CA1131845A - Blends of low molecular weight hydroxy-terminated polyesters and coatings based on these blends - Google Patents
Blends of low molecular weight hydroxy-terminated polyesters and coatings based on these blendsInfo
- Publication number
- CA1131845A CA1131845A CA282,417A CA282417A CA1131845A CA 1131845 A CA1131845 A CA 1131845A CA 282417 A CA282417 A CA 282417A CA 1131845 A CA1131845 A CA 1131845A
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- Prior art keywords
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- polyester
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Blends of low molecular weight hydroxy-terminated polyesters, based on diols, such as 2,2,4-trimethyl-1,3-pentane diol, and diacids or their esters, such as iso-phthalic acid, and methyl esters of short chain aliphatic diacids, are provided. The blends can be crosslinked with conventional crosslinking agents such as nitrogen resins or polyisocyanates. The formulated coatings have high solids content of relatively low viscosities and are useful on e.g.
metallic substrates forming, upon curing, coatings having excellent tensile strength, hardness, and resistance to staining, weathering, and corrosive conditions.
Blends of low molecular weight hydroxy-terminated polyesters, based on diols, such as 2,2,4-trimethyl-1,3-pentane diol, and diacids or their esters, such as iso-phthalic acid, and methyl esters of short chain aliphatic diacids, are provided. The blends can be crosslinked with conventional crosslinking agents such as nitrogen resins or polyisocyanates. The formulated coatings have high solids content of relatively low viscosities and are useful on e.g.
metallic substrates forming, upon curing, coatings having excellent tensile strength, hardness, and resistance to staining, weathering, and corrosive conditions.
Description
~CKGROUND OF THE INVENTION
Field of Invention _.
This invention is related to lo~ molecular wei~ht polyesters and coatings based thereon and partlcularly to blends of low molecular weight hydroxy-terminated polyesters and thermosetting coating compositions prepared therefrom.
Description of Prior Art Polyesters are well known in the prior art~ Their preparation and utilization in a large ~ariety of coating applications have been amply documented. The prior art is replete with polyesters of various end groups and of wldely varying molecular weights.
United States Patent 3,296,211, issued January 3, 1967 to J. Winkler, et al., discloses hydroxy-terminated polyesters prepared from a mixture of di-primary and primary-:, , secondary diols and aliphatic diacids. Such compositionsare not commonly useful as coati~gs and suffer from the dis-advantage that during their preparation the components link up in a random fashion and there~ore it i~ difficult to control final properties, such as stain and salt spray resistance.
United Stated Patent 3,819,757, issued June 25, 1974 to J. Dorffel, et al., discloses coating compositions containing low molecular weight hy~roxy-terminated polyesters which require maleic or oxalic aclds for curing. Again, a possible dis-advantage of these compositions resides in the use of mixtures of different diol~ and mixturesof different diacids Conventional coating compositions comprise one or more film-formin~ constituents which, as the name im-plies, are primarily responsible for the formation of the ~30 coating film on the substrate. In the case of thermosetting
Field of Invention _.
This invention is related to lo~ molecular wei~ht polyesters and coatings based thereon and partlcularly to blends of low molecular weight hydroxy-terminated polyesters and thermosetting coating compositions prepared therefrom.
Description of Prior Art Polyesters are well known in the prior art~ Their preparation and utilization in a large ~ariety of coating applications have been amply documented. The prior art is replete with polyesters of various end groups and of wldely varying molecular weights.
United States Patent 3,296,211, issued January 3, 1967 to J. Winkler, et al., discloses hydroxy-terminated polyesters prepared from a mixture of di-primary and primary-:, , secondary diols and aliphatic diacids. Such compositionsare not commonly useful as coati~gs and suffer from the dis-advantage that during their preparation the components link up in a random fashion and there~ore it i~ difficult to control final properties, such as stain and salt spray resistance.
United Stated Patent 3,819,757, issued June 25, 1974 to J. Dorffel, et al., discloses coating compositions containing low molecular weight hy~roxy-terminated polyesters which require maleic or oxalic aclds for curing. Again, a possible dis-advantage of these compositions resides in the use of mixtures of different diol~ and mixturesof different diacids Conventional coating compositions comprise one or more film-formin~ constituents which, as the name im-plies, are primarily responsible for the formation of the ~30 coating film on the substrate. In the case of thermosetting
2 -s compositions, it is common -to select as the film-formin~
I constituents of the compositions, blends of rnaterials, at least one oE which is polymerlc and has a typical number average molecular wei~ht of at least about 2,000, whi.ch co-react during the curin~ process to form a crosslinked polymeric film of very high molecular weight. For example, suitable known compo~ :
sitions of ~his type are blends of alkyd resins with melamine-formaldehyde or urea-formaldehyde resins. The resins them-selves are normally solid or semi-solid at ambient temperature and hence 1n order to:formulate coating compositions which.
are sufficiently fluid to be applied to substrates by con ventional means, the compositions usually include solvents for the resins, to lower the composition viscosity. A typical coating composition of this type can contain 40 percent or more by weight of solvent, usually a volatile organic liquid, ~ which must be removed during the curing process, thus presenting - a waste disposal and potential atmospheric pollution p~obIem.
United 5tates Patent~3,857,817, issued December 31, 1974 to B. C. Henshaw, et al., discloses high solids coating compo sitions.based on low molecular weight polyesters and thereby obviating the need for the inclusion of large amounts of organic solv.entsO However, in Example lO of this patent it is pointed ; out that any deviation from the indicated structures results in films having markedly inferior properties. -.
Vnited States Patent 3,893,959, issued July 8, 1975 to R. E. Layman, discloses alkyd resins which are polyesters of rather complex compositions. A mixture of mono~, di , and tri-carboxylic acids is utilized. The dicarboxylic acid compo-nent is made up of at least three different varieties, among 3Q which are the phthalic acids and, optionally, aliphatic di-carboxylic acids. The diol component comprises at least two : 3 -.~
.~3~ 5 kinds, one of which is a hindered diol such as 2,2,4-trl--methyl-1,3-pentane diol. Such compositions suEfer from the above described d.isadvantage of randomness and are too viscous for high solids applications.
SUMMARY OF THE INVENTION
According to the present invention there is provided a blend of hydroxy-terminated polyesters consisting essentially of:
(A) 20-80 parts by weight, based on the weight of the blend,of a polyester of th~ following struc-ture: :
.~ ' C,H3 ~~ 1 ~CH3 HO - - CH-C-CH2-OC-X-Co - -CH2-C - CH- OH
_ -n or the isomeric ester through the secondary hydroxyl group, wherein X~ CH-CH~
:~ and wherein n=0-10 with n=0-3 predominating; and (B) 80-20 parts by weight, based on the weight of the blend, of a polyester of the following general structure:
.~'' ' .
.~
. CH3 O " ~3 HO - -~ CH-C-CH2-OC~cH2~mcO ~ - CH2-C --CH -- OH
_ ~ n ~: - 4 -~3 ~
or the isomeric ester throu~h the secondary hydroxyl group, wherein n=0-10 with n=0-3 predominatlng and wherein m-2-12 with m-2-4 predominating.
According to the present inve~tion there is further provided a high solids coating composition consisting essen-tially of:
(A) 30-80 parts by weight, based on the weight of (A) plus (B), of a blend of hydroxy-terminated polyesters described above; and (B) 70~20 parts by weight) based on the weight of (A) plus (B), of a nitrogen resin crosslinking agent or a polyisocyanate.
It is also contemplated that the coating composition of this invention can contain rheology control agents, pigments, dispersants, adhes~on promoters, and other adjuvants.
DESCRIPTION OF THE INVENTION
~: .
The blend of low molecular weight hydroxy-texminated polyesters of this invention comprises polyesters based on 2,2,4-trimethyl-1,3-pentane diol (TMPD) as the diol coMponent.
It has been found unexpectedly that the exact ~ature - of the diol can be determinative of the properties of the poly-ester blend of this invention. When neopentyl glycol was used in place of TMPD, the polyester components were of very high viscosity, partially solid at room temperature.
To obtain the two polyester componenlts of the blend, - TMPD is reacted separately with iso-phthalic acid (IP~ or its esters such as dimethyl iso-phthalate, other phthalic acids and their esters, male.ic acid and its esters or ~etrahydrophthalic acid, its anhydride or esters, cyclohexane 1,2-dicarboxylic acid, it~ anhydride or esters, and the isomeric naphthalene dicarboxylic 5 _ acids, their esters or anhydrides and with an aliphatic dicarboxylic acid, its esters or mixtures thereof. The aliphatic dicarboxylic acid is of the general formula HooctcH2~ COOH, where m is generally 2-4, although m=l or 4-12 is also possible. In one preferred composition, a mixture of dicarboxylic acids or their esters is utilized, the mixture containing succinic, glutaric, and adipic acids.
The choic~ of a speciEic ratio of aliphatic esters can depend on the final polyester property desired, such as flexibility lQ or softness. In one preferred composition this ratio is 1:2:1 by weight.
During the preparation of the two components o the blend of polyesters, the starting diol component, TMPD, can and probably does react at either of its two hydroxyl groups.
Although the polyester components are represented by the following two formulae, it is contemplated that the isomeric products, ; through the secondary hydroxyl groups, can also be present:
. CH3 0 ,CH3 HO - - CH-C-CH2-OC-X--CO - 1 2 : , CH3CH C~3 CH3 CHCH3 n where X = -CH=C~
2~ ~ , ~ , ~ , ,~ .
and n = 0-10, and , ~3~
C 8 ~ CH3 HO - ~ CH-C-CH2-OC~Cl~2tmCO - - CH2-C ~ CEI ~ OH
CH3Cll CH3 C~3 C~CH3 _ CH3 ~ ~H3 .
where n = 0-10 and m = 2-12.
For optimum final coating properties it has been found that it is important to control not only the composi-tion of each component of the blend and their ratios to each other but also the molecular weight of each of the components of the blend. The average number average molecular weight must not exceed approximately 1,000. It is of course recog-nized by the skilled workers, that a polyester itself is a mixture of different molecular weight species, that is the value of n~in the above structures can vary. I~ is preferred that ~alues of n be 0, l, 2 or 3, although there are usually obtained smaller amounts of higher molecular weight species also, n up to and including 10. In some typical reactions for the preparation of the components of the blend of poly~
esters o~ this invention, the following data show the molecular weight species obtained by gel permeation chromatography uti}izing a polypropylene glycol standard and the corresponding values of n. For the TMPD/IPA reactions a molar ratio of 2.1:1 of the reactants is utilized, for the TMPD/ aliphatic carboxylic methyl esters (dimethyl succinate:dimethyl glutarate:dimethyl adipate = 1:2:1, by weight) reactions the molar ratio is 1O8:1.
I constituents of the compositions, blends of rnaterials, at least one oE which is polymerlc and has a typical number average molecular wei~ht of at least about 2,000, whi.ch co-react during the curin~ process to form a crosslinked polymeric film of very high molecular weight. For example, suitable known compo~ :
sitions of ~his type are blends of alkyd resins with melamine-formaldehyde or urea-formaldehyde resins. The resins them-selves are normally solid or semi-solid at ambient temperature and hence 1n order to:formulate coating compositions which.
are sufficiently fluid to be applied to substrates by con ventional means, the compositions usually include solvents for the resins, to lower the composition viscosity. A typical coating composition of this type can contain 40 percent or more by weight of solvent, usually a volatile organic liquid, ~ which must be removed during the curing process, thus presenting - a waste disposal and potential atmospheric pollution p~obIem.
United 5tates Patent~3,857,817, issued December 31, 1974 to B. C. Henshaw, et al., discloses high solids coating compo sitions.based on low molecular weight polyesters and thereby obviating the need for the inclusion of large amounts of organic solv.entsO However, in Example lO of this patent it is pointed ; out that any deviation from the indicated structures results in films having markedly inferior properties. -.
Vnited States Patent 3,893,959, issued July 8, 1975 to R. E. Layman, discloses alkyd resins which are polyesters of rather complex compositions. A mixture of mono~, di , and tri-carboxylic acids is utilized. The dicarboxylic acid compo-nent is made up of at least three different varieties, among 3Q which are the phthalic acids and, optionally, aliphatic di-carboxylic acids. The diol component comprises at least two : 3 -.~
.~3~ 5 kinds, one of which is a hindered diol such as 2,2,4-trl--methyl-1,3-pentane diol. Such compositions suEfer from the above described d.isadvantage of randomness and are too viscous for high solids applications.
SUMMARY OF THE INVENTION
According to the present invention there is provided a blend of hydroxy-terminated polyesters consisting essentially of:
(A) 20-80 parts by weight, based on the weight of the blend,of a polyester of th~ following struc-ture: :
.~ ' C,H3 ~~ 1 ~CH3 HO - - CH-C-CH2-OC-X-Co - -CH2-C - CH- OH
_ -n or the isomeric ester through the secondary hydroxyl group, wherein X~ CH-CH~
:~ and wherein n=0-10 with n=0-3 predominating; and (B) 80-20 parts by weight, based on the weight of the blend, of a polyester of the following general structure:
.~'' ' .
.~
. CH3 O " ~3 HO - -~ CH-C-CH2-OC~cH2~mcO ~ - CH2-C --CH -- OH
_ ~ n ~: - 4 -~3 ~
or the isomeric ester throu~h the secondary hydroxyl group, wherein n=0-10 with n=0-3 predominatlng and wherein m-2-12 with m-2-4 predominating.
According to the present inve~tion there is further provided a high solids coating composition consisting essen-tially of:
(A) 30-80 parts by weight, based on the weight of (A) plus (B), of a blend of hydroxy-terminated polyesters described above; and (B) 70~20 parts by weight) based on the weight of (A) plus (B), of a nitrogen resin crosslinking agent or a polyisocyanate.
It is also contemplated that the coating composition of this invention can contain rheology control agents, pigments, dispersants, adhes~on promoters, and other adjuvants.
DESCRIPTION OF THE INVENTION
~: .
The blend of low molecular weight hydroxy-texminated polyesters of this invention comprises polyesters based on 2,2,4-trimethyl-1,3-pentane diol (TMPD) as the diol coMponent.
It has been found unexpectedly that the exact ~ature - of the diol can be determinative of the properties of the poly-ester blend of this invention. When neopentyl glycol was used in place of TMPD, the polyester components were of very high viscosity, partially solid at room temperature.
To obtain the two polyester componenlts of the blend, - TMPD is reacted separately with iso-phthalic acid (IP~ or its esters such as dimethyl iso-phthalate, other phthalic acids and their esters, male.ic acid and its esters or ~etrahydrophthalic acid, its anhydride or esters, cyclohexane 1,2-dicarboxylic acid, it~ anhydride or esters, and the isomeric naphthalene dicarboxylic 5 _ acids, their esters or anhydrides and with an aliphatic dicarboxylic acid, its esters or mixtures thereof. The aliphatic dicarboxylic acid is of the general formula HooctcH2~ COOH, where m is generally 2-4, although m=l or 4-12 is also possible. In one preferred composition, a mixture of dicarboxylic acids or their esters is utilized, the mixture containing succinic, glutaric, and adipic acids.
The choic~ of a speciEic ratio of aliphatic esters can depend on the final polyester property desired, such as flexibility lQ or softness. In one preferred composition this ratio is 1:2:1 by weight.
During the preparation of the two components o the blend of polyesters, the starting diol component, TMPD, can and probably does react at either of its two hydroxyl groups.
Although the polyester components are represented by the following two formulae, it is contemplated that the isomeric products, ; through the secondary hydroxyl groups, can also be present:
. CH3 0 ,CH3 HO - - CH-C-CH2-OC-X--CO - 1 2 : , CH3CH C~3 CH3 CHCH3 n where X = -CH=C~
2~ ~ , ~ , ~ , ,~ .
and n = 0-10, and , ~3~
C 8 ~ CH3 HO - ~ CH-C-CH2-OC~Cl~2tmCO - - CH2-C ~ CEI ~ OH
CH3Cll CH3 C~3 C~CH3 _ CH3 ~ ~H3 .
where n = 0-10 and m = 2-12.
For optimum final coating properties it has been found that it is important to control not only the composi-tion of each component of the blend and their ratios to each other but also the molecular weight of each of the components of the blend. The average number average molecular weight must not exceed approximately 1,000. It is of course recog-nized by the skilled workers, that a polyester itself is a mixture of different molecular weight species, that is the value of n~in the above structures can vary. I~ is preferred that ~alues of n be 0, l, 2 or 3, although there are usually obtained smaller amounts of higher molecular weight species also, n up to and including 10. In some typical reactions for the preparation of the components of the blend of poly~
esters o~ this invention, the following data show the molecular weight species obtained by gel permeation chromatography uti}izing a polypropylene glycol standard and the corresponding values of n. For the TMPD/IPA reactions a molar ratio of 2.1:1 of the reactants is utilized, for the TMPD/ aliphatic carboxylic methyl esters (dimethyl succinate:dimethyl glutarate:dimethyl adipate = 1:2:1, by weight) reactions the molar ratio is 1O8:1.
3~
TM~D/IPA
run #1:
molecular weight: 150 410 680 980 1040 (shoulder) n: 0 1 2 3 run #2:
molecular weight: 140 380 640 910-970 ( shoulder) n: 0 1 2 3 It is contemplated that, on the average, at least 70% by weight of this polyester component is n = 3 or less.
TMPD/aliphatic:
.
run #1:
molecular weight: 142 230 390 650 9S0 n: 0 (half- 1 2 3 ester) run #2:
; molecular weight: 143 220 390 640 940 n: 0 (half~ 1 2 3 ester) It is contemplated that, on the average, at least 55~ by weight of this polyester component is n = 3 or less.
~ .
For best overall properties for the coating composition of this invention a low final acid number is desired for the poly-ester components of the blend. The acid number is usually 40 or ~; below but it is preferred that the acid number not exceed 12.
The acid number is the number of milligrams of potassium hydroxide required to neutralize a l-gram sample of the polyester.
C~
The individual polyeste.r components of the blend can be present in the relative weight ratios of from 10:90 to 90:10. It is preferred for op-timum final coating properties that the ratio of the polyester containing the aromatic di-carboxylic acid moiety to the polyester containing the aliphatic dicarboxylic acid moiety be from 80:20 to 40:60 and most preferably 65:35.
The blend of hydroxy-terminated polyesters of this invention can comprise 30~80~ by weight of ~he film-forming composition and preferably 50-70%. The relative amounts of the polyester blend to the crosslinking agent, the total comprising the film-forming composition, can depend on the type of crosslinking agent utilized and on the amount and type of catalyst to be included.
The Eormulated high solids coating compositions of this invention can he applied to a substrate at.a solids content of approximately 95% by weight. A chaxacteristic property of these compositions is the pronounced lowering of viscosity with only a slight increase in temperature from ambient.:
This property can be utilized to enhance, ~O,the spray atomiza-tion during application. In contrast, conventional coating compositions usually exhibit a more linear lowering of viscosity with inoreased temperatures.
: The blend of hydroxy-terminat~d polyesters o~ this invention,~when combined with a crosslinking agent such as a nitrogen resin crosslinking agent or a polyisocyanate, form the coating compositi.on of this invention.
The nitrogen resin crosslinking agents are well known in the art. They are the alkylated products of amino resins, g _ /
the latter prepared by the condensations of at least one aldehyde with at least one oE urea, N,N'-ethyleneurea, dicyandiamide, and aminotriazines such as melamines and guanamines. Among the aldehydes -that are suitable are formaldehyde, revertable polymers thereof such as paraformal-dehyde, acetaldehyde, crotonaldehyde, and acrolein. Pre~
ferred are formaldehyde and revertable polymers thereof.
The amino-resins are alkylated with at least one and up to six alkanol molecules containing 1 to 6 carbon atoms. The alkanols can be straight chain, branched, cyclic or mixtures thereof. Among preferred members of this class are the methylated melamine-formaldehyde resins such as hexam thoxy-methylmelamine. These liquid crosslinking agen~s have sub-stantially 100~ non-volatile content as measured by the oil method at 45C for 45 minutes. For the purposes of this invention it is important not to introduce extraneou~
diluents that would lower the final solids content of the coating. The hexamethoxymethylmelamines also offer fast rates and high efficiency of cure and result in coatings of high gloss and excellent chemical and stain resistance.
The polyisocyanates that can be utilized to cross-link or extend the hydroxy~terminated polyester blend are also well known. Among the preferred ones are included:
the biuret of hexamethylene dilsocyanate and various pre-polymers of isophorone diisocyanate and methylene bis~cyclo~
hexylisocyanate). Diisocyanates can also be utilized.
A preferred composition contains a polyester blend of TMPD/IPA and TMPD/aliphatic in an approximate weight ratio of 65:35, 55~75 parts, and a crosslinking agent, 45 25 parts.
-- 10 --~
~ ~.3~
For optimum properties in a final coatiny Eor use in the appliance industry, 65 parts of the above b:lend is pre-ferred together with 35 parts of a nitrogen resin cross-linking agent. It is understood that, in addition to the above components, the final coating composition can contain a vari~ty of additives and modifiers.
The coating composition of this invention can be cured to a tough, flexible coating upon haating in the absence or presence of additional catalyst. The use o~
acidic catalysts to cure coating compositions based on hydroxy-functional polyesters and complementary cross-linkers is well known in the art, para-toluenesulfonic acid ~PTSA) being a commonly used catalyst.
The amount and type of acid catalyst can depend, among other factors, on the amount and type of crosslinking agent utilized in the coating com~osition of this invention, on the desired curing temperature and time or on the method of application of the coating composition. For example, it was found that utilizing 20 parts by weight of a melamine-formaldehyde crosslinker with 80 parts of the hydroxy-terminated polyester blend of this invention required 0.4 part by weight of PTSA, while a 35/65 ratio of the same materials required approximately 0.5 part by weight of PTSA
to achieve the same approximate level of curing.
The method of application of ~he coating composition can affect the catalyst level when electrostatic spray appli-cation is utilized. For this application it is important that the coating compositio~ have high resistivity. As can be seen from the data below, increasing the level of catalyst, which ;~ 30 allows a higher rate of cure or curing at a lower temperature, 3~
decreases th~ resistivity of the composition as measured by a Ransburg Resistivity Meter having a pre~set gap between the electrodes and thereby providing relative resistivity values in megaohms. The pigmented coating composition utilized in this test is based on a poly-ester blend containing a polyester prepared from TMPD and IPA and a polyester prepared from TMPD and dimethyl aliphatic carboxylates (succina-te glu-tarate: adipate in a 1:2:1 approximate weight ratio), in a weight ratio of approximately 1O4/ and hexamethoxymethylmelamine, in a weight ratio of polyesters:crosslinker of approximately 2:1; measurements are at 25C:
Catal~st Level (~) Relative Resistivity (Megaohm) o 10 0.20 3.~
0.25 ~ l.g .: , .
0.30 1.75 0.35 1.4 0.40 1.2 Curing of the coating composition of this lnvention can be carried out at various temperatures, usually between 125~180C and preferably between 150-17SC. The length of time of curing can also vary but 20-30 minutes afEord well cured coatings.
The coating composition of this invention can contain, in additi~n to a blend of polyesters and a crosslinking agent, other components to enhance various properties of the composi-tlon or the final coating therefrom, such as pigments, pigment - 12 ~
~.t3~
stabilizers, rheology ccntrol agen-ts, for example acrylic polymers, cellulosics, finely divided fumed ~silicas, dis-persants, adhesion promoting agents, e.g. epoxy resins, colorants, and the like.
For purposes of this invention, the coating composition can be prepared from the polyester blends followed by the addition of the o~her ingredients or by premixing the ingredients with each of the polyester com-ponents followed by blending.
The coating compositions of this invention are designed for application to metallic substratesl such as steel and` aluminum and can be applied with or without the presence of a primer. They can be applied by any conven-tional method of application such as spray-, dip-, roll-or brush-coating or by electrostatic methods. In this latter case~ high resistivity of the coating composition is an important factor.
The coating composition of this invention are useful as general industrial coatings, for example in the appliance industry, and provide coatings having excellent s~lvent and stain resistance, resistance to weathering and corrosive conditions, forward and reverse impact, hardness, high gloss, etc.
In the following Examples, illustrating the invention, all parts are by weight, unless otherwise lndicated.
.
.
EXAMPLE I
A. Preparation of a Polyester from 2,2 t 4-Trimethylpentane 1,3 diol and Iso~hthalic acid .
Into a five liter three necked flaslc equipped w.ith stirrer, thermometer, a packed column, condenser, and a Dean-Stark trap are placed TMPD, 1839.6 g; isophthalic acidr 996.0 g; oluene, 54.0 g; and dibutyltin dilaurate, 3.0 g.
The contents of the flask are heated to a maximum temperature of 208C for a total of eleven hours during which time a water-toluene a~eotrope is collected to remove the theoretical amount of water. The final pro~uct has a solids content of 98% in toluene, a viscosity of 32,750 centipoises, measured on a Brookfield viscometer, and an acid number o 5~4.
~ B. Preparation of a Polyester from - . 2,2,4-Trimethylpentane-1,3-diol and a Mixture of Dimethyl aliphatic arboxylates ~ _ : .~
Into an apparatus:described in A above are charged TMPD, 1839.6 g; a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate J in a weight ratio of 1:2.1, ~ :
~: 972.0 ~; and dihutyltin dilaurate, 3 g. The contents of the vessel are heated to a maximum of 202C for a total of nine hours during which time the theoretical amount of ~ethanol is collected. The final product has a Gardner~oldt viscosity of Q and a hydroxyl number of 213.
C. Preparation of_ Polyester Blend A blend of polyesters is prepared by stirrincJ
ogether 80 g of the polyester from A above and 20 q of the polyester from ~ above.
~3~5 D. Preparation of a Co~olyester Control Utilizing the apparatus described :in A above, the following components are placed in the reaction vessel:
; TMPD, 1839.6; dimethyl isophthalate~ 931.2 g; the mixed methyl esters of the aliphatic carboxylic acids shown in B above, 194.4 g; and dibutyltin dilaurate, 3 g. The contents are heated at a maximum temperature of 196C for 7.5 hours to remove the theoretical amount of methanol.
EXAMPLE II
A. Pigment Disp~sion ; A pigment dispersion is prepared from the following ingredients, by sand milling:
HexamethQxymethy1melamine 463.0 g.
Acrylic rheology control agent, at 60% solids, composition:
butyl-acrylate/styrene/hydroxyethyl acrylate/acrylic acid//38/50/8/4, solvent composition:cellosolve acetate/n-butanol/aliphatic hydro-carbon//61/8/31 234.9 g.
Dispersant, at 48~ solids, an isocyanate-modified methyl methacrylate/2-ethylhexyl acrylate//63/37 polymer, capped with mèrcaptosuccinic acid; described in Canadian ~ ~ Patent 968,092, Example I 9.1 g.
Amyl acetate 279.5 g.
Tio~ (rutile) 2013.4 g.
.~
B. Coating Composition Based on Polyester Blend from Exam~le IC
A coating composition is prepared by mixing together the following:
Pigment dispersion fxom A above 400.0 g.
Polyester Blend from Example IC 172.0 g.
Hexamethoxymethylmelamine18.8 g.
Toluene 12.0 g.
PTSA 120% in isopropanol)2.6 g.
C. Coating Composition Based on a Copolyester Con-trol from Example ID
A coating composition is prepared by mixing together the following:
lU~ Pigment dispersion from A above 400.0 g.
Copolyester Control from Example ID 169.1 g~
Hexamethoxymethylmelamine~ 18.8 g.
Toluene 12~0 g.
PTSA (20~ in lsopropanol~~.6 g.
D Preparation of Coatings The compositions from B and C above are applied to cold--rolled steel panels, treated with an iron phosphate con-version coating, by spraying and are cured at 163C for 30 min. The tabulation below shows that the coating composition 20 of this invention has ~xcellent stain and sQlvent resistance while the control fails to meet minimum requirements.
,~
, .
i~
~t3~ 5 Coating Composition Based On:
Test B C (control) Pencil hardness 4H 2H
Solvent resistance ~as measured by pencil hardness testing immediately after 50 double rub~ with methyl ethyl ketone) 4H F
Direct impact resistance 30 inch pound 10 10 40 inch pound 10 9~5 (some cracking) 50 inch pound 10 9.5 (some cracking) Reverse impact resistance 30 inch pound 9.0 9.0 40 inch pound 9.0 8.5 (cracking, delamination) 50 inch pound 8~5 8.5 (crackiny, delamination~
Stain resistance(l) .
mustard 10 lipstick 10 9 orange dye 10 8 Test carried out by placing staining agent on coating for a 72-hour period, followed by washing with soap and water.
The coating i~ rated immediately after the washing. A value of 10 indicates no effect by the staining agent. Minimum aaceptable value for most applications is 9.5.
EXAMPLE II_ A. Prepara~ion of a Polyester from Neopentyl ~ Iso-Dhthalic Acid - Control The procedure of Example IA is repeated, substituting neopentyl glycol (NPG) for TMPD. The -Einal product is a semi-solid at room temperature.
B. Preparation of a Polyester ~rom Neopentyl Glycol and a ~ixture of Dlmethyl Aliphatic Carboxvlates Control __ The procedure of Example IB is repea~ed, substituting neopentyl glycol for TMPD~ The final product is quite viscous and crystals are deposited upon standlng at room temperature.
C. Coating Composition Based on Control Polyester A ' ' ''' ' ' ''''' A coating composition is prepared by mixing together the pigment dispersion from Example IIA, 2643~0; the NPG ~ based polyester from ~ above, 1078.9 g.; an epoxy resin (available from Shell Chemical CoO as EPON* 828), 71.0 g. hexamethoxymethyl melamine, 124.1 g., and amyl acetate, 83.4 g. The final volume soli~s i5 80%.
D. Coating Composition Based on Control Polyester B''' ''' '''' '' A coating composition is prepared as above but substituting the NP& - based po3yester prepared in B above.
The final volume solids is 80%~
* denotes trade mark ~,0~."
~3~
E. Comparison oE Control Coating Compositions from C and D above with Coating Compositions Based on Polyes_ers from Example IA and_B
Coating compositions ~ased on polyesters from Example IA and B are prepared as in C above utili~ing the individual polyester components from Ex~mple IA and IB.
A comparison of these coating compositions, at 80% volume solids, with the control compositions prepared in C and D
above, at the same volume solids, shows that the latter . 10 are very viscous and thereafter are unsuitable, when blended, as high solids coating compositions in most applications:~
Viscosity (cps, BrookEield, . 2 rpm, 32C.) TMPD~IPA-based ~Ex. IIIE)580 (~3 spindle) NPG/IPA-based (control, Ex. IIIC) 2750 ~#3 spindle).
; ~ .
TMPD/aliphatic diesters (Ex.IIIE) 180 (~1 spindle) ; -~
: NPG/aliphatic diesters ~controlj 310 (~1 spindle) - Ex.IIID) ., ~ ~
'
TM~D/IPA
run #1:
molecular weight: 150 410 680 980 1040 (shoulder) n: 0 1 2 3 run #2:
molecular weight: 140 380 640 910-970 ( shoulder) n: 0 1 2 3 It is contemplated that, on the average, at least 70% by weight of this polyester component is n = 3 or less.
TMPD/aliphatic:
.
run #1:
molecular weight: 142 230 390 650 9S0 n: 0 (half- 1 2 3 ester) run #2:
; molecular weight: 143 220 390 640 940 n: 0 (half~ 1 2 3 ester) It is contemplated that, on the average, at least 55~ by weight of this polyester component is n = 3 or less.
~ .
For best overall properties for the coating composition of this invention a low final acid number is desired for the poly-ester components of the blend. The acid number is usually 40 or ~; below but it is preferred that the acid number not exceed 12.
The acid number is the number of milligrams of potassium hydroxide required to neutralize a l-gram sample of the polyester.
C~
The individual polyeste.r components of the blend can be present in the relative weight ratios of from 10:90 to 90:10. It is preferred for op-timum final coating properties that the ratio of the polyester containing the aromatic di-carboxylic acid moiety to the polyester containing the aliphatic dicarboxylic acid moiety be from 80:20 to 40:60 and most preferably 65:35.
The blend of hydroxy-terminated polyesters of this invention can comprise 30~80~ by weight of ~he film-forming composition and preferably 50-70%. The relative amounts of the polyester blend to the crosslinking agent, the total comprising the film-forming composition, can depend on the type of crosslinking agent utilized and on the amount and type of catalyst to be included.
The Eormulated high solids coating compositions of this invention can he applied to a substrate at.a solids content of approximately 95% by weight. A chaxacteristic property of these compositions is the pronounced lowering of viscosity with only a slight increase in temperature from ambient.:
This property can be utilized to enhance, ~O,the spray atomiza-tion during application. In contrast, conventional coating compositions usually exhibit a more linear lowering of viscosity with inoreased temperatures.
: The blend of hydroxy-terminat~d polyesters o~ this invention,~when combined with a crosslinking agent such as a nitrogen resin crosslinking agent or a polyisocyanate, form the coating compositi.on of this invention.
The nitrogen resin crosslinking agents are well known in the art. They are the alkylated products of amino resins, g _ /
the latter prepared by the condensations of at least one aldehyde with at least one oE urea, N,N'-ethyleneurea, dicyandiamide, and aminotriazines such as melamines and guanamines. Among the aldehydes -that are suitable are formaldehyde, revertable polymers thereof such as paraformal-dehyde, acetaldehyde, crotonaldehyde, and acrolein. Pre~
ferred are formaldehyde and revertable polymers thereof.
The amino-resins are alkylated with at least one and up to six alkanol molecules containing 1 to 6 carbon atoms. The alkanols can be straight chain, branched, cyclic or mixtures thereof. Among preferred members of this class are the methylated melamine-formaldehyde resins such as hexam thoxy-methylmelamine. These liquid crosslinking agen~s have sub-stantially 100~ non-volatile content as measured by the oil method at 45C for 45 minutes. For the purposes of this invention it is important not to introduce extraneou~
diluents that would lower the final solids content of the coating. The hexamethoxymethylmelamines also offer fast rates and high efficiency of cure and result in coatings of high gloss and excellent chemical and stain resistance.
The polyisocyanates that can be utilized to cross-link or extend the hydroxy~terminated polyester blend are also well known. Among the preferred ones are included:
the biuret of hexamethylene dilsocyanate and various pre-polymers of isophorone diisocyanate and methylene bis~cyclo~
hexylisocyanate). Diisocyanates can also be utilized.
A preferred composition contains a polyester blend of TMPD/IPA and TMPD/aliphatic in an approximate weight ratio of 65:35, 55~75 parts, and a crosslinking agent, 45 25 parts.
-- 10 --~
~ ~.3~
For optimum properties in a final coatiny Eor use in the appliance industry, 65 parts of the above b:lend is pre-ferred together with 35 parts of a nitrogen resin cross-linking agent. It is understood that, in addition to the above components, the final coating composition can contain a vari~ty of additives and modifiers.
The coating composition of this invention can be cured to a tough, flexible coating upon haating in the absence or presence of additional catalyst. The use o~
acidic catalysts to cure coating compositions based on hydroxy-functional polyesters and complementary cross-linkers is well known in the art, para-toluenesulfonic acid ~PTSA) being a commonly used catalyst.
The amount and type of acid catalyst can depend, among other factors, on the amount and type of crosslinking agent utilized in the coating com~osition of this invention, on the desired curing temperature and time or on the method of application of the coating composition. For example, it was found that utilizing 20 parts by weight of a melamine-formaldehyde crosslinker with 80 parts of the hydroxy-terminated polyester blend of this invention required 0.4 part by weight of PTSA, while a 35/65 ratio of the same materials required approximately 0.5 part by weight of PTSA
to achieve the same approximate level of curing.
The method of application of ~he coating composition can affect the catalyst level when electrostatic spray appli-cation is utilized. For this application it is important that the coating compositio~ have high resistivity. As can be seen from the data below, increasing the level of catalyst, which ;~ 30 allows a higher rate of cure or curing at a lower temperature, 3~
decreases th~ resistivity of the composition as measured by a Ransburg Resistivity Meter having a pre~set gap between the electrodes and thereby providing relative resistivity values in megaohms. The pigmented coating composition utilized in this test is based on a poly-ester blend containing a polyester prepared from TMPD and IPA and a polyester prepared from TMPD and dimethyl aliphatic carboxylates (succina-te glu-tarate: adipate in a 1:2:1 approximate weight ratio), in a weight ratio of approximately 1O4/ and hexamethoxymethylmelamine, in a weight ratio of polyesters:crosslinker of approximately 2:1; measurements are at 25C:
Catal~st Level (~) Relative Resistivity (Megaohm) o 10 0.20 3.~
0.25 ~ l.g .: , .
0.30 1.75 0.35 1.4 0.40 1.2 Curing of the coating composition of this lnvention can be carried out at various temperatures, usually between 125~180C and preferably between 150-17SC. The length of time of curing can also vary but 20-30 minutes afEord well cured coatings.
The coating composition of this invention can contain, in additi~n to a blend of polyesters and a crosslinking agent, other components to enhance various properties of the composi-tlon or the final coating therefrom, such as pigments, pigment - 12 ~
~.t3~
stabilizers, rheology ccntrol agen-ts, for example acrylic polymers, cellulosics, finely divided fumed ~silicas, dis-persants, adhesion promoting agents, e.g. epoxy resins, colorants, and the like.
For purposes of this invention, the coating composition can be prepared from the polyester blends followed by the addition of the o~her ingredients or by premixing the ingredients with each of the polyester com-ponents followed by blending.
The coating compositions of this invention are designed for application to metallic substratesl such as steel and` aluminum and can be applied with or without the presence of a primer. They can be applied by any conven-tional method of application such as spray-, dip-, roll-or brush-coating or by electrostatic methods. In this latter case~ high resistivity of the coating composition is an important factor.
The coating composition of this invention are useful as general industrial coatings, for example in the appliance industry, and provide coatings having excellent s~lvent and stain resistance, resistance to weathering and corrosive conditions, forward and reverse impact, hardness, high gloss, etc.
In the following Examples, illustrating the invention, all parts are by weight, unless otherwise lndicated.
.
.
EXAMPLE I
A. Preparation of a Polyester from 2,2 t 4-Trimethylpentane 1,3 diol and Iso~hthalic acid .
Into a five liter three necked flaslc equipped w.ith stirrer, thermometer, a packed column, condenser, and a Dean-Stark trap are placed TMPD, 1839.6 g; isophthalic acidr 996.0 g; oluene, 54.0 g; and dibutyltin dilaurate, 3.0 g.
The contents of the flask are heated to a maximum temperature of 208C for a total of eleven hours during which time a water-toluene a~eotrope is collected to remove the theoretical amount of water. The final pro~uct has a solids content of 98% in toluene, a viscosity of 32,750 centipoises, measured on a Brookfield viscometer, and an acid number o 5~4.
~ B. Preparation of a Polyester from - . 2,2,4-Trimethylpentane-1,3-diol and a Mixture of Dimethyl aliphatic arboxylates ~ _ : .~
Into an apparatus:described in A above are charged TMPD, 1839.6 g; a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate J in a weight ratio of 1:2.1, ~ :
~: 972.0 ~; and dihutyltin dilaurate, 3 g. The contents of the vessel are heated to a maximum of 202C for a total of nine hours during which time the theoretical amount of ~ethanol is collected. The final product has a Gardner~oldt viscosity of Q and a hydroxyl number of 213.
C. Preparation of_ Polyester Blend A blend of polyesters is prepared by stirrincJ
ogether 80 g of the polyester from A above and 20 q of the polyester from ~ above.
~3~5 D. Preparation of a Co~olyester Control Utilizing the apparatus described :in A above, the following components are placed in the reaction vessel:
; TMPD, 1839.6; dimethyl isophthalate~ 931.2 g; the mixed methyl esters of the aliphatic carboxylic acids shown in B above, 194.4 g; and dibutyltin dilaurate, 3 g. The contents are heated at a maximum temperature of 196C for 7.5 hours to remove the theoretical amount of methanol.
EXAMPLE II
A. Pigment Disp~sion ; A pigment dispersion is prepared from the following ingredients, by sand milling:
HexamethQxymethy1melamine 463.0 g.
Acrylic rheology control agent, at 60% solids, composition:
butyl-acrylate/styrene/hydroxyethyl acrylate/acrylic acid//38/50/8/4, solvent composition:cellosolve acetate/n-butanol/aliphatic hydro-carbon//61/8/31 234.9 g.
Dispersant, at 48~ solids, an isocyanate-modified methyl methacrylate/2-ethylhexyl acrylate//63/37 polymer, capped with mèrcaptosuccinic acid; described in Canadian ~ ~ Patent 968,092, Example I 9.1 g.
Amyl acetate 279.5 g.
Tio~ (rutile) 2013.4 g.
.~
B. Coating Composition Based on Polyester Blend from Exam~le IC
A coating composition is prepared by mixing together the following:
Pigment dispersion fxom A above 400.0 g.
Polyester Blend from Example IC 172.0 g.
Hexamethoxymethylmelamine18.8 g.
Toluene 12.0 g.
PTSA 120% in isopropanol)2.6 g.
C. Coating Composition Based on a Copolyester Con-trol from Example ID
A coating composition is prepared by mixing together the following:
lU~ Pigment dispersion from A above 400.0 g.
Copolyester Control from Example ID 169.1 g~
Hexamethoxymethylmelamine~ 18.8 g.
Toluene 12~0 g.
PTSA (20~ in lsopropanol~~.6 g.
D Preparation of Coatings The compositions from B and C above are applied to cold--rolled steel panels, treated with an iron phosphate con-version coating, by spraying and are cured at 163C for 30 min. The tabulation below shows that the coating composition 20 of this invention has ~xcellent stain and sQlvent resistance while the control fails to meet minimum requirements.
,~
, .
i~
~t3~ 5 Coating Composition Based On:
Test B C (control) Pencil hardness 4H 2H
Solvent resistance ~as measured by pencil hardness testing immediately after 50 double rub~ with methyl ethyl ketone) 4H F
Direct impact resistance 30 inch pound 10 10 40 inch pound 10 9~5 (some cracking) 50 inch pound 10 9.5 (some cracking) Reverse impact resistance 30 inch pound 9.0 9.0 40 inch pound 9.0 8.5 (cracking, delamination) 50 inch pound 8~5 8.5 (crackiny, delamination~
Stain resistance(l) .
mustard 10 lipstick 10 9 orange dye 10 8 Test carried out by placing staining agent on coating for a 72-hour period, followed by washing with soap and water.
The coating i~ rated immediately after the washing. A value of 10 indicates no effect by the staining agent. Minimum aaceptable value for most applications is 9.5.
EXAMPLE II_ A. Prepara~ion of a Polyester from Neopentyl ~ Iso-Dhthalic Acid - Control The procedure of Example IA is repeated, substituting neopentyl glycol (NPG) for TMPD. The -Einal product is a semi-solid at room temperature.
B. Preparation of a Polyester ~rom Neopentyl Glycol and a ~ixture of Dlmethyl Aliphatic Carboxvlates Control __ The procedure of Example IB is repea~ed, substituting neopentyl glycol for TMPD~ The final product is quite viscous and crystals are deposited upon standlng at room temperature.
C. Coating Composition Based on Control Polyester A ' ' ''' ' ' ''''' A coating composition is prepared by mixing together the pigment dispersion from Example IIA, 2643~0; the NPG ~ based polyester from ~ above, 1078.9 g.; an epoxy resin (available from Shell Chemical CoO as EPON* 828), 71.0 g. hexamethoxymethyl melamine, 124.1 g., and amyl acetate, 83.4 g. The final volume soli~s i5 80%.
D. Coating Composition Based on Control Polyester B''' ''' '''' '' A coating composition is prepared as above but substituting the NP& - based po3yester prepared in B above.
The final volume solids is 80%~
* denotes trade mark ~,0~."
~3~
E. Comparison oE Control Coating Compositions from C and D above with Coating Compositions Based on Polyes_ers from Example IA and_B
Coating compositions ~ased on polyesters from Example IA and B are prepared as in C above utili~ing the individual polyester components from Ex~mple IA and IB.
A comparison of these coating compositions, at 80% volume solids, with the control compositions prepared in C and D
above, at the same volume solids, shows that the latter . 10 are very viscous and thereafter are unsuitable, when blended, as high solids coating compositions in most applications:~
Viscosity (cps, BrookEield, . 2 rpm, 32C.) TMPD~IPA-based ~Ex. IIIE)580 (~3 spindle) NPG/IPA-based (control, Ex. IIIC) 2750 ~#3 spindle).
; ~ .
TMPD/aliphatic diesters (Ex.IIIE) 180 (~1 spindle) ; -~
: NPG/aliphatic diesters ~controlj 310 (~1 spindle) - Ex.IIID) ., ~ ~
'
Claims (12)
1. A polyester blend consisting essentially of:
(A) 10-90 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein X =
-CH=CH-, . , , , , , , , and wherein n = 0-10 and at least 70% by weight is n = 3 or less; and (B) 90-10 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, where n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-12, said polyester blend having a number-average molecular weight of not more than 1000.
(A) 10-90 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein X =
-CH=CH-, . , , , , , , , and wherein n = 0-10 and at least 70% by weight is n = 3 or less; and (B) 90-10 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, where n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-12, said polyester blend having a number-average molecular weight of not more than 1000.
2. The polyester blend of Claim 1 wherein X is and m = 2-4.
3. The polyester blend of Claim 1 wherein said component (A) is 40-80 parts by weight of the blend and said component (B) is 60-20 parts by weight of the blend.
4. The polyester blend of Claim 3 wherein said component (A) is based on isophthalic acid and said component (B) is based on a mixture of succinic, glutaric, and adipic acids in an approximate weight ratio of 1:2:1.
5. A high solids coating composition consisting essentially of:
(A) 30-80 parts by weight, based on the weight of (A) plus (B), of a polyester blend consisting essentially of (1) 10-90 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereoE, wherein X=
-CH=CH-, , , , , , , , , and wherein n = 0-10 and at least 70% by weight is n = 3 or less; and (2) 90-10 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-12, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 70-20 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin or a polyisocyanate cross-linking agent.
(A) 30-80 parts by weight, based on the weight of (A) plus (B), of a polyester blend consisting essentially of (1) 10-90 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereoE, wherein X=
-CH=CH-, , , , , , , , , and wherein n = 0-10 and at least 70% by weight is n = 3 or less; and (2) 90-10 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-12, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 70-20 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin or a polyisocyanate cross-linking agent.
6. The coating composition of Claim 5 wherein X - and m = 2-4.
7. The coating composition of Claim 5 wherein component (A)(l) is 40-80 parts by weight of said polyester blend and component (A)(2) is 60-20 parts by weight of said polyester blend.
8. The coating composition of Claim 7 wherein component (A)(l) is based on iso-phthalic acid and component (A)(2) is based on a mixture of succinic, glutaric, and adipic acidsin an approximate weight ratio of 1:2:1.
9. The coating composition of Claim 7 consisting essentially of 55-75 parts by weight of said polyester blend and 45-25 parts by weight of said crosslinking agent.
10. The coating composition of Claim 7 additionally containing pigment, rheology control agent, adhesion promoting agent, dispersant, and catalyst.
11. A coating composition comprising (A) 55-75 parts by weight, based on the weight of (A) plus (B), of a polyester blend consisting essentially of (1) 40-80 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less; and (2) 60-20 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-4, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 45-25 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin crosslinking agent
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less; and (2) 60-20 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-4, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 45-25 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin crosslinking agent
12. A coating composition comprising (A) 65 parts by weight, based on the weight of (A) plus (B), of a polyester blend consisting essentially of (1) 65 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less; and (2) 35 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-4, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 35 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin crosslinking agent.
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less; and (2) 35 parts by weight, based on the weight of the blend, of a polyester of the following structure:
its isomer through the secondary hydroxyl group or mixtures thereof, wherein n = 0-10 and at least 65% by weight is n = 3 or less and wherein m = 2-4, said polyester blend having a number-average molecular weight of not more than 1000; and (B) 35 parts by weight, based on the weight of (A) plus (B), of a nitrogen-containing resin crosslinking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70436676A | 1976-07-12 | 1976-07-12 | |
| US704,366 | 1985-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131845A true CA1131845A (en) | 1982-09-14 |
Family
ID=24829171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,417A Expired CA1131845A (en) | 1976-07-12 | 1977-07-11 | Blends of low molecular weight hydroxy-terminated polyesters and coatings based on these blends |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS538653A (en) |
| AT (1) | AT357245B (en) |
| AU (1) | AU519914B2 (en) |
| CA (1) | CA1131845A (en) |
| DE (1) | DE2731488A1 (en) |
| FR (1) | FR2358442A1 (en) |
| GB (1) | GB1561076A (en) |
| NL (1) | NL186772C (en) |
| ZA (1) | ZA774147B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4369283A (en) | 1981-03-06 | 1983-01-18 | E. I. Du Pont De Nemours & Company | High solids can coating composition containing epoxy, acrylic and aminoplast resins |
| JPH0534248Y2 (en) * | 1986-04-24 | 1993-08-31 | ||
| DE4039220A1 (en) * | 1990-12-08 | 1992-06-11 | Basf Lacke & Farben | COATING AGENTS WITH A HIGH SOLID CONTENT |
| JP5483670B2 (en) * | 2008-12-26 | 2014-05-07 | 竹本油脂株式会社 | Non-aqueous pigment dispersant and pigment composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3296211A (en) * | 1961-11-01 | 1967-01-03 | Aerojet General Co | Hydroxy-terminated polyesters |
| ES382338A1 (en) * | 1969-12-15 | 1972-11-16 | Koppers Co Inc | A procedure for preparing a polyester resin. (Machine-translation by Google Translate, not legally binding) |
| DE2146754C3 (en) * | 1971-09-18 | 1982-05-27 | Chemische Werke Hüls AG, 4370 Marl | Coating agents |
| AU466953B2 (en) * | 1972-05-24 | 1975-11-13 | Dulux Australia Limited | Thermosetting coating compositions |
| US3893959A (en) * | 1973-10-24 | 1975-07-08 | American Cyanamid Co | Alkyl resin containing an oligomer mixture of unsaturated long chain fatty acids |
-
1977
- 1977-07-08 AU AU26882/77A patent/AU519914B2/en not_active Expired
- 1977-07-11 GB GB29002/77A patent/GB1561076A/en not_active Expired
- 1977-07-11 CA CA282,417A patent/CA1131845A/en not_active Expired
- 1977-07-11 ZA ZA00774147A patent/ZA774147B/en unknown
- 1977-07-11 FR FR7721330A patent/FR2358442A1/en active Granted
- 1977-07-11 AT AT495977A patent/AT357245B/en not_active IP Right Cessation
- 1977-07-12 JP JP8350077A patent/JPS538653A/en active Granted
- 1977-07-12 DE DE19772731488 patent/DE2731488A1/en active Granted
- 1977-07-12 NL NLAANVRAGE7707759,A patent/NL186772C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2358442B1 (en) | 1984-05-11 |
| AU2688277A (en) | 1979-01-11 |
| AU519914B2 (en) | 1982-01-07 |
| NL7707759A (en) | 1978-01-16 |
| GB1561076A (en) | 1980-02-13 |
| AT357245B (en) | 1980-06-25 |
| ZA774147B (en) | 1978-05-30 |
| JPS6138218B2 (en) | 1986-08-28 |
| DE2731488A1 (en) | 1978-01-19 |
| JPS538653A (en) | 1978-01-26 |
| FR2358442A1 (en) | 1978-02-10 |
| DE2731488C2 (en) | 1989-03-02 |
| ATA495977A (en) | 1979-11-15 |
| NL186772C (en) | 1991-02-18 |
| NL186772B (en) | 1990-09-17 |
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