CA1269480A - Resinous composition for a top coat - Google Patents
Resinous composition for a top coatInfo
- Publication number
- CA1269480A CA1269480A CA000514951A CA514951A CA1269480A CA 1269480 A CA1269480 A CA 1269480A CA 000514951 A CA000514951 A CA 000514951A CA 514951 A CA514951 A CA 514951A CA 1269480 A CA1269480 A CA 1269480A
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- Prior art keywords
- acid
- resin
- mole
- polyester resin
- resinous
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract of the disclosure A resinous composition for a top coat comprising a polyester resin modified with a laetone, said polyester resin being characterized in that 10 to 80 mole % of acid component is an alicyclic polycarboxylic acid or anhydride thereof, and 10 to 100 mole % of the carboxyl groups capable of developing a resinous acid value is derived from a polycarboxylic acid which will show a potentiometric midpoint potential in a non aqueous potentiometric titration, and the state being incorporated into the resin, of -350 mV or more.
The coating composition based on said resinous composition is specifically useful as a top coat for automobile bodies in the two-tone-color coating.
The coating composition based on said resinous composition is specifically useful as a top coat for automobile bodies in the two-tone-color coating.
Description
~ ~J~ 8~
The present invention relates to a resinous composition for a top coat and more specifically, to a resinous composition for a top coat which is particularly useful for the coating of automobile bodies in the so-called two-tone-color coating.
Since a polyester resin can result a coating with excellent film properties as weather resistance, flame resistance, chemical resistance and the like, it is being watched with keen interest in various technical fields and especially in an automobile industry as a resinous vehicle for a top coat. Usually, a polyester resin is compounded with an aminoaldehyde resin and thus obtained composition is applled and baked to give a tough coating being excellent in mechanical properties and inter coat adhesion and the like. Nevertheless, such a composition has scarcely been used in an automobile industry as a top-coat because the coating has the problems of cissing, loss in gloss and in contrast factor, and heretofore proposed polyester resins each has a problem or poor compatibility with amino resin.
Recently, various attempts have been made to improve the properties of an oil-~ree polyester resin. For example, in Japanese Patent ~pplication Kokai No. 20068/81, published February 25, 1981, a large quantity o~ saturated alicyclic carboxylic acid or a combination of a saturated alicyclic polycarboxylic acid and ..
L~
an aromatic polycarboxylic acid are used as acid components of said polyester resin thereby attaining the improvements in cissing, loss in gloss and weather resistance of the coating and compatibility of the resin with an amino plast res~n; and in Japanese Patent Application Kokai Nos. 111864/83 and 111865/83 both published July 4, 1983, a large quantity of alicyclic polycarboxylic acid is used as an acid component and a comparatively long methylene chain is included in either one of dicarboxylic acid or diol component, or in a lactone to be used 10 for the modification of the formed polyester, thereby improving durability, adhesion properties, elongation and softness of the coating. These studies are noteworthy in a sense that they cut a path to the practical use of polyester resin, as a resinous vehicle, in an automobile top coat or coating composition to be 15 applied to flexible materials as fender, bumper and other parts.
In a top coating of automobile bodies and especially in a two-tone-color coating, the main color composition is first applied and baked, and without sanding operation, the second color 20 composition is then applled and baked. At that time there often arises often arises an interface adhesive failure between the first and the second color coatings.
~ ~ ~ 9 ~ ~
This is especially true when a solid color coating composition is applied on a metallic coat, which combination is most important and in great demand at the present moment.
What is worse still, it has been found that the higher the baking temperature of metallic coat, the poorer the two-tone adhesion.
Under the circumstances, it has long been desired to provide a polyester resin composition for a top coat which is excellent in weather resistance, film properties and curing properties, said composition being suitable forming a high build coating and to a two-tone-color coating and especially recoating of solid color onto a metallic coat, and giving an excellent two-tone adhesion over a wide range of baking conditions.
The present invention therefore provides a polyester resin which will fulfill the abovesaid requirements.
According to the invention there is provided a reslnous composition for a top coat comprising a polyester resin modified with a lactone, said polyester rcsin being composed of alcohol and acid components, lO to 80 mole ~ of the acid component being an alicyclic polycarboxylic acid or anhydride thereof and lO to 100 mole ~ of the carboxyl groups capable of developing a resinous acid value being derived from a polycarboxylic acid showing a titration midpoint potential in a non-a~ueous potentiometric titration, under the state being incorporated into the resin, of -350 mV or more, and said lactone being represented by the formula:
.
. .
.
' o O-~CH2)n~C=O
in which n is an integer of 4 to 10, and included in an amount corresponding to 5 to 30~ by weight of the total weight of the resin.
The lactone modlfied polyester resin of the present invention may be successfully and advantageously prepared by using a similar, but slightly modified method as described in Japanese Patent Application Xokai No. 4054/84. That is, a polyester resin having as acid components (a) mole of a saturated alicyclic polycarboxylic acid (A), (b) mole of a polycarboxylic acld (B) whose titration midpoint potential in non-aqueous potentiometric titration, under the state being lncorporated into the resin, is -350mV or more, and (c) mole of other poly- and/or mono-carboxylic acid (C) (wherein a+b+c=l.o mole; 0 < c mole and 10 < a x 100 < ~0 mole %) a+b+c is prepared by the combination of steps or reacting an acid mixture of (a) mole of the acld (A), (b-bl) mole of the acid (B) o and (c) mole of the acid (C), with a polyhydric alcohol to obtain a polyester prepolymer haviny a resinous acid value of M, in which M = N(l-x/100) and then adding (bl) mole of the acid (~) and continuing the esterification until it reaches to a resinous acid value of N.
In the abovesaid statement, (bl) is equal to (b) or less than (b), and denotes the molar amount of said (B) acid to be charged at~a later stage, which is determined by the following equation:
- x N x W
bl = 10,0 , ,, X --~ . p 5610~ f l - 100 wherein N stands for the resinous acid value (KOH mg required for the neutralization of lg of resinous solid matter); W is the weight of polyester resin; f is the number of Eunctional groups possessed by (B); P is the reaction percentage of (B) at the later charging stage; x is the mole% o~ (~) occupied in the carboxyl groups capable of developing a resinous acid value and determined in a range of 10 ~ x < 100.
Thus obtained polyester resin which i5 composed of alcohol and acid components, l0 to 80 mole% of the acid component being an alicyclic polycarboxylic acid and 10 to l00 mole%
of the carboxyl groups capable of developing a resinous acid value being derived from a polycarboxylic acid which will show a titration midpoint potential in a non-aqueous .~, potentiometric titration, under the state being incorporated into the resin, of -350mV or more, is then reacted with a lactone of the formula:
y~c=o wherein n is an integer of 4 to 10 in amount corresponding to 5 to 3~% by weight of the total weight o~ the resin, to obtain the present lactone modified polyester resin.
Amotlg the said acid components, examples of saturated alicyclic polycarboxylic acid (A) are cyclohexane ring beariny alicyclic acids as, for example, l,l~cyclohexane dicarboxylic acid, hexahydrophthalic acid and its anhydride, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, methylhexahydrophthalic acid and .its anhydride, hexahydrotrimellitic acid and its anhydride, and hexahydro-2-methyl-trimellitic acid and its anhydride.
Examples of polycarboxylic acid (~ aving the titration midpoint potential in non-a~ueous potentiometric titration, under the state being incororated into a resin, of -35~mV or more are aromatic polycarboxylic acids as phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride and the like. Such polycarboxylic acid per se will, in general, show, when made an electric potential-TBAH titer curve from the test results of non-aqueous potentiometric titration, a curve having multi-stage inflection points, and however, when incorporated in to a polyester chain, at least one carboxyl group will remain in a free state and the corresponding curve will have the diminished number of inflection points, accordingly.
Under such conditions, if a polycarboxylic acid is possessed of such acid strength that the aforesaid titration midpoint potential is -350mV or more, then such a member may advantageously be used for the object of the present invention.
As the acid components, other poly- and/or mono-carboxylic acids (C) than the abovesaid (A) and (B) may be present, if desired. Such acid (C) may be any of the members customarily used as an acid component of polyester resin, including aliphatic or partially saturated alicycllc acids, like succinic acid and its anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid and the like.
Futhermore, monocarboxylic acids as benzoic acid, p-t-butyl benzoic acid and the like may be added for the purpose of regulating the molecular weight of the resin.
The polyhydric alcohol component to be reacted with said acid mixture is not of specific type and suitably selected from the members customarily used for the preparation of polyester resins. Examples of such members are ethyleneglycol, diethyleneglycol, propyleneglycol, neopentylglycol, 1,2-bu~yleneglycol, 1,3-butyleneglycol, ~,3-butyleneglycol, 1,4-butyleneglycol, 1,6-hexanediol, 1,5-pentanediol, ~,5-hexanediol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, diglycerin, sorbitol, 1,4-cyclohexane dimethanol and the like.
AS already stated, the present acid controlled modified polyester resin must be of the nature such that 10 to 80 mole% of the total acid components be occupied by said saturated alicyclic polycarboxylic acid (A) and 10 to 100 mole% of .the carboxyl groups capable of developing a resinous acid value be derived from polycarboxylic acids (~) having a titration midpoint potential in a non-aqueous potent.iometric titration, under a state such that carboxylic acid is capable of developing a resinous acid value, of -~50mV or more. This is because, if the content of saturated alicyclic polycarboxylic acid is less than 10 mole~ of the total acid components, weather resistance may not be improved, whereas if it exceeds the upper limit of 80 mole~, the chamical resistance be lowered. As to the ratio oE carboxyl groups responsible for the development of the resinous acid value, if the amount of said polycarboxylic acid having the specified cid strength is less than 10 mole%, then there is a general trend towards producing coating of insuEficient gloss and curing properties and hence, the object of the present invention cannot be attained.
In an actual preparation of said acid controlled modified polyester resin, a polyester prepolymer is first prepared by using an acidic mixture of said acid (A) and poly- and/or mono-carboxylic acid (C) including, as desired, a part of the polycarboxylic acid (B), together with a polyhydric alcohol, and to thus obtained polyester prepolymer, the whole or remaining parts of the acid (B) is then added and the esterification is continued to obtain the intended product. As to the amounts of polycarboxylic acid (B) to be charyed in the first and in the second stage of reaction, the later charging amount (bl mole) is calculated beforehand from the abovesaid equation using a number of valiable, i.e.
(f): number of functional groups possessed by the acid (B), (N): resinous acid value, (W): weight oE the resin, (x): mole% oE the carboxyl groups derived from the acid (B) occupied in the total carboxyl groups capable of developiny resinous acid value, and (P): reaction percentage o the later charging acid (B), and the amount (b mole) o said acid (B) to be charged in the first stage is determined as (l-bl) mole.
Incidentally, in the abovesaid equation, the reaction percentage (P) is the value showing the meaning of what % of carboxyl groups in the polycarboxylic acid ~B) should be reacted in order that the acid is surely incorporated into the polyester chain through an esterification, and said (P) is, for example, 50% or more in the case of dicarboxylic acid as phthalic anhydride, and about 34% or more in the case of tricarboxylic acid as trimellitic acid.
The esterification of polycarboxylic acids with a polyhydric _ 9 _ .
o alcohol may be carried out in a conventional way and no particualr technique is required therefor.
In a preferred embodiment, the esterification shall be continued until the resinous acid value comes to 1 to 135 in the first step for obtaining a polyester prepolymer and to 1 to 150 in the second step for obtaining an acid controlled modified polyester resin. As to a number average molecular weight of the polyester resin, it may be freely selected in the range which is cornmon in the heretofore proposed polyester resins for coatiny use.
In this way, an acid controlled modified polyester resin having alcohol and acid components, 1~ to ~0 mole% of said acid component being an alicyclic polycarboxylic acid (A) and 10 to 100 mole% of the carboxyl yroups capable of developiny a resinous acid value being derived from a polycarboxylic acid (B) showing a titration midpoint potential in a non-a~ueous potentiometrlc titration, under the state being incorporated into the resin, of -350 mV or more, can be obtained.
According to the present invention, the abovesaid polyester resin is then reacted with a lactone of the formula:
O-(CH2)n-cl=o wherein n is an integer o~ 4 to 10, to obtain an acid controlled, lactone-modified polyester resin.
Examples of said lactone are ~-caprolactone, ~-enantholactone, ~-caprylolactone, and their ring substituted derivativ~s. Particularly preferred members are the lactones having 6 to 8 carbon atoms.
Lactone modiEication may be carried out in a conventional way by adding a lactone to the abovesaid acid controlled modified polyester resin and heating the mixture.
At this time, the added lactone is rin~-opened and reacted with a hydroxyl goup of said polyester resin to give a lactone modified resin.
In this reaction, it is preferred to use a catalyst as tin compounds, or~anic lead or manganese salts, and the like.
Particularly preferred members are the tin compounds of the formula:
X X / X' sno or Sn X , X X' wherein X stands for an alkyl, an aryl, an aralkyl, or an aryloxy group, and X' is an alkyl, an aryl, an aralkyl, an acyloxy, a haloyen or hydroxyl group.
As, for example, tetraphennyl tin, tetraoctyl tin, diphenyl tin dilaurate, tri-n~butyl tin hydroxide, tri-n-butyl tin acetate, dimethyl tin oxide, dibutyl tin oxide, dilauryl tin oxide, di-n-butyl tin dichloride, dioctyl tin dichloride and the like, and lead acetate, manganese acetate, lead 2-ethyl hexane acetate, lead salicylate, lead benzoate and the like.
The lactone moiety of thus obtained polyester resin is believed, under the state incorporated into the polyester chain, to produce an optimum flexibility oE the resin. The :
::
presence of lactone in the polyester resin is, thus, important in this invention and however, the lactone amount should preferably be limitted in a range corresponding to 5 to 30~ of tlle total weight of the resin. This is because, if the lactone amount is less than 5% by weight of the total resin, it is unable to get the desired elongation, Erichsen test results and impact resistance, and if it is over the upper limit of 30~ by weight of the total resin, there will give a coating with inferior properties especially in respect of tensile strength, hardness, chemical resistance and water resistance. These are undesirable for the intended object of having a resinous composition for a top coat.
The present resinous composition has many desirable properties as follows.
~ince an alicyclic polycarboxylic acid is used as a part of acid component oE the polyester resin, an excellent weather resistance is given to the coating.
Since the resin is modified with a lactone, impact resistance of the coating is greatly improved.
From the abovesaid two characteristics, an improved solubility is given to the resin and hence a high solid coating composition can be formulated with the present resinous composition.
Since a reactive hydroxyl group is given to the resin by the lactone modification and the carboxyl groups capable of developing a resinous acid value are controlled in kind, the reactivity of the resin towards curiny with a crosslinkiny agent as aminoaldehyde resin, isocyanate compound and the like is yreatly improved.
Eurthermore, very surprisinyly, it has been found that the present resinous composition has an excellent two-tone adhesion especially in the case of a solid color coating on a metallic coat. Thus, the present resinous composition is an ideal resinous vehicle for a top coat composition to be used in two-tone color coating.
The exact reasons why the present resinous composition can give an excellent two-tone adhesion have not been found yet, and however, the following two might do much toward the same in cooperation witll each other. That is, since an alicyclic polycarboxylic acid and a lactone are included as constituting elements oE the resin, wetting pro~erty of the coatiny composition towards a clear coat customarily applied onto a metallic coat is yreatly improved.
Secon~ly, when a solid color coating is baked at a higher temperature and then allowed to cool to a room temperature, a yreat internal stress is inevitably generated by shrinking within the coatiny and however, when the lactone is included in the polyester resin, the abovesaid internal stress is greatly relieved by the presence o~ methylene chain of said lactone. These however, should not be taken as being limitative for the present invention.
; The present inventors have also found that a similar ~ resinous composition having the desired properties can be .
provided even i~ the base resin, i.e. oil-free ~olyester resin, is replaced by an alkyd resin whose oil lenyth is up to 3~ of the total weight of the resin. Therefore, the term "polyester resin" as used herein denotes both of an oil-free polyester resin and an alkyd resin whose oil length is up to 30~ of the total weight of the resin.
The invention shall be now more fully explained in the following Examples~ Unless otherwise being stated, all parts and percentages are by weight.
() Example 1 Preparation of ~-caprolactone modified polyester resin composition Composition of -caprolactone modified polyester resin ~
hexahydro phthalic anhydride 12.15 uarts isopllthalic acid 52.18 trimethylol propane 1~.34 neopentyl ylycol 32.29 1,6~hexanedio1 7.12 -caprolactone 15.46 dibutyl tin oxide _ 0.025 Total 129.565 Into a reaction tank fitted with a heating device, a stirrer, a reflux condenser, a water separator, a fractionating column, and a thermometer, the abovementioned materials excluding isophthalic acid and -caprolactone were placed and the mixture was heat melted.
~t.~80 Stirrin~ was then started and the mixture was heated to
The present invention relates to a resinous composition for a top coat and more specifically, to a resinous composition for a top coat which is particularly useful for the coating of automobile bodies in the so-called two-tone-color coating.
Since a polyester resin can result a coating with excellent film properties as weather resistance, flame resistance, chemical resistance and the like, it is being watched with keen interest in various technical fields and especially in an automobile industry as a resinous vehicle for a top coat. Usually, a polyester resin is compounded with an aminoaldehyde resin and thus obtained composition is applled and baked to give a tough coating being excellent in mechanical properties and inter coat adhesion and the like. Nevertheless, such a composition has scarcely been used in an automobile industry as a top-coat because the coating has the problems of cissing, loss in gloss and in contrast factor, and heretofore proposed polyester resins each has a problem or poor compatibility with amino resin.
Recently, various attempts have been made to improve the properties of an oil-~ree polyester resin. For example, in Japanese Patent ~pplication Kokai No. 20068/81, published February 25, 1981, a large quantity o~ saturated alicyclic carboxylic acid or a combination of a saturated alicyclic polycarboxylic acid and ..
L~
an aromatic polycarboxylic acid are used as acid components of said polyester resin thereby attaining the improvements in cissing, loss in gloss and weather resistance of the coating and compatibility of the resin with an amino plast res~n; and in Japanese Patent Application Kokai Nos. 111864/83 and 111865/83 both published July 4, 1983, a large quantity of alicyclic polycarboxylic acid is used as an acid component and a comparatively long methylene chain is included in either one of dicarboxylic acid or diol component, or in a lactone to be used 10 for the modification of the formed polyester, thereby improving durability, adhesion properties, elongation and softness of the coating. These studies are noteworthy in a sense that they cut a path to the practical use of polyester resin, as a resinous vehicle, in an automobile top coat or coating composition to be 15 applied to flexible materials as fender, bumper and other parts.
In a top coating of automobile bodies and especially in a two-tone-color coating, the main color composition is first applied and baked, and without sanding operation, the second color 20 composition is then applled and baked. At that time there often arises often arises an interface adhesive failure between the first and the second color coatings.
~ ~ ~ 9 ~ ~
This is especially true when a solid color coating composition is applied on a metallic coat, which combination is most important and in great demand at the present moment.
What is worse still, it has been found that the higher the baking temperature of metallic coat, the poorer the two-tone adhesion.
Under the circumstances, it has long been desired to provide a polyester resin composition for a top coat which is excellent in weather resistance, film properties and curing properties, said composition being suitable forming a high build coating and to a two-tone-color coating and especially recoating of solid color onto a metallic coat, and giving an excellent two-tone adhesion over a wide range of baking conditions.
The present invention therefore provides a polyester resin which will fulfill the abovesaid requirements.
According to the invention there is provided a reslnous composition for a top coat comprising a polyester resin modified with a lactone, said polyester rcsin being composed of alcohol and acid components, lO to 80 mole ~ of the acid component being an alicyclic polycarboxylic acid or anhydride thereof and lO to 100 mole ~ of the carboxyl groups capable of developing a resinous acid value being derived from a polycarboxylic acid showing a titration midpoint potential in a non-a~ueous potentiometric titration, under the state being incorporated into the resin, of -350 mV or more, and said lactone being represented by the formula:
.
. .
.
' o O-~CH2)n~C=O
in which n is an integer of 4 to 10, and included in an amount corresponding to 5 to 30~ by weight of the total weight of the resin.
The lactone modlfied polyester resin of the present invention may be successfully and advantageously prepared by using a similar, but slightly modified method as described in Japanese Patent Application Xokai No. 4054/84. That is, a polyester resin having as acid components (a) mole of a saturated alicyclic polycarboxylic acid (A), (b) mole of a polycarboxylic acld (B) whose titration midpoint potential in non-aqueous potentiometric titration, under the state being lncorporated into the resin, is -350mV or more, and (c) mole of other poly- and/or mono-carboxylic acid (C) (wherein a+b+c=l.o mole; 0 < c mole and 10 < a x 100 < ~0 mole %) a+b+c is prepared by the combination of steps or reacting an acid mixture of (a) mole of the acld (A), (b-bl) mole of the acid (B) o and (c) mole of the acid (C), with a polyhydric alcohol to obtain a polyester prepolymer haviny a resinous acid value of M, in which M = N(l-x/100) and then adding (bl) mole of the acid (~) and continuing the esterification until it reaches to a resinous acid value of N.
In the abovesaid statement, (bl) is equal to (b) or less than (b), and denotes the molar amount of said (B) acid to be charged at~a later stage, which is determined by the following equation:
- x N x W
bl = 10,0 , ,, X --~ . p 5610~ f l - 100 wherein N stands for the resinous acid value (KOH mg required for the neutralization of lg of resinous solid matter); W is the weight of polyester resin; f is the number of Eunctional groups possessed by (B); P is the reaction percentage of (B) at the later charging stage; x is the mole% o~ (~) occupied in the carboxyl groups capable of developing a resinous acid value and determined in a range of 10 ~ x < 100.
Thus obtained polyester resin which i5 composed of alcohol and acid components, l0 to 80 mole% of the acid component being an alicyclic polycarboxylic acid and 10 to l00 mole%
of the carboxyl groups capable of developing a resinous acid value being derived from a polycarboxylic acid which will show a titration midpoint potential in a non-aqueous .~, potentiometric titration, under the state being incorporated into the resin, of -350mV or more, is then reacted with a lactone of the formula:
y~c=o wherein n is an integer of 4 to 10 in amount corresponding to 5 to 3~% by weight of the total weight o~ the resin, to obtain the present lactone modified polyester resin.
Amotlg the said acid components, examples of saturated alicyclic polycarboxylic acid (A) are cyclohexane ring beariny alicyclic acids as, for example, l,l~cyclohexane dicarboxylic acid, hexahydrophthalic acid and its anhydride, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, methylhexahydrophthalic acid and .its anhydride, hexahydrotrimellitic acid and its anhydride, and hexahydro-2-methyl-trimellitic acid and its anhydride.
Examples of polycarboxylic acid (~ aving the titration midpoint potential in non-a~ueous potentiometric titration, under the state being incororated into a resin, of -35~mV or more are aromatic polycarboxylic acids as phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride and the like. Such polycarboxylic acid per se will, in general, show, when made an electric potential-TBAH titer curve from the test results of non-aqueous potentiometric titration, a curve having multi-stage inflection points, and however, when incorporated in to a polyester chain, at least one carboxyl group will remain in a free state and the corresponding curve will have the diminished number of inflection points, accordingly.
Under such conditions, if a polycarboxylic acid is possessed of such acid strength that the aforesaid titration midpoint potential is -350mV or more, then such a member may advantageously be used for the object of the present invention.
As the acid components, other poly- and/or mono-carboxylic acids (C) than the abovesaid (A) and (B) may be present, if desired. Such acid (C) may be any of the members customarily used as an acid component of polyester resin, including aliphatic or partially saturated alicycllc acids, like succinic acid and its anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid and the like.
Futhermore, monocarboxylic acids as benzoic acid, p-t-butyl benzoic acid and the like may be added for the purpose of regulating the molecular weight of the resin.
The polyhydric alcohol component to be reacted with said acid mixture is not of specific type and suitably selected from the members customarily used for the preparation of polyester resins. Examples of such members are ethyleneglycol, diethyleneglycol, propyleneglycol, neopentylglycol, 1,2-bu~yleneglycol, 1,3-butyleneglycol, ~,3-butyleneglycol, 1,4-butyleneglycol, 1,6-hexanediol, 1,5-pentanediol, ~,5-hexanediol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, diglycerin, sorbitol, 1,4-cyclohexane dimethanol and the like.
AS already stated, the present acid controlled modified polyester resin must be of the nature such that 10 to 80 mole% of the total acid components be occupied by said saturated alicyclic polycarboxylic acid (A) and 10 to 100 mole% of .the carboxyl groups capable of developing a resinous acid value be derived from polycarboxylic acids (~) having a titration midpoint potential in a non-aqueous potent.iometric titration, under a state such that carboxylic acid is capable of developing a resinous acid value, of -~50mV or more. This is because, if the content of saturated alicyclic polycarboxylic acid is less than 10 mole~ of the total acid components, weather resistance may not be improved, whereas if it exceeds the upper limit of 80 mole~, the chamical resistance be lowered. As to the ratio oE carboxyl groups responsible for the development of the resinous acid value, if the amount of said polycarboxylic acid having the specified cid strength is less than 10 mole%, then there is a general trend towards producing coating of insuEficient gloss and curing properties and hence, the object of the present invention cannot be attained.
In an actual preparation of said acid controlled modified polyester resin, a polyester prepolymer is first prepared by using an acidic mixture of said acid (A) and poly- and/or mono-carboxylic acid (C) including, as desired, a part of the polycarboxylic acid (B), together with a polyhydric alcohol, and to thus obtained polyester prepolymer, the whole or remaining parts of the acid (B) is then added and the esterification is continued to obtain the intended product. As to the amounts of polycarboxylic acid (B) to be charyed in the first and in the second stage of reaction, the later charging amount (bl mole) is calculated beforehand from the abovesaid equation using a number of valiable, i.e.
(f): number of functional groups possessed by the acid (B), (N): resinous acid value, (W): weight oE the resin, (x): mole% oE the carboxyl groups derived from the acid (B) occupied in the total carboxyl groups capable of developiny resinous acid value, and (P): reaction percentage o the later charging acid (B), and the amount (b mole) o said acid (B) to be charged in the first stage is determined as (l-bl) mole.
Incidentally, in the abovesaid equation, the reaction percentage (P) is the value showing the meaning of what % of carboxyl groups in the polycarboxylic acid ~B) should be reacted in order that the acid is surely incorporated into the polyester chain through an esterification, and said (P) is, for example, 50% or more in the case of dicarboxylic acid as phthalic anhydride, and about 34% or more in the case of tricarboxylic acid as trimellitic acid.
The esterification of polycarboxylic acids with a polyhydric _ 9 _ .
o alcohol may be carried out in a conventional way and no particualr technique is required therefor.
In a preferred embodiment, the esterification shall be continued until the resinous acid value comes to 1 to 135 in the first step for obtaining a polyester prepolymer and to 1 to 150 in the second step for obtaining an acid controlled modified polyester resin. As to a number average molecular weight of the polyester resin, it may be freely selected in the range which is cornmon in the heretofore proposed polyester resins for coatiny use.
In this way, an acid controlled modified polyester resin having alcohol and acid components, 1~ to ~0 mole% of said acid component being an alicyclic polycarboxylic acid (A) and 10 to 100 mole% of the carboxyl yroups capable of developiny a resinous acid value being derived from a polycarboxylic acid (B) showing a titration midpoint potential in a non-a~ueous potentiometrlc titration, under the state being incorporated into the resin, of -350 mV or more, can be obtained.
According to the present invention, the abovesaid polyester resin is then reacted with a lactone of the formula:
O-(CH2)n-cl=o wherein n is an integer o~ 4 to 10, to obtain an acid controlled, lactone-modified polyester resin.
Examples of said lactone are ~-caprolactone, ~-enantholactone, ~-caprylolactone, and their ring substituted derivativ~s. Particularly preferred members are the lactones having 6 to 8 carbon atoms.
Lactone modiEication may be carried out in a conventional way by adding a lactone to the abovesaid acid controlled modified polyester resin and heating the mixture.
At this time, the added lactone is rin~-opened and reacted with a hydroxyl goup of said polyester resin to give a lactone modified resin.
In this reaction, it is preferred to use a catalyst as tin compounds, or~anic lead or manganese salts, and the like.
Particularly preferred members are the tin compounds of the formula:
X X / X' sno or Sn X , X X' wherein X stands for an alkyl, an aryl, an aralkyl, or an aryloxy group, and X' is an alkyl, an aryl, an aralkyl, an acyloxy, a haloyen or hydroxyl group.
As, for example, tetraphennyl tin, tetraoctyl tin, diphenyl tin dilaurate, tri-n~butyl tin hydroxide, tri-n-butyl tin acetate, dimethyl tin oxide, dibutyl tin oxide, dilauryl tin oxide, di-n-butyl tin dichloride, dioctyl tin dichloride and the like, and lead acetate, manganese acetate, lead 2-ethyl hexane acetate, lead salicylate, lead benzoate and the like.
The lactone moiety of thus obtained polyester resin is believed, under the state incorporated into the polyester chain, to produce an optimum flexibility oE the resin. The :
::
presence of lactone in the polyester resin is, thus, important in this invention and however, the lactone amount should preferably be limitted in a range corresponding to 5 to 30~ of tlle total weight of the resin. This is because, if the lactone amount is less than 5% by weight of the total resin, it is unable to get the desired elongation, Erichsen test results and impact resistance, and if it is over the upper limit of 30~ by weight of the total resin, there will give a coating with inferior properties especially in respect of tensile strength, hardness, chemical resistance and water resistance. These are undesirable for the intended object of having a resinous composition for a top coat.
The present resinous composition has many desirable properties as follows.
~ince an alicyclic polycarboxylic acid is used as a part of acid component oE the polyester resin, an excellent weather resistance is given to the coating.
Since the resin is modified with a lactone, impact resistance of the coating is greatly improved.
From the abovesaid two characteristics, an improved solubility is given to the resin and hence a high solid coating composition can be formulated with the present resinous composition.
Since a reactive hydroxyl group is given to the resin by the lactone modification and the carboxyl groups capable of developing a resinous acid value are controlled in kind, the reactivity of the resin towards curiny with a crosslinkiny agent as aminoaldehyde resin, isocyanate compound and the like is yreatly improved.
Eurthermore, very surprisinyly, it has been found that the present resinous composition has an excellent two-tone adhesion especially in the case of a solid color coating on a metallic coat. Thus, the present resinous composition is an ideal resinous vehicle for a top coat composition to be used in two-tone color coating.
The exact reasons why the present resinous composition can give an excellent two-tone adhesion have not been found yet, and however, the following two might do much toward the same in cooperation witll each other. That is, since an alicyclic polycarboxylic acid and a lactone are included as constituting elements oE the resin, wetting pro~erty of the coatiny composition towards a clear coat customarily applied onto a metallic coat is yreatly improved.
Secon~ly, when a solid color coating is baked at a higher temperature and then allowed to cool to a room temperature, a yreat internal stress is inevitably generated by shrinking within the coatiny and however, when the lactone is included in the polyester resin, the abovesaid internal stress is greatly relieved by the presence o~ methylene chain of said lactone. These however, should not be taken as being limitative for the present invention.
; The present inventors have also found that a similar ~ resinous composition having the desired properties can be .
provided even i~ the base resin, i.e. oil-free ~olyester resin, is replaced by an alkyd resin whose oil lenyth is up to 3~ of the total weight of the resin. Therefore, the term "polyester resin" as used herein denotes both of an oil-free polyester resin and an alkyd resin whose oil length is up to 30~ of the total weight of the resin.
The invention shall be now more fully explained in the following Examples~ Unless otherwise being stated, all parts and percentages are by weight.
() Example 1 Preparation of ~-caprolactone modified polyester resin composition Composition of -caprolactone modified polyester resin ~
hexahydro phthalic anhydride 12.15 uarts isopllthalic acid 52.18 trimethylol propane 1~.34 neopentyl ylycol 32.29 1,6~hexanedio1 7.12 -caprolactone 15.46 dibutyl tin oxide _ 0.025 Total 129.565 Into a reaction tank fitted with a heating device, a stirrer, a reflux condenser, a water separator, a fractionating column, and a thermometer, the abovementioned materials excluding isophthalic acid and -caprolactone were placed and the mixture was heat melted.
~t.~80 Stirrin~ was then started and the mixture was heated to
2~0~. At this time, from 200C to 240C, the temperature was raised at a constant speed in 3 hours. The formed condensation water was successively distilled out o the system. When the tank content was reached to 24UC, the mixture was maintained at the same tempearature for 30 minutes, 3 parts of xylene were then gradually added, and reaction was switched to a condensation in the presence of said solvent and continued until the resinous aci~ value reached to 2Ø The tank was then allowed to cool to lOO~C
to obtain a polyester preplolymer A-l.
Next, 52.18 parts of isophthalic acid were added to the reaction tank and the mixture was heated to 220C. At this time, from 1~0C to 220C, the temperature was gradually raised at a constant speed in 3 hours. The reaction was continued at 220C until the resinous acid value came to 10 and thereafter, the mixture was allowed to cool to obtain a polyester prepolyrner ~-2, 20 mole~ of whose acid component being occupied by the abovementioned alicyclic polycarboxylic acid and 80 mole~ of the carboxyl yroups capable of developing the resinous acid value being based on isophthalic acid. This resin showed a titration midpoint potential of -310mV in a non-aqueous potentiometric titration. 15.46 parts of -caprolactone and B.5 parts of xylene were then added to the reaction ~ank and the whole content was maintained at 150C for a several hours, while checking the amount of unreacted -caprolactone by lR
,, ~
means. When the reaction rate reached to 98% or more, the reaction was stopped and the mixture was allowed to cool.
Thereafter, the tank content was diluted with 32.7 parts of xylene to obtain ~-caprolactone modiEied polyester resin varnish A, the amount of ~-caprolactone beiny 15 wt% of the total weiyht of the resin, the solid content being 70.1~, varnish viscosity (Gardner, 25C) beiny V and resinous acid value being 8.8.
Examples 2 to 3 The same procedures as stated in ~xample 1 were repeated with the materials shown in Table 1 and -caprolactone modified polyester resin varnishes B and C were obtained.
The cahracteristics of these varnishes are shown in Table 1.
Examples 4 to 5 The same procedures as stated in Example 1 were repeated with the materials shown in Table 1 and ~-caprolactone modiEied polyester resin varnishes D and E were obtained.
~mong the carboxyl groups capable of developin~ resinous acid value, 85 mole~ was derived from phthalic anhydride in Example 4 and 90 mole% was derived from tetrachlorophthalic anhydride in Example 5. The titration midpoint potentials in non-aqueous potentiometric titration of these resins were -290 mV and -120 mV. The characteristics of the resin varnishes are shown in Table 1.
ZS Examples 6 to 9 The same procedures as stated in Example 1 were repeated with the materials shown in Table 1 and -caprolactone ~, ~
o modified polyester resin varnishes E` to I were obtained.
'l'he characteristics of these varnishes are shown in Table 1.
Example 10 Using 3-methyl hexahydro phthalic anhydride as an alicyclic polycarboxylic acid and the materials shown in Table 1 and ollowing the procedures of Example 1, a -caprolactone modified polyester resin varnish J was obtained, the characteristics o~ said varnish being shown in Table 1.
Example 11 Using the same materials and the same procedures as stated in Example 1, but charging -caprolactone together with other materials in the first step of reaction and increasing the amount of dibutyl tin oxide from ~.025 part to ~.~75 part, -caprolactone modified polyester resin varnish K was lS prepared by both ester exchange reaction and esterification reaction. 'l'he characteristics of this varnish are shown in Table 1.
~omparative Examples 1 to 6 Using the materials shown in Table 1 and following the procedures given in Example 1, various comparative resin varnishes were prepared.
Tlle varnishes L and M o~ Comparative Examples 1 and 2 were ~ased on polyester reslns containing no alicyclic polycarboxylic acid and no lactone.
~5 The varnish N of Comparative Example 3 was based on polyester resin containing no lactone, whose carboxyl groups capable of developin~ a resinous acid value were derived ~, ~
. . .
~;9'~
Erom the polycarboxylic acid showing a titration midpoint potential in non-aqueous potentiometric titration, of -400 mV. The varnish ~ of Comparative Example 4 was based on a polyester resin modified with 40 wt% lactone, whose carboxyl groups capable of developing the resinous acid value were derived from the polycarboxylic acid showing a titration midpoint potential in a non-aqueous potentiometric titration, under the state incorporated into the resin, of -400 mV. The varnishes P and ~ of ~omparative Examples 5 and 6 each was based on a polyester resin modified with a lactone, but including no alicyclic polycarboxylic acid.
The characteristics of these varnishes are shown in Table 1.
- 18 - ~
'l'able 1 Resin compositions and characteristics of resinous varnishes Example No. 1 2 3 varnish A B C
S Polyester 1st step hexahydrophthalic anhydride 12.1524.1741.~5 isophthalic acid
to obtain a polyester preplolymer A-l.
Next, 52.18 parts of isophthalic acid were added to the reaction tank and the mixture was heated to 220C. At this time, from 1~0C to 220C, the temperature was gradually raised at a constant speed in 3 hours. The reaction was continued at 220C until the resinous acid value came to 10 and thereafter, the mixture was allowed to cool to obtain a polyester prepolyrner ~-2, 20 mole~ of whose acid component being occupied by the abovementioned alicyclic polycarboxylic acid and 80 mole~ of the carboxyl yroups capable of developing the resinous acid value being based on isophthalic acid. This resin showed a titration midpoint potential of -310mV in a non-aqueous potentiometric titration. 15.46 parts of -caprolactone and B.5 parts of xylene were then added to the reaction ~ank and the whole content was maintained at 150C for a several hours, while checking the amount of unreacted -caprolactone by lR
,, ~
means. When the reaction rate reached to 98% or more, the reaction was stopped and the mixture was allowed to cool.
Thereafter, the tank content was diluted with 32.7 parts of xylene to obtain ~-caprolactone modiEied polyester resin varnish A, the amount of ~-caprolactone beiny 15 wt% of the total weiyht of the resin, the solid content being 70.1~, varnish viscosity (Gardner, 25C) beiny V and resinous acid value being 8.8.
Examples 2 to 3 The same procedures as stated in ~xample 1 were repeated with the materials shown in Table 1 and -caprolactone modified polyester resin varnishes B and C were obtained.
The cahracteristics of these varnishes are shown in Table 1.
Examples 4 to 5 The same procedures as stated in Example 1 were repeated with the materials shown in Table 1 and ~-caprolactone modiEied polyester resin varnishes D and E were obtained.
~mong the carboxyl groups capable of developin~ resinous acid value, 85 mole~ was derived from phthalic anhydride in Example 4 and 90 mole% was derived from tetrachlorophthalic anhydride in Example 5. The titration midpoint potentials in non-aqueous potentiometric titration of these resins were -290 mV and -120 mV. The characteristics of the resin varnishes are shown in Table 1.
ZS Examples 6 to 9 The same procedures as stated in Example 1 were repeated with the materials shown in Table 1 and -caprolactone ~, ~
o modified polyester resin varnishes E` to I were obtained.
'l'he characteristics of these varnishes are shown in Table 1.
Example 10 Using 3-methyl hexahydro phthalic anhydride as an alicyclic polycarboxylic acid and the materials shown in Table 1 and ollowing the procedures of Example 1, a -caprolactone modified polyester resin varnish J was obtained, the characteristics o~ said varnish being shown in Table 1.
Example 11 Using the same materials and the same procedures as stated in Example 1, but charging -caprolactone together with other materials in the first step of reaction and increasing the amount of dibutyl tin oxide from ~.025 part to ~.~75 part, -caprolactone modified polyester resin varnish K was lS prepared by both ester exchange reaction and esterification reaction. 'l'he characteristics of this varnish are shown in Table 1.
~omparative Examples 1 to 6 Using the materials shown in Table 1 and following the procedures given in Example 1, various comparative resin varnishes were prepared.
Tlle varnishes L and M o~ Comparative Examples 1 and 2 were ~ased on polyester reslns containing no alicyclic polycarboxylic acid and no lactone.
~5 The varnish N of Comparative Example 3 was based on polyester resin containing no lactone, whose carboxyl groups capable of developin~ a resinous acid value were derived ~, ~
. . .
~;9'~
Erom the polycarboxylic acid showing a titration midpoint potential in non-aqueous potentiometric titration, of -400 mV. The varnish ~ of Comparative Example 4 was based on a polyester resin modified with 40 wt% lactone, whose carboxyl groups capable of developing the resinous acid value were derived from the polycarboxylic acid showing a titration midpoint potential in a non-aqueous potentiometric titration, under the state incorporated into the resin, of -400 mV. The varnishes P and ~ of ~omparative Examples 5 and 6 each was based on a polyester resin modified with a lactone, but including no alicyclic polycarboxylic acid.
The characteristics of these varnishes are shown in Table 1.
- 18 - ~
'l'able 1 Resin compositions and characteristics of resinous varnishes Example No. 1 2 3 varnish A B C
S Polyester 1st step hexahydrophthalic anhydride 12.1524.1741.~5 isophthalic acid
3-methyl hexahydro phthalic anhydride -caprolactone trimethylol propane 10.3410.3410.34 neouentyl glycol 32.2932.0931.80 1,6-hexanediol 7.12 7.07 7.01 coconut fatty acid 2nd SteL) isophthalic acid 52.1838.Y219.30 phthalic anhydride tetrachloro phthalic anllyclride 3rd step ~-caprolactone 15.4615.7216.11 wt% of the total resin (~) 15 15 15 alicyclic polycarboxylic acid (mole~) 20 40 70 titration midpoint potential (mV) -310 -310 -310 oil length (%) Characteristics of varnish non-volatile content (%) 70.1 69.8 69.8 varnish viscosity Y W T-U
resin. acid value of the finished resin 8.8 8.7 8.7 . , ~
.:.. ;~., ' ~9~30 Table 1 (continued) Example No. 4 5 6 varnish ~ E F
Polyester 1st step hexahydrophthalic anhydride 29.0726.38 30.13 isophthalic acid 31.2128.32 3-methyl hexahydro phthalic anhydride -caprolactone trimethylol propane 10.3415.38 1~.34 neopentyl glycol 32.0127.70 31.99 1,6-hexanediol 7.066.11 7.05 coconut Eatty acid 2nd step isouhthalic acid 32.34 phtllalic anllydride 2.~5 tetrachloro phthalic anhydride 9.5U
3rd step -caprolactone 15.8716.55 4.73 wt~ of the total resin (%) 15 15 5 alicyclic polycarboxylic acid (mole~)50 50 50 titration midpoint potential (mV) -290 -120 -310 oil lenyth (~) Characteristics of varnish non-volatile content (%) 70.075.2 7U.4 varnish viscosity V-W U-V Y
resin. acid value of the finished resin 8.5 18.1 9.6 , Table 1 (continued) E'xample No. 7 8 9 varnish G H
Polyester 1st step S hexahydrophthalic anhydride30.13 26.7423.60 isophthalic acid 3-methyl hexahydro phthalic anhydride ~-caprolactone trimethylol propane 10.34 16.8623.37 neopentyl glycol 31.99 23.6315.26 1,6-hexanediol 7.05 5.21 3.37 coconut fatty acid 9.97 19.94 2nd step isophthalic acid 32.34 28.7125.07 lS phthalic anllydride tetrachloro pllthalic anhydride 3rd step ~-caprolactone 38.50 10.0122.61 wt~ of the total resin (~) 30 10 10 20 alicyclic polycarboxylic acid (mole%) 50 50 50 titration midpoint potential (mV) -310 -310 -310 oil length (%) 10 20 Characteristics of varnish non-volatile content (%) 70,2 70.1 70.0 varnish viscosity P-Q V S
resin. acid value of the finished resin 7.0 8.9 7.8 j :
Table 1 (continued) ~xample No. 10 11 varnish J K
Polyester 1st step hexahydrophthalic anllydride 12.15 isophthalic acid 3-methyl hexahydro phthalic anhydride12.56 -caprolactone 15.46 trimethylol propane lU.34 10.34 neopentyl ylycol 32.29 32.29 1,6-hexanediol 7.12 7.12 coconut Eatty acid 2nd step isoptlthalic acid 52.18 52.18 phthalic anhydride tetrachloro phthalic anhydride 3rd 9 tep ~-caprolactone 15.26 wt~ of the total resin (~) 15 15 20 alicyclic polycarboxylic acid (mole%) 20 20 titration midpoint potential (mV)-310 -310 oil length (~) Characteristics of varnish non-volatile content (~) 70.3 69.8 varnish viscosity W>X X-W
resin. acid value of the finished resin 8.5 8.4 ~,:
. . .
,. :.
~ ' ~
Table 1 (contir-ued) Comparative Example No. 1 2 3 varnish L M N
Polyester 1st step hexahydropllthalie anhydride 41.95 isophthalic aeid 41023 19.30 phthalic anhydride 38.91 9.07 adipie acid trimethylol propane 32.28 22.90 lU.34 neopentyl ylycol 5.01 16.67 31.80 1,6-hexanediol 1.12 3.67 7.01 eoeonut fatty aeid 29.92 19.95 2nd step isouhthalie aeid phthalie anhydricle tetraehloro phthalie anllydride 3rd step ~-eaprolaetone wt~ of the total resin (~) 20 alieyelie polyearboxylie aeid (mole%) 0 0 70 titration midpoint potential (mV)-290 -310 -400 oil length (~) 30 20 Charaeteristies of varnish non-volatile content (%)60.260.5 7~.2 varnish viscosity V-W U X-Y
resin. aeid value of the finished resin 8.1 8.1 9.9 (3 Table 1 (continued) ~omparative Example No. 4 5 6 varnish o P Q
Polyester 1st step hexahydrophthalic anhydride30.26 isophthalic acid 32.49 707.0 707.0 phthalic anhydride adipic acid 155.U 155.0 trimethylol propane 11.31 223.0 223.0 neopentyl glycol 30.85 319.0 319.0 1,6-hexanediol 6.80 188.0 188.0 coconut fatty acid 2nd step isophthalic acid phthalic anhydride tetrachloro phthalic anhydride 3rd step -caprolactone 5~.89 210.0 840.0 wt% of the total resin (%) 40 13 37.5 2~ alicyclic polycarboxylic acid (mole%) 50 0 titration midpoint potential (mV) -400 310 -310 oil length (~) Characteristics of varnish non-volatile content (~) 69.8 70.2 7U.4 varnish viscosity Q V-W T>U
resinO acid value of the finished resin 8.5 13.0 9.2 L~
Example 12 Using the lactone modified polyester resin varnish obtained in Example 1, a white colored dispersion paste was prepared as prescribed in the following Table A and then, a white colored coating composition as prescribed in ~'able B.
Table A
Formulation of white colored dispersion paste Titanium white (Note 1) 62 parts resin varnish . 23 xylene 9 Solvesso 100 ~c~ 6 Total100 parts Note 1: Titanium CR-95, manufactured by Ishihara Sangyo K.K.
Table B
E`ormulation of white colored coating composition white colored dispersion paste 100 parts resin varnish 44 melamine resin (Note 2) 26 n-butanol 3.5 triethylamine 0.5 surface conditioner _0.3 Total 174.3 parts Note 2: U-ban 128, manufactured by Mitui Toatu K.K.
Thus obtained coating composition was diluted with a mixed solvent of Solvesso 100/toluene/methyl isobutyl ketone/butyl acetate = 60/20/10/10, to a viscosity of 23 seconds/No.4 Ford Cup (20C).
, For the subsequent test purpose, the coatiny substrates were prepared as Eollows.
~PC-l du11 steel plate was degreased, treated with zinc pllospllate, subjected to a cationic electrodeposition and then coated with an inter coat.
Eor 2-tone adhesion test, thus coated plate was further applied with a metallic coat, by using 2 coat 1 bake system with an acrylic resin/melamine resin based metallic coating composition.
The metallic coat was baked at 180C for 3U minutes.
Onto thus prepared coating substrates, i.e. steel plate with an inter coat and steel plate with a metallic coat, the abovesaid diluted top coat composition was spray-coated so as to give a dry film thickness of 3~ to 40~ , and the coated plates were, after standlng ~or a defined period of time, baked at 14~C for 3U minutes. Thus obtained coatings were tested and evaluated as Eollows.
1) E`inishing appearance Finishing appearance was evaluated by visual observation of glossr cissing and surface condition of the coating. l`est results are given as O --no such defects X .- some defects, no yood 2) Pencil hardness test 3) Impact strenyth test ~u Pont type ~ = 1/2" 500g
resin. acid value of the finished resin 8.8 8.7 8.7 . , ~
.:.. ;~., ' ~9~30 Table 1 (continued) Example No. 4 5 6 varnish ~ E F
Polyester 1st step hexahydrophthalic anhydride 29.0726.38 30.13 isophthalic acid 31.2128.32 3-methyl hexahydro phthalic anhydride -caprolactone trimethylol propane 10.3415.38 1~.34 neopentyl glycol 32.0127.70 31.99 1,6-hexanediol 7.066.11 7.05 coconut Eatty acid 2nd step isouhthalic acid 32.34 phtllalic anllydride 2.~5 tetrachloro phthalic anhydride 9.5U
3rd step -caprolactone 15.8716.55 4.73 wt~ of the total resin (%) 15 15 5 alicyclic polycarboxylic acid (mole~)50 50 50 titration midpoint potential (mV) -290 -120 -310 oil lenyth (~) Characteristics of varnish non-volatile content (%) 70.075.2 7U.4 varnish viscosity V-W U-V Y
resin. acid value of the finished resin 8.5 18.1 9.6 , Table 1 (continued) E'xample No. 7 8 9 varnish G H
Polyester 1st step S hexahydrophthalic anhydride30.13 26.7423.60 isophthalic acid 3-methyl hexahydro phthalic anhydride ~-caprolactone trimethylol propane 10.34 16.8623.37 neopentyl glycol 31.99 23.6315.26 1,6-hexanediol 7.05 5.21 3.37 coconut fatty acid 9.97 19.94 2nd step isophthalic acid 32.34 28.7125.07 lS phthalic anllydride tetrachloro pllthalic anhydride 3rd step ~-caprolactone 38.50 10.0122.61 wt~ of the total resin (~) 30 10 10 20 alicyclic polycarboxylic acid (mole%) 50 50 50 titration midpoint potential (mV) -310 -310 -310 oil length (%) 10 20 Characteristics of varnish non-volatile content (%) 70,2 70.1 70.0 varnish viscosity P-Q V S
resin. acid value of the finished resin 7.0 8.9 7.8 j :
Table 1 (continued) ~xample No. 10 11 varnish J K
Polyester 1st step hexahydrophthalic anllydride 12.15 isophthalic acid 3-methyl hexahydro phthalic anhydride12.56 -caprolactone 15.46 trimethylol propane lU.34 10.34 neopentyl ylycol 32.29 32.29 1,6-hexanediol 7.12 7.12 coconut Eatty acid 2nd step isoptlthalic acid 52.18 52.18 phthalic anhydride tetrachloro phthalic anhydride 3rd 9 tep ~-caprolactone 15.26 wt~ of the total resin (~) 15 15 20 alicyclic polycarboxylic acid (mole%) 20 20 titration midpoint potential (mV)-310 -310 oil length (~) Characteristics of varnish non-volatile content (~) 70.3 69.8 varnish viscosity W>X X-W
resin. acid value of the finished resin 8.5 8.4 ~,:
. . .
,. :.
~ ' ~
Table 1 (contir-ued) Comparative Example No. 1 2 3 varnish L M N
Polyester 1st step hexahydropllthalie anhydride 41.95 isophthalic aeid 41023 19.30 phthalic anhydride 38.91 9.07 adipie acid trimethylol propane 32.28 22.90 lU.34 neopentyl ylycol 5.01 16.67 31.80 1,6-hexanediol 1.12 3.67 7.01 eoeonut fatty aeid 29.92 19.95 2nd step isouhthalie aeid phthalie anhydricle tetraehloro phthalie anllydride 3rd step ~-eaprolaetone wt~ of the total resin (~) 20 alieyelie polyearboxylie aeid (mole%) 0 0 70 titration midpoint potential (mV)-290 -310 -400 oil length (~) 30 20 Charaeteristies of varnish non-volatile content (%)60.260.5 7~.2 varnish viscosity V-W U X-Y
resin. aeid value of the finished resin 8.1 8.1 9.9 (3 Table 1 (continued) ~omparative Example No. 4 5 6 varnish o P Q
Polyester 1st step hexahydrophthalic anhydride30.26 isophthalic acid 32.49 707.0 707.0 phthalic anhydride adipic acid 155.U 155.0 trimethylol propane 11.31 223.0 223.0 neopentyl glycol 30.85 319.0 319.0 1,6-hexanediol 6.80 188.0 188.0 coconut fatty acid 2nd step isophthalic acid phthalic anhydride tetrachloro phthalic anhydride 3rd step -caprolactone 5~.89 210.0 840.0 wt% of the total resin (%) 40 13 37.5 2~ alicyclic polycarboxylic acid (mole%) 50 0 titration midpoint potential (mV) -400 310 -310 oil length (~) Characteristics of varnish non-volatile content (~) 69.8 70.2 7U.4 varnish viscosity Q V-W T>U
resinO acid value of the finished resin 8.5 13.0 9.2 L~
Example 12 Using the lactone modified polyester resin varnish obtained in Example 1, a white colored dispersion paste was prepared as prescribed in the following Table A and then, a white colored coating composition as prescribed in ~'able B.
Table A
Formulation of white colored dispersion paste Titanium white (Note 1) 62 parts resin varnish . 23 xylene 9 Solvesso 100 ~c~ 6 Total100 parts Note 1: Titanium CR-95, manufactured by Ishihara Sangyo K.K.
Table B
E`ormulation of white colored coating composition white colored dispersion paste 100 parts resin varnish 44 melamine resin (Note 2) 26 n-butanol 3.5 triethylamine 0.5 surface conditioner _0.3 Total 174.3 parts Note 2: U-ban 128, manufactured by Mitui Toatu K.K.
Thus obtained coating composition was diluted with a mixed solvent of Solvesso 100/toluene/methyl isobutyl ketone/butyl acetate = 60/20/10/10, to a viscosity of 23 seconds/No.4 Ford Cup (20C).
, For the subsequent test purpose, the coatiny substrates were prepared as Eollows.
~PC-l du11 steel plate was degreased, treated with zinc pllospllate, subjected to a cationic electrodeposition and then coated with an inter coat.
Eor 2-tone adhesion test, thus coated plate was further applied with a metallic coat, by using 2 coat 1 bake system with an acrylic resin/melamine resin based metallic coating composition.
The metallic coat was baked at 180C for 3U minutes.
Onto thus prepared coating substrates, i.e. steel plate with an inter coat and steel plate with a metallic coat, the abovesaid diluted top coat composition was spray-coated so as to give a dry film thickness of 3~ to 40~ , and the coated plates were, after standlng ~or a defined period of time, baked at 14~C for 3U minutes. Thus obtained coatings were tested and evaluated as Eollows.
1) E`inishing appearance Finishing appearance was evaluated by visual observation of glossr cissing and surface condition of the coating. l`est results are given as O --no such defects X .- some defects, no yood 2) Pencil hardness test 3) Impact strenyth test ~u Pont type ~ = 1/2" 500g
4) accelerated weather resistance test 6~ gloss retention (%) was determined after haviny - 26 ~
o subjected to ~unshine Weather-O-meter for 20~ hours.
o subjected to ~unshine Weather-O-meter for 20~ hours.
5) Baked residue test 1.59 o~ the diluted coatiny composition (viscosity: 23 seconds/No. 4 Ford Cup, 20C) was heat-dried at lU5C for 3 hours and the baked residue was determined.
6) Two-tone adhesion test Cross-cuts with lmm width cut were made in lcm square coating with a rager and peel test was carried out with a @~ ~e JI~7ph~ 2~ e,~a~a~c) ;X3~ 4~h~e tape. The result was evaluated by the number of peeled out coatings in lcm square.
The test results are shown in Table 2.
Examples 13 to 22 Using the lactone modified polyester resin varnishes B to K
obtained in Examples 2 to 11, white colored coating compositions were prepared as in Example 12. However, in Example 16 usiny the lactone modified polyester resin varnish E, the following was used in place of the formulation Table B.
Table C
2~ Formulation of white colored coating composition for Example 16 white colored dispersion paste lU0 parts resin varnish E 44 melamine resin (Note 3) 16 n-butanol 3.5 triethylamine 0.5 surface conditioner 0.3 Total 164.3 parts Note 3: Cymel 303, trade mark of Mitui Toatu K.K.
(methylolated melamine) Thus obtalned coatiny compositions were applied onto the coating substrates and evaluated in the same way as stated in Example 12. The test results are shown in Table 2.
Comparative Examples 7 to 12 Usiny the polyester resin varnishes L to Q obtained in Comparative Examples 1 to ~, the coating compositions were prepared as in Example 12. The amounts of varnishes were controlled so as to give a defined amount of resin content.
These compositions were applied to the coating substrates and evaluated as ln Example 12. The test results are shown in Table 2.
- 2~ -tJ ~
tD ~ tD I--- tD tD X
rt i~ t) O fD tD P) t~
tDtD rt 1--- 3 ~ tD
D) ~D D) tn :J ~ tD
n rt rt - tD
tD ~ ~ tD CL
U~ C
I-- tD ~: ~ tD
OtD rt tn tD
r~ It rt ~
O~o tD ::1 ~-- ~5 t) ~D
tD
tn ~_.
~0 t) o ~:
o a~
~ om ~ o 3, o ~ P~
o rt tD
t,J ~3 I~ rt t:r o ~C 1~
o 1-- tD
C~ P,~ O ~--~- ~ o om ~ 1- ~ w ~
o o w rt tD
~_ rt o o a~
\ ~ P om ~ o t~ P
o ~
o rt tD
o l--o a~ ~o P O 1~
~ ~ 5~ tJ ~n o co rt o tD
C~
tD
~_ o O ~I _, Pm ,~
o ~ oW ~J O ~ a~
o ~ ~
o rt tD
i .:
N ~J Sl) ~ ~ ~ ~ ~ t~
U) C
~ ~1) ~ ~D ~ 5 O (D ~t V) (D
rt ~r p, o~ (D ::~
~S
tn ~, ,.~ .
(D
C
o o~ o~ W I ~ ,_ ~P o o O 0 o I~
o rt p~
C ~
o Ul W o~ ,_ o o . O p, ~, O ~
C
CL
c ~ It o ~:
o o~
~ m O ,, ~C ~
O W
C~
c l_ O ~ ~
o a~ _1 . ~ I o ~ H O
o a~
O (D
o a~
-I ~ (J~ ~ O o c~ ~_ ~-- .P
o r~
O
. .
' ' ' :
, ¢
n ~ x ~ ~ 3 31_ U) D
O (D (D P) O ~p) 1- ~
3 a, 1~ 3 3 ~U
D ~D r~ 1~ 3 ~ 1--~¢ ~¢ 1- 3 ~ ~D
P) (D ~ U~ ~ 3(D ~Z) ~ ¢ ~¢ 3 3 U~ C
O (D ~t tn(D O
,t ~¢
~ ~ p) D~D (D 3 ~¢ ~
(D X
,¢ ~) (D
,_. IJ
~ .
.
~r C
o ~C
O cn oo ~ o O ~ O O
o o , (D
~D
C
~ w m ~ o ~ 3 I~ . o 1~ o w o o ~ 1 3 (1:1 C
a~
C
~- ~ g w ~ ~ ~ I~ ~
o o UlW ~J O :~ 'a o ~J ~ oo o r~
~D
C
O
O Z
~n Ul O W
o 1-- r~
o C
~C g c~ ~ W ,~
a~ ~ Uol ~ ~
o c~ W rt O
o ' ' ' 8~) Table 2 (continued) Comparative Example 11 12 resin ~arnish P
melamine butylolated butylolated Finishiny appearance O O
Pencil hardness B 2B
impact strenyth 40 5U
accelerated weather resistance 35 25 baked residue (wt~) 65.2 66.4 2 tone adhesion 90/100 95/100 '~
The test results are shown in Table 2.
Examples 13 to 22 Using the lactone modified polyester resin varnishes B to K
obtained in Examples 2 to 11, white colored coating compositions were prepared as in Example 12. However, in Example 16 usiny the lactone modified polyester resin varnish E, the following was used in place of the formulation Table B.
Table C
2~ Formulation of white colored coating composition for Example 16 white colored dispersion paste lU0 parts resin varnish E 44 melamine resin (Note 3) 16 n-butanol 3.5 triethylamine 0.5 surface conditioner 0.3 Total 164.3 parts Note 3: Cymel 303, trade mark of Mitui Toatu K.K.
(methylolated melamine) Thus obtalned coatiny compositions were applied onto the coating substrates and evaluated in the same way as stated in Example 12. The test results are shown in Table 2.
Comparative Examples 7 to 12 Usiny the polyester resin varnishes L to Q obtained in Comparative Examples 1 to ~, the coating compositions were prepared as in Example 12. The amounts of varnishes were controlled so as to give a defined amount of resin content.
These compositions were applied to the coating substrates and evaluated as ln Example 12. The test results are shown in Table 2.
- 2~ -tJ ~
tD ~ tD I--- tD tD X
rt i~ t) O fD tD P) t~
tDtD rt 1--- 3 ~ tD
D) ~D D) tn :J ~ tD
n rt rt - tD
tD ~ ~ tD CL
U~ C
I-- tD ~: ~ tD
OtD rt tn tD
r~ It rt ~
O~o tD ::1 ~-- ~5 t) ~D
tD
tn ~_.
~0 t) o ~:
o a~
~ om ~ o 3, o ~ P~
o rt tD
t,J ~3 I~ rt t:r o ~C 1~
o 1-- tD
C~ P,~ O ~--~- ~ o om ~ 1- ~ w ~
o o w rt tD
~_ rt o o a~
\ ~ P om ~ o t~ P
o ~
o rt tD
o l--o a~ ~o P O 1~
~ ~ 5~ tJ ~n o co rt o tD
C~
tD
~_ o O ~I _, Pm ,~
o ~ oW ~J O ~ a~
o ~ ~
o rt tD
i .:
N ~J Sl) ~ ~ ~ ~ ~ t~
U) C
~ ~1) ~ ~D ~ 5 O (D ~t V) (D
rt ~r p, o~ (D ::~
~S
tn ~, ,.~ .
(D
C
o o~ o~ W I ~ ,_ ~P o o O 0 o I~
o rt p~
C ~
o Ul W o~ ,_ o o . O p, ~, O ~
C
CL
c ~ It o ~:
o o~
~ m O ,, ~C ~
O W
C~
c l_ O ~ ~
o a~ _1 . ~ I o ~ H O
o a~
O (D
o a~
-I ~ (J~ ~ O o c~ ~_ ~-- .P
o r~
O
. .
' ' ' :
, ¢
n ~ x ~ ~ 3 31_ U) D
O (D (D P) O ~p) 1- ~
3 a, 1~ 3 3 ~U
D ~D r~ 1~ 3 ~ 1--~¢ ~¢ 1- 3 ~ ~D
P) (D ~ U~ ~ 3(D ~Z) ~ ¢ ~¢ 3 3 U~ C
O (D ~t tn(D O
,t ~¢
~ ~ p) D~D (D 3 ~¢ ~
(D X
,¢ ~) (D
,_. IJ
~ .
.
~r C
o ~C
O cn oo ~ o O ~ O O
o o , (D
~D
C
~ w m ~ o ~ 3 I~ . o 1~ o w o o ~ 1 3 (1:1 C
a~
C
~- ~ g w ~ ~ ~ I~ ~
o o UlW ~J O :~ 'a o ~J ~ oo o r~
~D
C
O
O Z
~n Ul O W
o 1-- r~
o C
~C g c~ ~ W ,~
a~ ~ Uol ~ ~
o c~ W rt O
o ' ' ' 8~) Table 2 (continued) Comparative Example 11 12 resin ~arnish P
melamine butylolated butylolated Finishiny appearance O O
Pencil hardness B 2B
impact strenyth 40 5U
accelerated weather resistance 35 25 baked residue (wt~) 65.2 66.4 2 tone adhesion 90/100 95/100 '~
Claims (2)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A resinous composition for a top coat comprising a polyester resin modified with a lactone, said polyester resin being composed of alcohol and acid components, 10 to 80 mole % of the acid component being an alicyclic polycarboxylic acid or anhydride thereof and 10 to 100 mole % of the carboxyl groups capable of developing a resinous acid value being derived from a polycarboxylic acid showing a titration midpoint potential in a non-aqueous potentiometric titration, under the state being incorporated into the resin, of -350 mV or more, and said lactone being represented by the formula:
wherein n is an integer of 4 to 10, and included in an amount corresponding to 5 to 30% by weight of the total weight of the resin.
wherein n is an integer of 4 to 10, and included in an amount corresponding to 5 to 30% by weight of the total weight of the resin.
2. The composition according to claim 1 wherein the polyester resin is an alkyd resin whose oil length is up to 30% of the total weight of the resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170196A JPH0670205B2 (en) | 1985-07-31 | 1985-07-31 | Resin composition for top coating |
| JP170196/85 | 1985-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269480A true CA1269480A (en) | 1990-05-22 |
Family
ID=15900451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000514951A Expired - Fee Related CA1269480A (en) | 1985-07-31 | 1986-07-30 | Resinous composition for a top coat |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4731422A (en) |
| EP (1) | EP0211625B1 (en) |
| JP (1) | JPH0670205B2 (en) |
| KR (1) | KR940000534B1 (en) |
| AU (1) | AU585041B2 (en) |
| CA (1) | CA1269480A (en) |
| DE (2) | DE3667794D1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2748010B2 (en) * | 1989-02-01 | 1998-05-06 | 東洋紡績株式会社 | Method for producing block copolymerized polyester |
| KR950012768B1 (en) * | 1989-12-28 | 1995-10-21 | 고려화학주식회사 | Process for the preparation of low lemperatire curing polyester resin and powder paint composition |
| US5371172A (en) * | 1991-03-26 | 1994-12-06 | Showa Highpolymer Co., Ltd. | High-molecular unsaturated polyester resin |
| DE4237658A1 (en) * | 1992-11-07 | 1994-05-11 | Herberts Gmbh | Binder composition, coating compositions containing it, their production and use |
| JP2003003115A (en) * | 2001-06-22 | 2003-01-08 | Nippon Paint Co Ltd | Intermediate coating composition, method for forming multilayer coating film and multilayer coating film |
| DE102006048288A1 (en) * | 2006-10-12 | 2008-04-17 | Bayer Materialscience Ag | Polyester polyols, process for their preparation and their use |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT975289B (en) * | 1971-10-22 | 1974-07-20 | Ppg Industries Inc | FLEXIBLE POLYESTER-BASED COMPOSITION FOR COVERING COLARLY PARTS OF HOUSEHOLD APPLIANCES AND UTENSILS |
| GB1408141A (en) * | 1971-12-09 | 1975-10-01 | Laporte Ind | Polymeric compositions |
| US4128526A (en) * | 1976-12-23 | 1978-12-05 | General Electric Company | Copolyesters of poly(alkylene glycol aromatic acid esters) and diesters comprising aromatic diols |
| US4148765A (en) * | 1977-01-10 | 1979-04-10 | The Dow Chemical Company | Polyester resins containing dicyclopentadiene |
| JPS5538979A (en) * | 1978-09-12 | 1980-03-18 | Kawasaki Steel Corp | Manufacture of low yield point, high tensile hot rolled steel plate with superior workability |
| EP0057415B1 (en) * | 1981-01-30 | 1987-04-29 | Teijin Limited | Polyester resin composition |
| JPS5945359A (en) * | 1982-09-06 | 1984-03-14 | Nippon Paint Co Ltd | Paint composition |
| JPS59131667A (en) * | 1982-09-06 | 1984-07-28 | Nippon Paint Co Ltd | Resin composition for paint containing polyester resin modified with alicyclic acid and having controlled kind of acid at terminal |
| JPS5967248A (en) * | 1982-10-08 | 1984-04-16 | Daicel Chem Ind Ltd | Polyester compound |
| US4405764A (en) * | 1982-12-30 | 1983-09-20 | Mobil Oil Corporation | Thermosettable polyester resin compositions containing caprolactone |
| US4569973A (en) * | 1984-08-24 | 1986-02-11 | General Electric Company | Copolyetheresters from caprolactone |
-
1985
- 1985-07-31 JP JP60170196A patent/JPH0670205B2/en not_active Expired - Lifetime
-
1986
- 1986-07-29 US US06/890,484 patent/US4731422A/en not_active Expired - Fee Related
- 1986-07-29 AU AU60730/86A patent/AU585041B2/en not_active Expired
- 1986-07-30 CA CA000514951A patent/CA1269480A/en not_active Expired - Fee Related
- 1986-07-31 KR KR1019860006323A patent/KR940000534B1/en not_active IP Right Cessation
- 1986-07-31 EP EP86305910A patent/EP0211625B1/en not_active Expired
- 1986-07-31 DE DE8686305910T patent/DE3667794D1/en not_active Expired - Fee Related
- 1986-07-31 DE DE198686305910T patent/DE211625T1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR940000534B1 (en) | 1994-01-24 |
| US4731422A (en) | 1988-03-15 |
| EP0211625A3 (en) | 1987-09-02 |
| DE211625T1 (en) | 1987-07-23 |
| JPH0670205B2 (en) | 1994-09-07 |
| DE3667794D1 (en) | 1990-02-01 |
| AU6073086A (en) | 1987-02-05 |
| EP0211625A2 (en) | 1987-02-25 |
| JPS6230119A (en) | 1987-02-09 |
| AU585041B2 (en) | 1989-06-08 |
| EP0211625B1 (en) | 1989-12-27 |
| KR870001274A (en) | 1987-03-12 |
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