed 100 microns. The products thus obtained are generally applied by known methods such as that of the fluidized bed and electrostatic pulverization onto previously degreased heat-resistant materials such as metals or ceramics, after which cross-linking is carried out at temperatures .2~
..: `
of be~een 150 and 220C for between 5 and 40 minutes. The average thickness of the coating obtained upon the base is usually between 30 and 120 microns.
The compounds according to the invention make it possible to ob-tain coatings having superior or mechanical properties, such as resistance to impact and bending, and superior chemical properties, such as resistance to solvents.
Paints in powder form, in which the bonding agent is a constituent ~` according to the invention are used in automobiles, eonstruction, and agri-cultural machines as coatings for metallic surfacesO
The following examples are intended to be merely illustrative and ;~ non-restrictive the proportions being by weight unless otherwise indicated.
~PLE 1 The epoxy resin used in this example is ~raldite 7004, Trade Mark for epoxy resin sold by CIBA-GEIGY.
The cross-linking agent used is prepared by reacting 384 g (2 moles) of a trimellitic anhydride with 77,5 g (1,25 mole~ of ethylene glycol. The trimellitie anhydride is first plaeed in a reaetor swept with nitrogen which is heated to 230 C. The~ethylene glycol is then introduced progressively, the temperature in the reactor being maintained by external coolingO Two hours after the end of this addition, there is no further release of waterO
" The produet is then cast, cooled and ground and has the following charac-teristics: `
- acid index in an aqueous medium 463 - acid index in an alcohol medium 284 - melting point (ball-and-ring method) ~0C.
The paint powder composition is then prepared as follows:
- ~raldite resin lO0 parts - Cross-linking agent as prepared above 25 parts - . .
~L3.~ 7 ,, - TiO2 rutile ~- 50 parts - film-forming agent~ 2 parts me powdered components are thoroughly mixed and the mixture is extruded from a Buss mixer at a temperature of 100 C. ~he mixture is cooled, ; finely gro~md, and then screened through a 100 micron-mesh screen.
The paint powder mixture thus obtained is applied with an electro-static gun ~SAMES brand Trade Mark) to a steel plate which has been previous-ly degreased, the steel plate measuring 20 x 10 x 0,8 cmO This plate is then baked for 25 minutes at 200C.
~ 10 After cooling, the cured film of paint is checked for the follow-- ing properties:
- impact resistance : measured according to NFT 30039 - Ericson deep-drawing : " " " NFT 30019 ~ - ASTM bending : " " " ASTM D 522-60 - Persoz hardness (seconds): " " " NFT 30016 - MEK test a drop of methyl-ethyl ketone is : placed upon the coating, the spot is rubbed with a fingernail, and the time in minutes, required to remove .~ the coating, is noted.
:~ The res~ts are given in the table hereinbelowO
~A~PLE 2 The epoxy resin used in this example is the same as that used in . Example lo The cross-linking agent is prepared as in Example 1, but the trimellitic anhydride : ethylene glycol molecular ratio is as 2:1,50 The cross-linking agent thus obtained has the following characteristics:
:`
* titanium oxide rutile - Kronos CL 220 Trade;Mark sold by the Société
Industrielle du Titane Acronal 4F, Trade Mark sold by BASF.
. .
~ . . ~ ~, , . ' .
1~ 7 - acid index in an aqueous medium 390 - acid index in an alcohol medium 250 - melting point (ball-and-ring method)0 100 C
- As in Example 1~ painting is carried out with a powder mixture of the following composition:
- Araldite resin 7004100 parts - reticulant as prepared abovc 25 parts - TiO2 rutile* 50 parts - film-forming agent~ff~2 parts -~ titanium oxide rutile - Kronos CL 220, Trade Mark sold by the Société
Industrielle du Titane ~^-Acronal 4F, Trade Mark sold by BASF.
The paint powder mixture is applied to a steel plate as in Example 1. The characteristics of the coating are given in the table hereinbelow.
~''' .
,~ .
:' :
., - . ,.~. :, . .
~.2~7 :`
~ ll /l ': _ ..
N ~ o . ~ ~ C`l ~. S~ ~ jn ~ cil -. ~ _ -~ ~ H ~1: O ~1 `''~ ~i .____ .
' S: ~ 1~ ~) ,.' ~
_ ~_ _ ~ H o o ' ~1 ri ~
1~ ~ ~ ~
- . _ _ '',:
'
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A powdered saturated cross-linkable composition suitable for use as a bonding agent in a powdered paint mixture, said composition comprising at least one epoxy resin and a dianhydride cross-linking agent having at least one ester group function obtained by the reaction of trimellitic anhydride with a diol containing from 2 to 10 carbon atoms in a molar ratio of trimellitic anhydride to diol between 2:1 and 2:1.5 .
2. A composition according to claim 1 wherein the epoxy resin has an epoxy equivalent of between about 400 and 1500 and a melting point, measured by the ball-and-ring technique, of between about 50° and 120°C.
3. A composition according to claim 1 wherein the epoxy resin is the reaction product of a diphenol and an epihalohydrin.
4. A composition according to claim 1, characterized in that the epoxy-resin : cross-linking agent weight ratio is such that there is sub-stantial stoichiometric equilibrium, in the final cured polymer between the epoxy groups and the acid-anhydride groups.
5. A composition according to claim 1, characterized in that the epoxy resin has an epoxy equivalent of about 850 to 950, and in that the cross-linking agent has a trimellitic-anhydride : ethylene glycol ratio of between about 2 : 1 and 2 : 1.5, an acid index in an aqueous medium of between about 390 and 540, an acid index in an alcohol medium of between about 250 and 320, and a ball-and-ring melting point of between about 80 and 100°C.
6. A composition according to claim 1 wherein the epoxy resin has an epoxy equivalent of between about 500 and 1000 and a melting point, measured by the ball-and-ring technique, of between about 70° and 100°C.
7. A composition according to claim 1 further comprising paint additives selected from the group consisting of pigments, dyestuffs and fillers.
8. A process for preparing a paint composition in powder form, the bonding agent of which is a powdered composition according to claim 1 characterized in that the powdered composition is mixed together with a filler and paint additives at a temperature below or equal to 100°C, the resultant paint product being cooled, ground, and screened.
9. A process for obtaining a cured paint composition coating, which comprises applying the powdered composition of claim 1 together with paint additives to a substrate and then heating at between about 150 and 220°C for a period of between about 5 and 20 minutes to effect cross-linking of the composition.
10. A process according to claim 9 wherein cross-linking is carried out at between about 160° and 200°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR78.06608 | 1978-03-08 | ||
| FR7806608A FR2424307A2 (en) | 1978-03-08 | 1978-03-08 | SATURATED CROSS-LINKABLE COMPOSITIONS FOR POWDER PAINT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129587A true CA1129587A (en) | 1982-08-10 |
Family
ID=9205505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA322,917A Expired CA1129587A (en) | 1978-03-08 | 1979-03-07 | Saturated cross-linkable composition |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4471025A (en) |
| JP (1) | JPS54127440A (en) |
| CA (1) | CA1129587A (en) |
| CH (1) | CH639111A5 (en) |
| DE (1) | DE2908700A1 (en) |
| DK (1) | DK94379A (en) |
| FR (1) | FR2424307A2 (en) |
| IT (1) | IT7948225A0 (en) |
| NL (1) | NL7901846A (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650718A (en) * | 1985-08-19 | 1987-03-17 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents |
| US4703101A (en) * | 1985-08-19 | 1987-10-27 | Ppg Industries, Inc. | Liquid crosslinkable compositions using polyepoxides and polyacids |
| US4681811A (en) * | 1985-08-19 | 1987-07-21 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat |
| US4732790A (en) * | 1986-08-21 | 1988-03-22 | Ppg Industries, Inc. | Color plus clear application of thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides |
| US4732791A (en) * | 1986-08-21 | 1988-03-22 | Ppg Industries, Inc. | Color plus clear application of thermosetting high solids coating composition of epoxies, polyols and anhydrides |
| US4755582A (en) * | 1986-08-21 | 1988-07-05 | Ppg Industries, Inc. | Thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides |
| GB8701057D0 (en) * | 1987-01-16 | 1987-02-18 | Shell Int Research | Preparation of carboxylated amide binders |
| US4917955A (en) * | 1987-07-13 | 1990-04-17 | Ppg Industries, Inc. | Color plus clear composite coating having a catalyst-free base coat comprising polyepoxides and polyacid curing agents |
| US5055524A (en) * | 1987-07-16 | 1991-10-08 | Ppg Industries, Inc. | Polyol-modified polyanhydride curing agent for polyepoxide powder coatings |
| US4849283A (en) * | 1987-07-16 | 1989-07-18 | Ppg Industries, Inc. | Composite coatings employing polyepoxides and polyacid curing agents in base coats |
| US5043220A (en) * | 1987-11-16 | 1991-08-27 | The Sherwin-Williams Company | Substrate coated with a basecoat and/or a clearcoat of an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| US4859758A (en) * | 1987-11-16 | 1989-08-22 | The Sherwin-Williams Company | Acid-functional polymers derived from cellulose ester-unsaturated alcohol copolymers, which are reacted with cyclic anhydrides |
| US5411809A (en) * | 1987-11-16 | 1995-05-02 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound and an epoxy-functional compound |
| US4871806A (en) * | 1987-11-16 | 1989-10-03 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| DE4227580A1 (en) * | 1992-08-20 | 1994-02-24 | Basf Lacke & Farben | Process for the production of powder coatings and powder coatings produced by this process |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947717A (en) * | 1956-06-11 | 1960-08-02 | Devoe & Raynolds Co Inc | Epoxide resin compositions |
| US3062770A (en) * | 1960-03-21 | 1962-11-06 | Standard Oil Co | Composition consisting essentially of (alpha) a reaction product of trimellitic anhydride and alkylene oxide and (beta) an epoxy resin |
| US3182073A (en) * | 1962-04-27 | 1965-05-04 | Gen Electric | Trimellitic anhydride derivatives |
| US3188362A (en) * | 1962-07-06 | 1965-06-08 | Furane Plastics | Semi-rigid epoxy resin compositions and method |
| US3269975A (en) * | 1963-07-09 | 1966-08-30 | Hysol Corp | Tetracarboxylic acid hardeners for epoxy resins and powdered epoxy resin compositions including such hardeners |
| US3336251A (en) * | 1964-05-14 | 1967-08-15 | Shell Oil Co | Rapid curing fluidized bed coating composition |
| US3468824A (en) * | 1965-12-13 | 1969-09-23 | Morton Int Inc | Epoxy composition |
| US3437671A (en) * | 1966-06-10 | 1969-04-08 | Borden Co | Method of making polyesters by the reaction of anhydride acid halide with polyols and resultant adhesive compositions |
| US3431237A (en) * | 1967-03-27 | 1969-03-04 | Dow Chemical Co | Method of curing epoxy resins |
| US3555111A (en) * | 1968-03-19 | 1971-01-12 | Dexter Corp | Fast cure epoxy resin coating powders containing adducts of trimellitic anhydride and polyols |
| DE2556182B2 (en) * | 1975-12-13 | 1980-01-24 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of reactive powder resin mixtures |
-
1978
- 1978-03-08 FR FR7806608A patent/FR2424307A2/en active Granted
-
1979
- 1979-03-06 IT IT7948225A patent/IT7948225A0/en unknown
- 1979-03-06 DE DE19792908700 patent/DE2908700A1/en not_active Withdrawn
- 1979-03-07 CH CH220979A patent/CH639111A5/en not_active IP Right Cessation
- 1979-03-07 NL NL7901846A patent/NL7901846A/en not_active Application Discontinuation
- 1979-03-07 DK DK94379A patent/DK94379A/en not_active Application Discontinuation
- 1979-03-07 CA CA322,917A patent/CA1129587A/en not_active Expired
- 1979-03-07 JP JP2659879A patent/JPS54127440A/en active Pending
-
1983
- 1983-12-06 US US06/558,584 patent/US4471025A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DK94379A (en) | 1979-09-09 |
| IT7948225A0 (en) | 1979-03-06 |
| FR2424307A2 (en) | 1979-11-23 |
| JPS54127440A (en) | 1979-10-03 |
| DE2908700A1 (en) | 1979-09-13 |
| FR2424307B2 (en) | 1980-10-10 |
| CH639111A5 (en) | 1983-10-31 |
| NL7901846A (en) | 1979-09-11 |
| US4471025A (en) | 1984-09-11 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |