CA1244598A - Aromatic acid catalysts providing improved humidity resistance - Google Patents
Aromatic acid catalysts providing improved humidity resistanceInfo
- Publication number
- CA1244598A CA1244598A CA000466141A CA466141A CA1244598A CA 1244598 A CA1244598 A CA 1244598A CA 000466141 A CA000466141 A CA 000466141A CA 466141 A CA466141 A CA 466141A CA 1244598 A CA1244598 A CA 1244598A
- Authority
- CA
- Canada
- Prior art keywords
- integer
- curable composition
- alkyl
- sulfonic acid
- acid
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Abstract
Abstract of the Disclosure Curable compositions with improved humidity resistance are com-posed of an active hydrogen-containing resin which is essentially free of glycidyl groups, a curing agent present externally and/or internally as a part of the active hydrogen-containing resin, and a catalytic amount of a sulfonic acid having a molecular weight of less than 500 and represented by the following structural formula:
wherein: Z is a radical independently selected from C1 to C20 alkyl, C3 to C20 cylcoalkyl, C6 to C18 aryl, halogen, alkoxy, hydroxyl, and aryloxy;
is independently selected from hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl and C6 to C18 aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2;
x is an integer from 1 to 3, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2.
wherein: Z is a radical independently selected from C1 to C20 alkyl, C3 to C20 cylcoalkyl, C6 to C18 aryl, halogen, alkoxy, hydroxyl, and aryloxy;
is independently selected from hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl and C6 to C18 aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2;
x is an integer from 1 to 3, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2.
Description
AROMATIC ACID CATALYSTS
PROVIDING IMPROVED HU~IDITY RESISTANCE
Baclcground of _he Invention The present invention relates to the use of sulfonic acids as catalysts in resinous compositions.
Resinous compositions which are cured with aminoplast curinV
agents generally use an acid catalyst. A substantial number of acid cata- -lysts are known and have been conventionally utilized such as boric acid, phosphoric acid, and a variety of sulfonic acids, for example, para-toluenesulfonic acid and methanesulfonic acid and disulfonic acids such as dinonylnaphthalene disulfonic acid and benzene disulfonic acid. U.S.
PROVIDING IMPROVED HU~IDITY RESISTANCE
Baclcground of _he Invention The present invention relates to the use of sulfonic acids as catalysts in resinous compositions.
Resinous compositions which are cured with aminoplast curinV
agents generally use an acid catalyst. A substantial number of acid cata- -lysts are known and have been conventionally utilized such as boric acid, phosphoric acid, and a variety of sulfonic acids, for example, para-toluenesulfonic acid and methanesulfonic acid and disulfonic acids such as dinonylnaphthalene disulfonic acid and benzene disulfonic acid. U.S.
2,631,138, U.S. 2,961,424, U.S. 3,474,054, U.S. 3,97~,478, and 4,083,830 describe such catalysts.
Although effective for the majority of uses, many of the Icnown sulfonic and disulfonic acid catalysts have limitations in particular applications. For instance, these materials often contribute to impaired humidity resistance in some coating compositions. There is therefore a need for a strong acid catalyst which will not only provide a-rapid, effec-tive cure at a moderate temperature, but also provide improved humidity resistance.
Summary of the _nvention In accordance with the present invention there is provided an improved curable composition comprising an active hydrogen-containing resin which is essentially free of glycidyl groups, a curing agent present externally and/or internally a8 a part of the active hy!drogen-containing 5~
resin, and as acid atalyst a cataly~ic amount of a sulfonic acid having a molecular weight of less than 500 and represented by the following struc-tural formula:
~ (Z)y -- (COOR)W
(S03H)x (I) wherein: Z is a radical independently selected from Cl to C20 alkyl, C3 to C20 cycloalkyl, C6 to Clg aryl, halogen, alkoxy, hydroxyl, and aryloxy;
R is independently selected from hydrogen, Cl to C20 alkyl, C3 to C20 cyloalkyl, and C6 to Clg aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2; and x is an integer from l to 3, with the proviso that when w is 0, y is an integer from l to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from l to 2 and x is an integer from 1 to 2.
Detailed Descr~ption of the Invention _ _ __ _ The aromatic sulfonic acid catalysts oE the present invention have a molecular weight of less than 500 and can be represented by the following structural formula:
~ (Z)y O --- (COOR)W "
(S03~1)x (I) 591~
In the above formula (I) Z is a radical independently selected - from Cl to C20 alkyl radicals, C3 to C20 cycloalkyl rad;cals, C6 to Clg aryl radicals, halogen radicals, alkoxy radicals, hydroxyl, and aryloxy radicals. In the above formula, y is an integer from 0 to 4, preferably 1 to 2, w is an integer from 0 to 2, preferably 1, and x is an integer from 1 to 3, preferably 1 to 2, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer fro,n 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2. R in the above fonnula includes hydrogen, C6 to Clg aryl, Cl to C20 alkyl and C3 to C20 cycloallcyl radicals. It should be understood that the aforesaid alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals can be substituted with a variety of substituents so long as they do not detract frorn the properties of the sulfonic acid catalysts.
Substituents representative of Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, chloro, bromo, fluoro, methoxy, ethoxy, butoxy, hexyloxy, and phenoxy. Preferably Z is a Cl to Clo alkyl, for example, methyl and y is an integer from 1 to 2.
Substituents representative of R in formula (I), above, include methyl, ethyl, propyl, isopropyl, and 2-ethylhexyl; preferably R is isopro- -pyl or 2-ethylhexyl.
Preferred compounds for use as catalysts in accordance with the claimed invention include toluene 2,4-disulfonic acid, 1,3-xylene-4,6-disulfonic acid, 2-ethylhexyl o-sulfobenzoate, 2-propyl o-sulfobenzoate, 2-propyl 3,5-disulfobenzoate, and 2-ethylhexyl 3,5-disulfobenzoate. Although these isomers are most prevalent, other position isomers are also formed. -It should be understood that amine and partial amine salts of the sulfonic acid catalysts of the present ;nvention are also useful.
The disulfonic acids of the present invention represented by formula (I) above can be prepared by art recognized methods, for example by alcoholysis of the corresponding chlorosulfonation products of the parent aromatic compound. The parent aromatic compound :is added to an excess of chlorosulfonic acid at ambient temperature. The mixture is then heated at a temperature and for a period depending upon the reactivity of the aromatic compound, cooled and diluted with sulfuric acid. An organic solvent s~ch as methylene chloride is added to facilitate the separation of the disul-fonyl chloride and the organic layer is washed, dried and the solvent evaporated to yield the disulfonyl chloride. Conversion of the disulfonyl chlorides to the free acids is accomplished by heating the disulfonyl chlo-ride with excess alcohol such as methanol, ethanol, or isopropyl alcohol.
Further details are not felt to be necessary for an understanding of the present invention ho~ever if details are desired reference is made to Suter, Or~anic Reactions, Volume III, page 141, John Wiley and Son Publishers, New York, copyright 1944.
The mono- and disulfobenzoates represented by formula (I) above can be prepared by reacting the chloride of the desired sulfcbenzoate with an alcohol, for example, isopropanol or 2-ethylhexanol. The necessary chloride of the desired acid can be prepared, for example, from the disodium salt of the sulfobenzoic acid and, for example, phosphorus pentachloride.
Alternatively the mono- and disulfobenzoates can be prepared via a trans-esterification reaction between a sulfobenzoate prepared by the route described above and a desired alcohol.
The sulfonic acid catalysts o the present invention are useful as catalysts in curable compositions which are capable of acid catalyzed cross- :
linking and comprise in addition to the catalyst an active hyclrogen-containing resin which is essentially free of glycidyl groups and a crosslinking agent present externally and/or internally as a part of the active hydrogen-containing resin. Although a variety of polymeric polyols can be used herein as the active hydrogen-containing resin, the sulfonic acids of the present invention are particularly useful in compositions prepared with polymeric polyols which are sensitive to humidity since the catalyst con-tributes toward good hu~idity resistance of the final cured coating.
Exemplary of useful polymeric polyols are polyether polyols, polyester polyols, acrylic polyols and polyurethane polyols which are ]i, disclosed in U.S. 4,154,891, column 3, lines 26 to 68, column 4, lines l to 68, column 5, lines 1 to 68, and column 6, lines 1 to Z.
The polymeric polyols useful in preparing the composition of the present invention have a hydroxyl number ranging from about 48 to about 435, and an acid value raaging from 0 to about 160.
The aforedescribed polyols require a csosslinking or curing agent to cure to a durable film. The crosslinking agent is responsive to acid catalysts and can be present externally or internally as part of the active llydrogen-containing resin. Examples of external curing agents are aminoplast 2() resins and phenoplast resins, with the aminoplast resins being preferred.
The aforesaid external crosslinking agents are described in detail in U.S.
Although effective for the majority of uses, many of the Icnown sulfonic and disulfonic acid catalysts have limitations in particular applications. For instance, these materials often contribute to impaired humidity resistance in some coating compositions. There is therefore a need for a strong acid catalyst which will not only provide a-rapid, effec-tive cure at a moderate temperature, but also provide improved humidity resistance.
Summary of the _nvention In accordance with the present invention there is provided an improved curable composition comprising an active hydrogen-containing resin which is essentially free of glycidyl groups, a curing agent present externally and/or internally a8 a part of the active hy!drogen-containing 5~
resin, and as acid atalyst a cataly~ic amount of a sulfonic acid having a molecular weight of less than 500 and represented by the following struc-tural formula:
~ (Z)y -- (COOR)W
(S03H)x (I) wherein: Z is a radical independently selected from Cl to C20 alkyl, C3 to C20 cycloalkyl, C6 to Clg aryl, halogen, alkoxy, hydroxyl, and aryloxy;
R is independently selected from hydrogen, Cl to C20 alkyl, C3 to C20 cyloalkyl, and C6 to Clg aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2; and x is an integer from l to 3, with the proviso that when w is 0, y is an integer from l to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from l to 2 and x is an integer from 1 to 2.
Detailed Descr~ption of the Invention _ _ __ _ The aromatic sulfonic acid catalysts oE the present invention have a molecular weight of less than 500 and can be represented by the following structural formula:
~ (Z)y O --- (COOR)W "
(S03~1)x (I) 591~
In the above formula (I) Z is a radical independently selected - from Cl to C20 alkyl radicals, C3 to C20 cycloalkyl rad;cals, C6 to Clg aryl radicals, halogen radicals, alkoxy radicals, hydroxyl, and aryloxy radicals. In the above formula, y is an integer from 0 to 4, preferably 1 to 2, w is an integer from 0 to 2, preferably 1, and x is an integer from 1 to 3, preferably 1 to 2, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer fro,n 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2. R in the above fonnula includes hydrogen, C6 to Clg aryl, Cl to C20 alkyl and C3 to C20 cycloallcyl radicals. It should be understood that the aforesaid alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals can be substituted with a variety of substituents so long as they do not detract frorn the properties of the sulfonic acid catalysts.
Substituents representative of Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, chloro, bromo, fluoro, methoxy, ethoxy, butoxy, hexyloxy, and phenoxy. Preferably Z is a Cl to Clo alkyl, for example, methyl and y is an integer from 1 to 2.
Substituents representative of R in formula (I), above, include methyl, ethyl, propyl, isopropyl, and 2-ethylhexyl; preferably R is isopro- -pyl or 2-ethylhexyl.
Preferred compounds for use as catalysts in accordance with the claimed invention include toluene 2,4-disulfonic acid, 1,3-xylene-4,6-disulfonic acid, 2-ethylhexyl o-sulfobenzoate, 2-propyl o-sulfobenzoate, 2-propyl 3,5-disulfobenzoate, and 2-ethylhexyl 3,5-disulfobenzoate. Although these isomers are most prevalent, other position isomers are also formed. -It should be understood that amine and partial amine salts of the sulfonic acid catalysts of the present ;nvention are also useful.
The disulfonic acids of the present invention represented by formula (I) above can be prepared by art recognized methods, for example by alcoholysis of the corresponding chlorosulfonation products of the parent aromatic compound. The parent aromatic compound :is added to an excess of chlorosulfonic acid at ambient temperature. The mixture is then heated at a temperature and for a period depending upon the reactivity of the aromatic compound, cooled and diluted with sulfuric acid. An organic solvent s~ch as methylene chloride is added to facilitate the separation of the disul-fonyl chloride and the organic layer is washed, dried and the solvent evaporated to yield the disulfonyl chloride. Conversion of the disulfonyl chlorides to the free acids is accomplished by heating the disulfonyl chlo-ride with excess alcohol such as methanol, ethanol, or isopropyl alcohol.
Further details are not felt to be necessary for an understanding of the present invention ho~ever if details are desired reference is made to Suter, Or~anic Reactions, Volume III, page 141, John Wiley and Son Publishers, New York, copyright 1944.
The mono- and disulfobenzoates represented by formula (I) above can be prepared by reacting the chloride of the desired sulfcbenzoate with an alcohol, for example, isopropanol or 2-ethylhexanol. The necessary chloride of the desired acid can be prepared, for example, from the disodium salt of the sulfobenzoic acid and, for example, phosphorus pentachloride.
Alternatively the mono- and disulfobenzoates can be prepared via a trans-esterification reaction between a sulfobenzoate prepared by the route described above and a desired alcohol.
The sulfonic acid catalysts o the present invention are useful as catalysts in curable compositions which are capable of acid catalyzed cross- :
linking and comprise in addition to the catalyst an active hyclrogen-containing resin which is essentially free of glycidyl groups and a crosslinking agent present externally and/or internally as a part of the active hydrogen-containing resin. Although a variety of polymeric polyols can be used herein as the active hydrogen-containing resin, the sulfonic acids of the present invention are particularly useful in compositions prepared with polymeric polyols which are sensitive to humidity since the catalyst con-tributes toward good hu~idity resistance of the final cured coating.
Exemplary of useful polymeric polyols are polyether polyols, polyester polyols, acrylic polyols and polyurethane polyols which are ]i, disclosed in U.S. 4,154,891, column 3, lines 26 to 68, column 4, lines l to 68, column 5, lines 1 to 68, and column 6, lines 1 to Z.
The polymeric polyols useful in preparing the composition of the present invention have a hydroxyl number ranging from about 48 to about 435, and an acid value raaging from 0 to about 160.
The aforedescribed polyols require a csosslinking or curing agent to cure to a durable film. The crosslinking agent is responsive to acid catalysts and can be present externally or internally as part of the active llydrogen-containing resin. Examples of external curing agents are aminoplast 2() resins and phenoplast resins, with the aminoplast resins being preferred.
The aforesaid external crosslinking agents are described in detail in U.S.
3,919,351, column 5, lines 34 to 68 and column 6, lines 1 to 25 The curing agent can aLso be part of the active hydrogen-containing resin. ~xamples of resins of this type are interpolymers of an N-alkoxymethyl substituted unsaturated carboxylic acid a~ide with at least one other mono--mer having a C~2~C ~ group, said interpoly~ers being characteri~ed by S~
having amido hydrogen atoms replaced by the structure RCHORl, wherein R is selected from the group consisting of hydrogen and saturated lower aliphatic hydrocarbon radicals and Rl is a member of the class consisting of hydrogen and lower alkyl radicals with the proviso that the interpolymer having a hydroxyl number of at least 10. In general, these interpolymers can be produced in two ways. In the first method, the unsaturated carboxylic acid amide chosen is an N-alkoxymethyl acrylamide (i.e., a materia] having an -NHRCHORl group in the molecule). This N-alkoxymethyl acrylamide is then polymerized with at least one other monomer having a CH2=C group to pro-duce a useful interpolymer. In the second method, an unsaturated carboxylicacid amide, e.g., acrylamide is polymerized with at least one other monomer having a CH2=C ~ group and is then reacted with an aldehyde to form a useful interpolymer.
Examples of useful interpolymers and their method of manufacture are disclosed in U.5. Patents Nos. Z,978,437, 3,037,963 and 3,079,43~
Additionally useful herein are a class of interpolymers of N-alkoxymethyl substituted unsaturated carboxylic acid amides, especially ~-alkoxymethyl acrylamides as described above, with polyethylenically unsaturated polyesters. The amido nitrogens of such an interpolymer are replaced by the structure -RCHORl, wherein R can be hydrogen or saturated lower aliphatic hydrocarbon radicals and Rl can be hydrogen or a Cl-Clo aliphatic hydrocarbon radical. Any number of unsaturated polyesters may be utili~ed so long as they are polyethylenically unsaturated.
Both of the aforesaid classes of interpolymers are capable of crosslinking without the necessity of adding ex~ernal crosslinking resin.
It is noted that although an external crosslinking resin is not necessary -for those aforedescribed interpolymers capable of internal crosslinking, satis~actory results are attainable if an external curing agent is also added. For this purpose, the aminoplast and phenoplast crosslinking resins described above can be utilized.
When added externally, the crosslinking resin is usually present in an amount of from about 10 percent to about 90 percent by weight based on the total weight of the resinous components of composition. When the curing agent is present internally it is usually present in an amount of from about 5 to 95 percent by weight of the interpolymer, the percentages being ~ased upon the total weight of the resinous composition.
The acid catalysts of the claimed invention are utilized in a catalytic amount; that is, an amount sufficient to acce]erate the cure of a coating composition to a commercially acceptable rate. Typically, the catalyst is adde~ to the composition immediately prior to use in an amount ranging from about 0.1 percent to about 20 percent by weight, preferably 0.1 to 5 percent by weight, the percentages being based on the total weight of the resinous components of composition.
In addition to the aforedescribed components, the curable compositions of the present invention ordinarily contain other optional ingredients such as pigments, fillers, plasticizers, flow control agents and other formulating additives. The compositions are typically contained in a solvent which can be any solvent or solvent mixture in which the materials employed are compatible and soluble to the desired extent. For example, suitable solvents include methyl amyl ketone, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
The curable compositions herein can be applied in any conventional manner, including brushing, flow coating, spraying, and the like. They are ~2~5~
preferably intended for application on metallic substrates such as steel or aluminum, primed or unprimed, alhough they can readily be applied over any substrate.
The curable compositions of the presenlt invention can be cured thermally. The temperature utilized for cure of the claimed compositions varies widely depending upon the particular catalyst and resin system chosen.
Typically temperatures between about 60C and about 200C are utilized, preferably between about 100C and 150C. The length of time for cure can also vary widely, however, from about 2 to 90 minutes is typical.
In addition to use in coating compositions, the acid catalysts of the present invention are also useful in other curable compositions such as molding and laminating compositions.
The following examples are submitted for the purpose of further illustrating the nature of the present invention and should not be construed as a limitation on the scope thereof.
Example I
Preparation of 2-propyl 3,5-disulfobenzoate 7 Into a one-liter, four-necked, round bottom flask equipped withthermometer, distillation head, and glass stirrer with TEFLON ~ddle were charged 101.6 grams of 3,5-bis(chlorosulfonyl)benzoyl chloride* and 600 grams of isopropyl alcohol. The solution was distilled to a pot temperature of 105C, cooled to 80C, charged with a second 600 gram aliquot of iso-propyl alcohol and distilled once again to 2 pot temperature of 105 C.
The resultant 2-propyl 3,5~disulfobenzoate was a light brown, hazy liquid having an acid value of 202.~ and being free of residual chloride (deter-mined using the silver nitrate test).
* The 3,5-bis(chlorosulfonyl)benzoyl chloride was prepared in the following manner:
~ m~ ~t~6~/~
s~
Example II
Preparation of 2-Ethylhexyl 3,5-di~ulfobenzoate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head, and a glass stirrer with TEFLON paddle were ch~rged 177 grams of 2-propyl 3,5-disulfobenzoate solution in isopropyl alco~ol and 200 grams of 2-ethylhexanol. The solution was vacuum distilled to a pot temperature of 105C and then held at this temperature for an additional three hours. The resultant 2-ethylhexyl 3,5-dis~lfobenzoate was a brown viscous oil with an acid value of 165.
Example III
Preparation of 2-pr~pyl o-sulfobenzoate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head, condenser and glass stirrer with TEFL~N
paddle were charged 117.4 grams of methyl o-(chlorosulfonyl)benzoate and 200 grams of isopropyl alcohol. The mixture was distilled to a pot tem-perature of 105C and the residue tested for the presence of chloride ion using the silver nitrate test. Additional 200 gram aliquots of isopropyl alcohol were added and distillation carried out in the same manner until the reaction mixture was found to be free of chloride ion by the silver nitrate test. The resultant 2-propyl o-sulfobenzoate was a straw colored liquid having an acid value of 182.
*(cont.) Into a three-liter, round bottom flask equipped with a glass stirrer with TEFLON paddle, thermometer, condenser, and air aspirator were charged 152.4 grams of moist disodium 3,5-disulfonatobenzoic acid and 416.4 grams of phosphorus pentachloride. The mixture was warmed slowly to 110C
and refluxed for 10 hours. A total of 21 grams of liquid was distilled off to a pot temperature of 140 C. The reaction mixture was then cooled to 0C
and quenched with 200 grams of ice water. Subsequently, 300 grams of methyl-ene chloride were added and the solution was stirred for one hour. The methylene chloride layer was then separated9 washed once with cold water (300 gram5), dried over magnesium sulfate and filtered. The resultant yel-low solution was concentrated in vacuo to yield the 3,5-bis(chloroc:ulEonyl) benæoyl chLoride product as a yellow crystalline product havin~ a melting point within the range of ~5C to 87C.
Example ~V
Preparation of 2- ~ fob n~oate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head9 and glass stirrer with TEFL~ paddle were charged 82.5 grams of 2-propyl o-sulfobenzoate solution in isopropanol and 100 grams of 2-ethylhexanol. The solution was vacuum distilled to a pot temperature of 105C and subsequently the vacuum was turned off and the reaction mixture held at 105C for one hour. The resultant 2-ethylhexyl o-sulfoben~oate was a brown liquid with an acid value of 1~2.
Example V
The following example illustrates the effect of prolonged hulnidity exposure on cured films of coating compositioQs incorporating sulfonic acid catalysts of the present invention. These results are compared to results of cured films of the same coating compositions incorporating the conven-tional acid catalyst, para-toluenesulfonic acid. This example demonstrates the excellent humidity resistance of the aromatic disulfonic acid catalysts of the present invention. The following buse coating compositions were utili7ed:
Composition A: 80 percent resin solids content Parts by Weight Percent of Ingredients _ (grams) Resin Solids Acrylic Resinl 81.4 59 Crosslinking Agent2 40.0 41 Aluminum Pigment 4.6 Methyl amyl ketone20.4 Cellulose Acetate Butyrate 12.0 ~2~5~
IThis acrylic resin was prepared from 50 percent hydroxy-propyl acrylate, 4~ percent butyl methacrylate, and 1 percent methacrylic acid. It had an acid value of 7.3.
Commercially available from American Cyanamid as C~EL 303.
Composition B: 84 percent resin solids content _ ._ Parts by Weight Percent of Ingredients (grams) Resin Solids Acrylic Resin3 631.6 60 Crosslinking Agent4 32Q 40 10Aluminum Pigment 36.9 Methyl Amyl Ketone 344.8 3This acrylic resin has a 76 percent resin solids content on methyl amyl ketone and a hydroxyl number of ~7. It is co~ner-~ially available from Rohm and Haas as ACRYEOID~ T-400.
4Same as 2 above.
Each catalyst and selected base coating composition were mixed in the amounts shown below in the table and drawn down with a 3-mil draw bar over primed pretreated steel panels (commercially available from Hooker Chemical Company as BONDERIT~ 40).
All acids were added at equal equivalents. T~e panels were baked for 20 minutes at 180 F (82 C~. Each panel was evaluated for gloss (mea-sured with a gloss meter) and then subjected to prolonged humidity exposure ~4 hours at 140F ~60C) in a QCT-Condensing Humidity Test Chamber.) After exposure, the panels were a~ain evaluated for gloss. Percent gloss reten-tion was determined as follows: _ Final Gloss (after exposure) X 100%
Initial Gloss -~ rr~d~ ~ Q ~
~2~59~
o C ., L ~J ~t C') 'D CO ~ C~, ~-1 1 ~1 ~
P~ ~
o , O
Q~ _ <1: L, O O ~--' I` ~ O O
U~ 01 c~O ~
o o ~ _ ~a .,1 ~q 00 r~ O
.~1 0 ~
c~o E ~ E
.rl C ~0 bO bO bO t~O bO 0~ b~
O ~ ~D CO OD ~D `D
a~ ~o ~ ~ ¢ ¢ P~ ~ ~q ¢ '1 o ~~ ~ I ~ bO
O bO u~ O
e, ~ O ~ bO ~ O ~
tl) h C) bO I ~ Vl oo Lf~ _ ~ a) a~ O ^ bOO ~.) X ~-- X ~ O _ ~ (U
U~ ~ ~ ~ o ~ ~ o ~ ~ ~ o ~ ~ ~ o C ~ ~ N Q. ITI 1~ N
) 1 1 ~X ~ U~ 5: 0 ~C C O O O t:
v E ~ ~ J ~ C (~ I N 1,~ ~
rd ~ ~ ) O o ~ t a) I o I o I o ~ _ p~ ~) bO ~ ~ ~ 4-1 I ~7 /
having amido hydrogen atoms replaced by the structure RCHORl, wherein R is selected from the group consisting of hydrogen and saturated lower aliphatic hydrocarbon radicals and Rl is a member of the class consisting of hydrogen and lower alkyl radicals with the proviso that the interpolymer having a hydroxyl number of at least 10. In general, these interpolymers can be produced in two ways. In the first method, the unsaturated carboxylic acid amide chosen is an N-alkoxymethyl acrylamide (i.e., a materia] having an -NHRCHORl group in the molecule). This N-alkoxymethyl acrylamide is then polymerized with at least one other monomer having a CH2=C group to pro-duce a useful interpolymer. In the second method, an unsaturated carboxylicacid amide, e.g., acrylamide is polymerized with at least one other monomer having a CH2=C ~ group and is then reacted with an aldehyde to form a useful interpolymer.
Examples of useful interpolymers and their method of manufacture are disclosed in U.5. Patents Nos. Z,978,437, 3,037,963 and 3,079,43~
Additionally useful herein are a class of interpolymers of N-alkoxymethyl substituted unsaturated carboxylic acid amides, especially ~-alkoxymethyl acrylamides as described above, with polyethylenically unsaturated polyesters. The amido nitrogens of such an interpolymer are replaced by the structure -RCHORl, wherein R can be hydrogen or saturated lower aliphatic hydrocarbon radicals and Rl can be hydrogen or a Cl-Clo aliphatic hydrocarbon radical. Any number of unsaturated polyesters may be utili~ed so long as they are polyethylenically unsaturated.
Both of the aforesaid classes of interpolymers are capable of crosslinking without the necessity of adding ex~ernal crosslinking resin.
It is noted that although an external crosslinking resin is not necessary -for those aforedescribed interpolymers capable of internal crosslinking, satis~actory results are attainable if an external curing agent is also added. For this purpose, the aminoplast and phenoplast crosslinking resins described above can be utilized.
When added externally, the crosslinking resin is usually present in an amount of from about 10 percent to about 90 percent by weight based on the total weight of the resinous components of composition. When the curing agent is present internally it is usually present in an amount of from about 5 to 95 percent by weight of the interpolymer, the percentages being ~ased upon the total weight of the resinous composition.
The acid catalysts of the claimed invention are utilized in a catalytic amount; that is, an amount sufficient to acce]erate the cure of a coating composition to a commercially acceptable rate. Typically, the catalyst is adde~ to the composition immediately prior to use in an amount ranging from about 0.1 percent to about 20 percent by weight, preferably 0.1 to 5 percent by weight, the percentages being based on the total weight of the resinous components of composition.
In addition to the aforedescribed components, the curable compositions of the present invention ordinarily contain other optional ingredients such as pigments, fillers, plasticizers, flow control agents and other formulating additives. The compositions are typically contained in a solvent which can be any solvent or solvent mixture in which the materials employed are compatible and soluble to the desired extent. For example, suitable solvents include methyl amyl ketone, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
The curable compositions herein can be applied in any conventional manner, including brushing, flow coating, spraying, and the like. They are ~2~5~
preferably intended for application on metallic substrates such as steel or aluminum, primed or unprimed, alhough they can readily be applied over any substrate.
The curable compositions of the presenlt invention can be cured thermally. The temperature utilized for cure of the claimed compositions varies widely depending upon the particular catalyst and resin system chosen.
Typically temperatures between about 60C and about 200C are utilized, preferably between about 100C and 150C. The length of time for cure can also vary widely, however, from about 2 to 90 minutes is typical.
In addition to use in coating compositions, the acid catalysts of the present invention are also useful in other curable compositions such as molding and laminating compositions.
The following examples are submitted for the purpose of further illustrating the nature of the present invention and should not be construed as a limitation on the scope thereof.
Example I
Preparation of 2-propyl 3,5-disulfobenzoate 7 Into a one-liter, four-necked, round bottom flask equipped withthermometer, distillation head, and glass stirrer with TEFLON ~ddle were charged 101.6 grams of 3,5-bis(chlorosulfonyl)benzoyl chloride* and 600 grams of isopropyl alcohol. The solution was distilled to a pot temperature of 105C, cooled to 80C, charged with a second 600 gram aliquot of iso-propyl alcohol and distilled once again to 2 pot temperature of 105 C.
The resultant 2-propyl 3,5~disulfobenzoate was a light brown, hazy liquid having an acid value of 202.~ and being free of residual chloride (deter-mined using the silver nitrate test).
* The 3,5-bis(chlorosulfonyl)benzoyl chloride was prepared in the following manner:
~ m~ ~t~6~/~
s~
Example II
Preparation of 2-Ethylhexyl 3,5-di~ulfobenzoate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head, and a glass stirrer with TEFLON paddle were ch~rged 177 grams of 2-propyl 3,5-disulfobenzoate solution in isopropyl alco~ol and 200 grams of 2-ethylhexanol. The solution was vacuum distilled to a pot temperature of 105C and then held at this temperature for an additional three hours. The resultant 2-ethylhexyl 3,5-dis~lfobenzoate was a brown viscous oil with an acid value of 165.
Example III
Preparation of 2-pr~pyl o-sulfobenzoate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head, condenser and glass stirrer with TEFL~N
paddle were charged 117.4 grams of methyl o-(chlorosulfonyl)benzoate and 200 grams of isopropyl alcohol. The mixture was distilled to a pot tem-perature of 105C and the residue tested for the presence of chloride ion using the silver nitrate test. Additional 200 gram aliquots of isopropyl alcohol were added and distillation carried out in the same manner until the reaction mixture was found to be free of chloride ion by the silver nitrate test. The resultant 2-propyl o-sulfobenzoate was a straw colored liquid having an acid value of 182.
*(cont.) Into a three-liter, round bottom flask equipped with a glass stirrer with TEFLON paddle, thermometer, condenser, and air aspirator were charged 152.4 grams of moist disodium 3,5-disulfonatobenzoic acid and 416.4 grams of phosphorus pentachloride. The mixture was warmed slowly to 110C
and refluxed for 10 hours. A total of 21 grams of liquid was distilled off to a pot temperature of 140 C. The reaction mixture was then cooled to 0C
and quenched with 200 grams of ice water. Subsequently, 300 grams of methyl-ene chloride were added and the solution was stirred for one hour. The methylene chloride layer was then separated9 washed once with cold water (300 gram5), dried over magnesium sulfate and filtered. The resultant yel-low solution was concentrated in vacuo to yield the 3,5-bis(chloroc:ulEonyl) benæoyl chLoride product as a yellow crystalline product havin~ a melting point within the range of ~5C to 87C.
Example ~V
Preparation of 2- ~ fob n~oate Into a one-liter, four-necked round bottom flask equipped with a thermometer, distillation head9 and glass stirrer with TEFL~ paddle were charged 82.5 grams of 2-propyl o-sulfobenzoate solution in isopropanol and 100 grams of 2-ethylhexanol. The solution was vacuum distilled to a pot temperature of 105C and subsequently the vacuum was turned off and the reaction mixture held at 105C for one hour. The resultant 2-ethylhexyl o-sulfoben~oate was a brown liquid with an acid value of 1~2.
Example V
The following example illustrates the effect of prolonged hulnidity exposure on cured films of coating compositioQs incorporating sulfonic acid catalysts of the present invention. These results are compared to results of cured films of the same coating compositions incorporating the conven-tional acid catalyst, para-toluenesulfonic acid. This example demonstrates the excellent humidity resistance of the aromatic disulfonic acid catalysts of the present invention. The following buse coating compositions were utili7ed:
Composition A: 80 percent resin solids content Parts by Weight Percent of Ingredients _ (grams) Resin Solids Acrylic Resinl 81.4 59 Crosslinking Agent2 40.0 41 Aluminum Pigment 4.6 Methyl amyl ketone20.4 Cellulose Acetate Butyrate 12.0 ~2~5~
IThis acrylic resin was prepared from 50 percent hydroxy-propyl acrylate, 4~ percent butyl methacrylate, and 1 percent methacrylic acid. It had an acid value of 7.3.
Commercially available from American Cyanamid as C~EL 303.
Composition B: 84 percent resin solids content _ ._ Parts by Weight Percent of Ingredients (grams) Resin Solids Acrylic Resin3 631.6 60 Crosslinking Agent4 32Q 40 10Aluminum Pigment 36.9 Methyl Amyl Ketone 344.8 3This acrylic resin has a 76 percent resin solids content on methyl amyl ketone and a hydroxyl number of ~7. It is co~ner-~ially available from Rohm and Haas as ACRYEOID~ T-400.
4Same as 2 above.
Each catalyst and selected base coating composition were mixed in the amounts shown below in the table and drawn down with a 3-mil draw bar over primed pretreated steel panels (commercially available from Hooker Chemical Company as BONDERIT~ 40).
All acids were added at equal equivalents. T~e panels were baked for 20 minutes at 180 F (82 C~. Each panel was evaluated for gloss (mea-sured with a gloss meter) and then subjected to prolonged humidity exposure ~4 hours at 140F ~60C) in a QCT-Condensing Humidity Test Chamber.) After exposure, the panels were a~ain evaluated for gloss. Percent gloss reten-tion was determined as follows: _ Final Gloss (after exposure) X 100%
Initial Gloss -~ rr~d~ ~ Q ~
~2~59~
o C ., L ~J ~t C') 'D CO ~ C~, ~-1 1 ~1 ~
P~ ~
o , O
Q~ _ <1: L, O O ~--' I` ~ O O
U~ 01 c~O ~
o o ~ _ ~a .,1 ~q 00 r~ O
.~1 0 ~
c~o E ~ E
.rl C ~0 bO bO bO t~O bO 0~ b~
O ~ ~D CO OD ~D `D
a~ ~o ~ ~ ¢ ¢ P~ ~ ~q ¢ '1 o ~~ ~ I ~ bO
O bO u~ O
e, ~ O ~ bO ~ O ~
tl) h C) bO I ~ Vl oo Lf~ _ ~ a) a~ O ^ bOO ~.) X ~-- X ~ O _ ~ (U
U~ ~ ~ ~ o ~ ~ o ~ ~ ~ o ~ ~ ~ o C ~ ~ N Q. ITI 1~ N
) 1 1 ~X ~ U~ 5: 0 ~C C O O O t:
v E ~ ~ J ~ C (~ I N 1,~ ~
rd ~ ~ ) O o ~ t a) I o I o I o ~ _ p~ ~) bO ~ ~ ~ 4-1 I ~7 /
Claims (12)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a curable composition comprising an active hydrogen-containing resin which is essentially free of glycidyl groups, a curing agent present externally and/or internally as a part of the active hydrogen-containing resin, and an acid catalyst, wherein the improvement comprises using as the acid catalyst a catalytic amount of a sulfonic acid having a molecular weight of less than 500 and represented by the following structural formula:
wherein: Z is a radical independently selected from C1 to C20 alkyl, C3 to C20 cylcoalkyl, C6 to C18 aryl, halogen, alkoxy, hydroxyl, and aryloxy;
R is independently selected from hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl and C6 to C18 aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2;
x is an integer from 1 to 3, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2.
wherein: Z is a radical independently selected from C1 to C20 alkyl, C3 to C20 cylcoalkyl, C6 to C18 aryl, halogen, alkoxy, hydroxyl, and aryloxy;
R is independently selected from hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl and C6 to C18 aryl;
y is an integer from 0 to 4;
w is an integer from 0 to 2;
x is an integer from 1 to 3, with the proviso that when w is 0, y is an integer from 1 to 4 and x is an integer from 2 to 3 and when y is 0, w is an integer from 1 to 2 and x is an integer from 1 to 2.
2. The curable composition of Claim 1 wherein Z is C1 to C20 alkyl and y is 1.
3. The curable composition of Claim 1 wherein Z is C1 to C20 alkyl and y is 2.
4. The curable composition of Claim 2 wherein the sulfonic acid is toluene 2,4-disulfonic acid.
5. The curable composition of Claim 3 wherein the sulfonic acid is 1,3-xylene-4,6-disulfonic acid.
6. The curable composition of Claim 1 wherein R is C1 to C20 alkyl, x is 1, and w is 1.
7. The curable composition of Claim 1 wherein R is C1 to C20 alkyl and x is 2, and w is 1.
8. The curable composition of Claim 6 wherein the sulfonic acid is 2-ethylhexyl o-sulfobenzoate.
9. The curable composition of Claim 6 wherein the sulfonic acid is 2-propyl o-sulfobenzoate.
10. The curable composition of Claim 7 wherein the sulfonic acid is 2-propyl 3,5-disulfobenzoate.
11. The curable composition of Claim 7 wherein the sulfonic acid is 2-ethylhexyl 3,5-disulfobenzoate.
12. The curable composition of Claim 1 wherein the sulfonic acid catalyst is present in an amount ranging from 0.1 to 20 percent by weight based on the resinous components of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/551,389 US4500680A (en) | 1983-11-14 | 1983-11-14 | Aromatic acid catalysts providing improved humidity resistance |
| US551,389 | 1995-11-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244598A true CA1244598A (en) | 1988-11-08 |
Family
ID=24201079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000466141A Expired CA1244598A (en) | 1983-11-14 | 1984-10-23 | Aromatic acid catalysts providing improved humidity resistance |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4500680A (en) |
| EP (1) | EP0144810B1 (en) |
| AT (1) | ATE45757T1 (en) |
| CA (1) | CA1244598A (en) |
| DE (1) | DE3479513D1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812215A (en) * | 1986-12-29 | 1989-03-14 | Ppg Industries, Inc. | Low temperature curable aqueous electrodepositable coating compositions |
| US5256493A (en) * | 1990-04-26 | 1993-10-26 | Szita Jeno G | Sulfonimide catalysts for coatings |
| ATE137783T1 (en) * | 1990-04-26 | 1996-05-15 | Cytec Tech Corp | SULFONIMIDE CATALYSTS FOR COATING AGENTS |
| US5068273A (en) * | 1990-06-27 | 1991-11-26 | Sun Chemical Corporation | Thermosetting composition |
| US5312877A (en) * | 1993-02-12 | 1994-05-17 | Sun Chemical Corporation | High solids coating composition |
| FR2796379B1 (en) | 1999-07-13 | 2002-05-24 | Commissariat Energie Atomique | SULFONIC AND PHOSPHONIC ACIDS AND THEIR USE AS DOPANTS FOR THE MANUFACTURE OF POLYANILINE CONDUCTIVE FILMS AND FOR THE MANUFACTURE OF POLYANILINE CONDUCTIVE COMPOSITE MATERIALS |
| CN103130689B (en) * | 2013-03-08 | 2014-07-02 | 中国科学院长春应用化学研究所 | Amphiphilic compound, and preparation method and metal salt thereof |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2141893A (en) * | 1935-08-17 | 1938-12-27 | Gen Aniline Works Inc | Trifluoromethyl-aryl-sulphonic acids and a process of preparing them |
| US2227708A (en) * | 1938-08-09 | 1941-01-07 | Plaskon Co Inc | Formaldehyde-urea molding composition |
| NL182879B (en) * | 1951-02-26 | Dow Chemical Co | PROCEDURE FOR THE PREPARATION OF A HERBICIDE PREPARATION, AND SUITABLE SUBSTITUTED 2-PHENYL-2-ETHYLOXIRAN COMPOUNDS FOR THIS. | |
| US2961424A (en) * | 1958-04-29 | 1960-11-22 | Shell Oil Co | Resinous compositions comprising alpha, beta-alkylene oxide adduct of a polyol and resinous aminoplast and process of making same |
| US3293324A (en) * | 1962-11-08 | 1966-12-20 | American Cyanamid Co | 2-dimethylamino-2-methyl-1-propanol-p-toluene sulfonate with urea-formal-dehyde resin and alkyd resin |
| GB1053135A (en) * | 1963-03-13 | |||
| US3267174A (en) * | 1963-05-10 | 1966-08-16 | Union Carbide Corp | Acrylic coating composition containing an adduct of a triol with an alkylene oxide |
| US3474054A (en) * | 1966-09-13 | 1969-10-21 | Permalac Corp The | Surface coating compositions containing pyridine salts or aromatic sulfonic acids |
| DE1919678A1 (en) * | 1969-04-18 | 1970-11-05 | Bayer Ag | Alpha-methylol-benzoin-sulfonic acid ester |
| US3798262A (en) * | 1969-12-09 | 1974-03-19 | Merck & Co Inc | Sulfonylbenzenesulfonic acids |
| DE2107239B2 (en) * | 1971-02-16 | 1977-09-22 | Bayer Ag, 5090 Leverkusen | FAST NETWORKING BURNING SYSTEMS |
| DE2229364A1 (en) * | 1972-06-16 | 1974-01-03 | Reichhold Albert Chemie Ag | Heat curable binder - for powder coating is a polyester resin-amine resin pre-condensate |
| CH575987A5 (en) * | 1972-12-05 | 1976-05-31 | Hoechst Ag | |
| US3842021A (en) * | 1973-02-26 | 1974-10-15 | Eastman Kodak Co | Thermosetting polyester powder coating compositions |
| US3840591A (en) * | 1973-04-25 | 1974-10-08 | Ciba Geigy Corp | Process for the production of p-nitrotoluene-2-sulfonic acid |
| US3907706A (en) * | 1973-07-06 | 1975-09-23 | Minnesota Mining & Mfg | Latent catalyst systems for cationically polymerizable materials |
| US3919351A (en) * | 1973-08-29 | 1975-11-11 | Ppg Industries Inc | Composition useful in making extensible films |
| US4045411A (en) * | 1973-12-03 | 1977-08-30 | Cor Tech Research Limited | Mobile room-temperature stable acid catalyzed phenol formaldehyde resin compositions |
| US3979478A (en) * | 1974-05-01 | 1976-09-07 | King Industries, Inc. | Catalysis of amino resin cross-linking reactions with high molecular weight sulfonic acids |
| AU521787B2 (en) * | 1975-07-12 | 1982-04-29 | E. I. Dupont De Nemours And Company | Thermosetting. electrostatically sprayable compositions containing backed acid catalyst |
| US4192826A (en) * | 1976-07-12 | 1980-03-11 | E. I. Du Pont De Nemours And Company | Thermosetting, electrostatically sprayable compositions containing blocked acid catalyst |
| US4154891A (en) * | 1977-03-07 | 1979-05-15 | Ppg Industries, Inc. | Novel thermosetting resinous compositions |
| GB1577998A (en) * | 1977-09-28 | 1980-10-29 | Kansai Paint Co Ltd | Low temperature curing high solid acrylic copolymer-aminoplast resin coating compositions |
| US4200729A (en) * | 1978-05-22 | 1980-04-29 | King Industries, Inc | Curing amino resins with aromatic sulfonic acid oxa-azacyclopentane adducts |
| JPS5927469B2 (en) * | 1979-06-15 | 1984-07-05 | 株式会社クボタ | emergency shutoff valve |
| JPS563357A (en) * | 1979-06-18 | 1981-01-14 | Tokyo Keiki Co Ltd | Pilot operated type relief valve |
| US4247461A (en) * | 1979-11-16 | 1981-01-27 | Bristol-Myers Company | Esterification process using methoxymethyl-P-toluenesulfonate |
| EP0033038A1 (en) * | 1980-01-04 | 1981-08-05 | Ford Motor Company Limited | Thermosetting composition |
| US4281075A (en) * | 1980-01-04 | 1981-07-28 | Ford Motor Company | Sulfonate ester catalysts in thermosetting compositions |
| US4350790A (en) * | 1980-01-04 | 1982-09-21 | Ford Motor Company | Composition with latent reactive catalyst |
| US4454274A (en) * | 1982-09-29 | 1984-06-12 | Ppg Industries, Inc. | Aminoplast curable coating compositions containing cycloaliphatic sulfonic acid esters as latent acid catalysts |
-
1983
- 1983-11-14 US US06/551,389 patent/US4500680A/en not_active Expired - Fee Related
-
1984
- 1984-10-23 CA CA000466141A patent/CA1244598A/en not_active Expired
- 1984-11-12 EP EP84113624A patent/EP0144810B1/en not_active Expired
- 1984-11-12 DE DE8484113624T patent/DE3479513D1/en not_active Expired
- 1984-11-12 AT AT84113624T patent/ATE45757T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| US4500680A (en) | 1985-02-19 |
| EP0144810A3 (en) | 1986-04-02 |
| EP0144810B1 (en) | 1989-08-23 |
| DE3479513D1 (en) | 1989-09-28 |
| ATE45757T1 (en) | 1989-09-15 |
| EP0144810A2 (en) | 1985-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4596724A (en) | Anti-fouling coating composition, process for applying same and coating thereby obtained | |
| US4002699A (en) | Powder coating composition with hydroxy functional copolymer and amino functional crosslinking agent | |
| CA1244598A (en) | Aromatic acid catalysts providing improved humidity resistance | |
| CA1221196A (en) | Humidity resistant coatings employing branched polymers of t-butyl acrylate | |
| US4122233A (en) | Ultraviolet screening agents and coating materials containing organosilane ester groups | |
| GB2294044A (en) | Alkenyl and epoxy (meth)acrylates and polymers thereof | |
| US5319024A (en) | Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof | |
| US4795783A (en) | Organopolysiloxane containing coating compositions | |
| US5324807A (en) | Curable resin composition | |
| EP0376590A2 (en) | Monomer or polymer composition derived from acryloxy alkyl cyanoacetamides | |
| US5155170A (en) | Process for preparing low formaldehyde polyacetal containing coating | |
| US5212242A (en) | Coating composition based on a hydroxyl-containing addition polymer and an amino resin crosslinking agent, agent and containing acid catalysts having hydroxy groups | |
| JPH0660150B2 (en) | Polymerizable 3-Aroyloxyphenyl Carbamate and Method for Producing and Using the Same | |
| Culbertson et al. | Aminimides. VII. Homo-and Copolymerization Studies on 1, 1-Dimethyl-1-(2-hydroxypropyl) amine-Methacrylimide and 1, 1-Dimethyl-1-(2, 3-dihydroxypropyl) amine-Methacrylimide | |
| US4501854A (en) | Aminoplast curable compositions containing disulfonic acid esters as latent acid catalysts | |
| US4299979A (en) | Polymerizable monoethylenic carboxylic acids which decarboxylate on heating | |
| US4528320A (en) | Low temperature, moisture cure coating composition | |
| US4533595A (en) | Abrasion-resistant resinous articles | |
| KR910012118A (en) | Thermosetting paint composition and coloring film formation method | |
| US4323660A (en) | Composition with latent reactive catalyst - #5 | |
| US3454509A (en) | Castor oil modified acrylic coating compositions | |
| US4530960A (en) | Low temperature cure, activated ester coating composition with improved pot life | |
| KR100596514B1 (en) | Automotive paint composition | |
| KR0171043B1 (en) | Coating compositions containing 1,3-dialkylimidazole-2-thione catalysts | |
| JPH02265951A (en) | Hybrid amino resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |