AU615963B2 - Resinous composition, its preparation and coating composition containing the same - Google Patents

Description

(iY~ 6 15 t96 3 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 SUBSTITUTE COMPLETE SPECIICATION FOR OFFICE USE Form Short Title: int. Cl: Application Number: Lodged: Comple~i Specific ation-Lodged: Accepted: Lapsed: Published: Priority: Related Art: of 0 0 0 p000 0 0 TO BE COMPLETED BY APPICANT Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: NIPPON PAINT CO,, LTD 1-2, Oyodokita 2-cW~me, Oyodo-ku, Osaka-shi,

JAPAN

1-irotoshi Umemoto; Hisaki Tanabe; Mitsuo Yamada and Shinji, Nakano CTRIFFITH HACK CO.

7i YORK STREET SVYDNE Y NSW 2000

AUSTRALIA

40*0 00 @4 p O 44 0 0 04 4. 9 @4 @4 Cc Complete Specification for the invention entitled: RESINOUS COMPOSITION,, ITS PREPARA-T ION AND COATING COMPOSITION W~NTAINING THE SAME The following statement is a full description of this invention, including the best method of performing it known to me/us:- 7199A: JM GRIFFITH HACK LU., I ulI i, r -2- The present invention relates to a coating composition having improved curing property and storage stability. The invention also concerns a resin to be used in the coating s, composition and preparation thereof.

Background of the invention Since an aminoplast obtained by the reaction of a compound having amino group, acid amide bonding or the like, and formaldehyde, as, for example, melamine resin, urea resin, aniline-formaldehyde resin and the like, has such active group as active hydrogen, active methylol and active alkoxymethylene, it is generally combined with various resins for use as a coating having a functional group which is reactive with the abovesaid active group, such as hydroxyl group, isocyanate group or the like, including acrylic resin, alkyd r esin, polyester resin, epoxy resin, Spolyurethane resin, polyamide resin, polycarbonate resin and the like, and used as heat curing type coating composition.

.a Various isocyanate compounds are also used, with said Sbase resins, in heat curing type coating compositions.

20 However, such coating compositions generally require hiigh temperature baking, and in the combination of said resinhs and aminoplasts, the baking is carried out at about 140°C Sfor the combination of alkyd resin and melamine resin for automobile use and the baking is carried out at about 170°C and more for the combination of epoxy resin and amino resin for coil coating use.

From the standpoint of energy saving, it is, of course, desired to have a lower baking temperature and to this end various proposals have been made. One of the proposals ?o heretofore made is to increase an acid value and hydroxyl number of such resin as alkyd resin, thereby improving the reactivity with aminoplast, and to increase the molecular weight of the resin, thereby improving the curing property thereof. However, this inevitably is accompanied by such O c NV 72S/as 25.07.91 rr-I!

(I

ft t ft f *l t~ t ft I It ft ft ft ft f ft ft f -3problems as undesired increase in paint viscosity, lowering of storage stability and decrease in water resistance of the formed film. Attempts have also been made to increase the molecular weight of aminoplast and improve the curing property of the coating composition but the results have been proved to be rejected by the additional problem of poor compatibility with alkyd and other resins.

There is another proposal of adding an external catalyst as p-toluene sulfonic acid, phosphoric acid and the like to the combination of coating use resin and crosslinking agent. However, no satisfactory results are obtained because of the poor pigment dispersion stability, e.g. segregation, due to the presence of external acid catalyst, poor storage stability due to the gradual curing of the coating composition at room temperature and lowering of water resistance of the film. In the case that the isocyanate compounds are used as crosslinking agents, employment of external catalyst as tin compound, amino compound and the like, will cause decrease in pot-life of 20 the coating composition, resulting the inferior working properties thereof.

In light of the foregoing, it is an object of the present invention to provide a resin, a method for the preparation thereof, and a resinous composition containing the resin and a cross-linking agent selected from an aminopiast or isocyanate compound. Preferred resinous compositions can be cured without the use of an external catalyst, can be cured at a lower temperature or in a shorter period of time, have excellent storage stability, are capable of producing excellent film performance, and have improved colour stability over time.

In a first aspect, the present invention provides a resin having resinous acid value of M N obtainable by the reaction of a base resin having a functional group reactive with a cross-linking agent selected from an aminoplast or isocyanate compound, and a functional group reactive with a carboxyl group, the base resin having a resinous s.

IOFFIC,572Sas 25o7.9l L I -i

I*

-4acid value of M, wherein M is zero or any positive number; and an unsaturated cyclic polycarboxylic acid halviig a titration midpoint potential in a non-aqueous TBAH (tetrabutylammonium hydroxide) potentiometric titration of greater than -300mV; wherein N is a resinous acid value of from 2 to 50 afforded to the resin by the carboxyl groups derived from the unsaturated polycarboxylic acid In a second aspect, the present invention provides a method for preparing a resin according to the first aspect, the method comprising esterifying Wa parts by weight of the base resin having a resinous acid value of M; with Wb parts by weight of the polycarboxylic acid .o wherein N Wa Wb '(56100/E) P/100) -N 4' wherein E is 1 gram equivalent of the polycarboxylic acid P is the reaction of the polycarboxylic acid to be reacted with the base resin and N is the desired Sresinous acid value between 2 and In a third aspect, the present invention provides a resin obtainable by the reaction of a resin according to the first aspect or a resin prepared by the method of the second aspesct; and an alkyleneimine compound having at least one alkyleneimine .'ing of 2 to 3 carbon atoms, in an amount equivalent to a resinous acid value of from 0.01 to In a fourth aspect, the present invention provides a resinous composition comprising 45 to 95% by weight (solid) of a resin according to the first or third aspects, or a resin prepared by the method of the second aspect, and 5-55% by weight (solid) of a cross-linking agent selected from an aminoplast or isocyanate compound.

I 2 5 7 9 I 2S'S/as 25.07.91 h r I, In the present specification and claims the term "functional group reactive with a crosslinking agent" means "functional group which is reactive with active hydrogen, active methylol or active alkoxymethylene group possessed by aminoplast or functional group which is reactive with isocyanate possessed by isocyanate compound". The term "functional group reactive with carboxyl group" means "any functional group which is reactive with carboxyl group, including hydroxyl, acid amide bonding and the like". Also, the term "non-aqueous potentiometric titration" means "potentiometric titration wherein the test resin is dissolved in non-aqueous solvent and n-tetrabutylammonium hydroxide is used as titration reagent".

When a polycarboxylic acid is reacted with a resin having functional group reactive with carboxyl group, as, for example, hydroxyl, acid amide bonding or the like (hydroxyl can be the functional group reactive with carboxyl Sgroup and at the same time, the functional group reactive with a crosslinking agent), said acid may be incorporated by, for example, ester bonding, acid amide bonding or the like into the resin, thereby producing the resin in which a part of the carboxyl groups of the polycarboxylic acid are Smaintained in the polymer chain, affording a resinous acid value to the obtained resin.

The inventors have found that a so-called internal catalyst function may be successfully given to a coating composition of the present invention by the inclusion of an acid component in the resin which affords a resinous acid value to the resin. The inventors then, having studied the acidity and the amount of acid to be incorporated into the resin, have completed the invention. Accordingly, coating compositions of the present invention may be cured without the addition of an external catalyst.

The base resin is preferably selected from alkyd, polyester, acrylic, epoxy, polyurethane, polyamide, a polycarbonate resins and the like, which are curable with aminoplast or isocyanate compound. The heat curing may be i of any type of the following: 68 S/as 25.07.91 pr o toue -6reaction between hydroxyl and active methylol groups; reaction between hydroxyl and active alkoxymethylene groups; reaction between and active hydrogen bearing group as hydroxyl, carboxyl, amino or imino group, and isocyanate group and the like. Various other reactions have also been known. However, since they cannot constitute the characteristic feature of this invention and are well known in the art, the details are omitted.

For the sake of briefness, the invention will now be explained with the combination of a resin having both carboxyl and hydroxyl groups (the latter may also be the functional group reactive with crosslinking agent) and aminoplast(crosslinking agent).

Since hydroxyl group has such dual functions, when the hydroxyl bearing resin is reacted with a polycarboxylic acid, e.g. di-, tri-, or tetra-carboxylic acid, or its ranhydride, at least one of the carboxyl groups of said polycarboxylic acid may be reacted and used in the esterification, thereby taken into the polymer, and the remaining carboxyl group having not participated in the Sreaction may be left in the polymer in a state capable of affording resinous acid value to the obtained resin. The i| hydroxyl groups that are not reacted with the polycarboxylic acid may also be present in the obtained resin. The 2 resinous acid value afforded may be freely controlled by regulation of the amount of the polycarboxylic acid and reaction thereof.

When a potential-TBAH (tetrabutyl ammonium hydroxide) titer curve of a polycarboxylic acid is plotted from the results of its non-aqueous potentiometric titration, a plurality inflection points are seen which depend upon the type of the acid used. However, when the acid is incorporated into a resin by ester bonding, there remains, as already stated, at least one free carboxyl group, with the result that the number of inflection points will be reduced accordingly.

8j7'2S/as 25.07.91

I.

-7- In this invention, the polycarboxylic acid to be used and incorporated into a resin must be of such acidity that the titration midpoint potential in non-aqueous potentiometric titration is more than -300 mV, under the state of being incorporated into the resin, i.e. at the state of developing resinous acid value. The inventors have found the very important fact that with a polycarbozylic acid whose titration midpoint potential is less than -300 mV, the present object of curing promotion cannot be attained. The selection of an appropriate polycarboxylic acid is readily achieved by the adoption of simple test wherein the test acid is reacted with a hydroxy bearing resin and the titration midpoint potential is measured according to a normal procedure.

The polycarboxylic acids advantageously used in the present invention may include phthalic anhydride, pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, tetrachlorophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic anhydride, 20 tetrabromophthalic acid, HET acid, HET anhydride and the like.

It is essential that the abovesaid polycarboxylic acid be incorporated in a resin so as to give a resinous acid value of 2 to 50. This is because at a level of less 25 than 2, the present object of curing promotion cannot be attained; whereas, at a level of more than 50, there is a ,,trend that minimum film thickness causing no pinholes will be increased with resultant inferior storage stability of the coating composition and decreased water resistance of the formed film.

The present resin having a resinous acid value of M N may be advantageously prepared by the following method: Wa parts by weight (on solid basis) of a hydroxy bearing resin (hydroxy has dual tunctions as the group reactive with carboxyl group and as the group reactive with crosslinking agent) are reacted with Wb parts by weight of 976),722 S/as 25.Q7.91 -j-jjiw'*' /l i.

1 WJ /W M w w- r W W -8the polycarboxylic acid wherein Wb is determined by the following equation N Wa Wb (56100/E) P/100) -N in which E is 1 gram equivalent of the polycarboxylic acid; P is the reaction of the polycarboxylic acid to be reacted with the hydroxy bearing resin; and N is the desired resinous acid value in a range 2-50.

By determining the amount of polycarboxylic acid used with the abovesaid equation and controlling the reaction by nriasurement of resinous acid value, a specified amount of acid with specific acidity can be incorporated into the resin so as to afford the desired resinous acid value. The invention may include cold blend of more than two resins, Sproviding that the resinous acid value from the t:o4 abovementioned polycarboxylic acid is within the limit of 2 r to 50, regardless of the acid content of the respective resins.

20 Thus obtained resin is, in the combination of aminoplast, stable at normal temperatures, and can exhibit effectively the internal catalyst function when heated, thereby showing improved and accelerated curing. Thus, the curing may be carried out at a lower temperature or in a 4 25 shorter period of time as compared with those of heretofore known similar compositions. Moreover, the resulted film is it? excellent in many respects and can be comparable with those of the known similar compositions.

For example, in the combination of melamine resin as aminoplast and alkyd resin, the composition is usually baked and hardened, as practiced in an automobile industry, at 140oC for 30 minutes, However, by the adoption of the present invention, it is possible to carry out the same extent of baking at 70 to ll0C tr even less temperature, to obtain the similar product. No change in the film performance can be found out.

.7/as. 25.07.91 Ftr ilr AA I! 4 -9- In case that melamine resin is used as aminoplast, it should preferably be compatible with the present resin. In this regard, particular preference is given to the melamine resin having more than 2.0 alkoxy groups per molecule.

There is no particular limit in the number average molecular weight and it may be in a conventional range of 500 to 3,000 or the like.

Even in the combination with hexamethoxymethylol melamine, it is possible to attain a lower temperature curing and to provide a high solid coating composition.

Compositions of the present invention may be used as clear coatings or may be used to prepare a coloured paint by the addition of pigments and other additives, At the time when isocyanate compound is selected as a crosslinking agent and external catalyst is added to a coating composition, troubles have been always encountered in the pot-life of the composition.

However, with the present resin, it is possible to 4 obtain, without the necessity of adding an external catalyst, a coating composition which is capable of producing an excellent coating and shows an improved pot-life. Thus, in the present invention, is provided a Sresin being useful as resinous vehicle for coating composition, which is characterized by excellent curing property, storage stability and film performance, without the necessity of adding an external catalyst as in the conventional ones. Therefore, the invention is quite important from the standpoint of saving natural resources.

The alkyleneimine compounds used in the third aspect of the present invention have at least one alkyeneimine ring of 2 to 3 carbon atoms and are preferably compounds represented by the following generic formula:

R

2

R

6 R3 8, 2 cas 25.07.91 pgltsi wherein Rill R, R, R 4 and Reach represent hydrogen; alkyl group having I to 20 carbon atoms as methyl, ethyl, propyl and the like; aryl. as phenyl and the like; alkaryl as tolyl, xylyl and the like; and aralkyl as benzyl, phenethyl and the like; R 6 is hydrogen or alkyl having 1 to 6 carbon atoms; n is 0 or 1.

The abovementioned groups may further include substituents having no adverse effects on the fundamental properties of the imine in the intended reaction. Examples of such substituents are carbonyl, cyano, halogen, amino, hydroxyl, alkoxy, carbalkoxy and nitrile. Thus, the abovementioned groups may be, for example, cyanoalkyl, haloalkyl, aminoalkyl, carbalkoxyalkyl and the corresponding aryl, alkaryl and aralkyl groups.

Some of the compounds having 2 and more of such groups may not easily be prepared by the steric or interaction of these groups. Therefore, in many cases, R-R 6 are mostly composed of hydrogen.

Typical examples of alkyleneimine compounds are as follows: ethlenimie,1, 2-propylenleinhne, 2. 3-propylene.mife, 1, 2-dodecy2.eneimine, 1, t-dimethylethyleneimine, phnltyeemntlyehlniie penzylethyleneimine, toldieylethyleneimine, 25 2-hydroxyethylethyleneimine, amino-ethylethyleneimile, 2 -methylpropylenelmine, 3 -chloropropylethyleleimile, 'II p-chlorophenylethyleleiminfle mnthoxyethylethyJleneimine, carboethoxyethylethy~leimuine, N-ethylethyeneimine, N-butyl ethylene imile t N- (2 -aminoethyl) ethyl ene imine N- (2 -hydroxyethyl) ethylene imine N- (cyanoethyl) ethylene imine, N-phenylethyleleimnine, N-triethylethyleneimine, N- (p-chlorophelyl) ethylene imine, N- (2 -carbethoxy- 1-ethyl) ethyleneiniine.

Particularly useful memb~ers from the standvieW of availability and effectiveness are ethyleneimine, 1, 2-propyleleifife and N- (2 -hydroxyethyl) ethylene imine.

6$4 S/as 25.07.91 -11- Besides the abovesaid preferable members, other alkyleneimine compounds than those of said generic formula may be satisfactorily used. For example, good results are obtained with alkyleneimines having 2 and more of alkylenenimine rings as ethylene-l,2-bisaziridine, 1.2,4-tris(2,l-aziridinylethyl)-tri-mellitate and the like.

Therefore, in the present invention, the term "alkyleneimine compounds" may include substituted alkyleneimines and all of the abovementioned alkyleneimine compounds.

The reaction may be carried out by mixing the alkyleneimine compound and a resin according to the first aspect or a resin prepared by a method of the second aspect and heating the mixture at an elevated temperature, e.g. to 150*C.

The alkyleneimine compound is used in an amount Sequivalent to a resinous acid value of 0.01 to 50, thereby 9a, giving a resin having a resinous acid value based on the polycarboxylic acid of 2 to The inventors have surprisingly found that when the o 20 alkyleneimine compound is reacted with the resin so as to

S

8 lower the resinous acid value to the extent of 0.01 to but still maintaining in the final resin a resinous acid alue afforded by the carboxyl groups of the polycarboxylic acid of 2 to 50, and the thus obtained resin is used, 25 together with a crosslinking agent as aminoplast, for the preparation of coating composition, the so-called internal ooa catalyst function is effectively produced at the time of baking, thereby resulting in improved low temperature curing and improved storage stability of the composition.

Furthermore, very surprisingly, this coating composition has been proved to be possessed of excellent time color stability.

SThis invention will now be more fully explained in the following Examples. Unless otherwise stated, all parts and percentages are by weight.

N 2S/as 2 5.07.91 .1 p 1*.

-12-

I

Example 1 Preparation of resin of polyester resin whose acid value based on phthalic anhydride is 6 my the esterification of 249.2 parts by weight (in solid) of polyester resin A-i having, as acid components, isophthalic acid and adipic acid and having a resinous acid value of 2.0, and Wb parts by weight of phthalic anhydride which gives, under the state of developing resinous acid value, a titration midpoint potential of -290 mV in a non-aqueous potentiometric titration, to a resinous acid value of Composition of polyester resin A-i isophthalic acid adipic acid trimethylolpropane neopentylglycol 1, 6-hexanediol 127.31 parts 29.74 29.05 52.77 56.04 (0.766 mole) (0.2) Resin weight (Wa) 249,2 parts Calculation of Wb of phthalic anhydride: resin weight of polyester A-1 Wa=249.2 resinous acid value based on phthalic anhydride 1 gram equivalent of phthalic anhydride E-74.1 reaction of phthalic anhydride to be reacted with polyester A-l p60.0 From the abovesaid equation: ,b 5.04 (0.034 mole) Inrto a reaction vessel fitted with heating device, stirrer, refluxing device, water separator, fractionator and thermometer, were placed the abovesaid 5 starting materials for polyester resin A-I and the mixture was heated.

Stirring was commenced at the stage when they were melted to a stirrable condition, and the vessel temperature was raised to 220 C. At this time, from 160 to 2200C, said temperature S 872S/as 25.07.91 7 -13was raised in 3 hours at a constant rate. The formed condensed water was continuously removed out of the system.

When reached to 220"C, the reaction vessel was maintained at the same temperature for 1 hour and then gradually added with 5 parts of xylene as a refluxing solvent. The reaction was then switched to a condensation in the presence of solvent and continued for a while. At the stage when the resinous acid valv2e reached to 2.0, the reaction was covered and the content was allowed to cool to 100 0 C to obtain polyester resin A-1.

Next, 5.04 parts (0.034 mole) of phthalic anhydride were placed in said reaction vessel, temperature was raised to 16Q'C and the reaction was continued. When the resinous acid value reached to 8.0, the reac,.ion was stopped and the content was allowed to cool. Thereafter, 118.2 parts of xylene and 13.7 parts of Cellosolve acetate were added to obtain polyester resin varnish L. This varnish showed non-volatile content 69.8%, Viscosity (Gardner viscosity, 0 C) U-V, and resinous acid value 8.2.

Each of the polyester resin A-I and the resin varnish L were diss;olved in pyridine, and subjected to a non-aqueous potentiometric titration using, as a titration reagent, n-tetrabutylammonium hydroxide. The titrtaion curves are shown in Fig. 1. As is clear from the drawing, titration midpoint potential of polyester resin A-1 (curve 2) is -310 mV, which coincides with the ti 'hion midpoint potential of polyester resin having as saA component, isophthalic acid alone (see Table From this, it was 1' confirmed that the carboxyl groups in polyester resin A-i showing a resinous acid value of 2.0 were all derived from isophthalic acid. However, in the titration curve of polyester resin L, there are two inflection points and the titration midpoint potentials are -290 mV and -310 mV, which are well in accord with the titration midpoint potentials (-290 mV and -310 mV) of polyester resins having as acid component, phthalic a)nhydride and isophthalic acid alone, respectively. (see Table 1).

S 2S/as 25.07.91 iB I:i

I~

IIa 1 I- I. "1 11 1, 11 tiE -14- Therefore, it was confirmed that the carboxyl groups of polyester resin L capable of developing resinous acid value were derived from both phthalic anhydride and isophthalic acid and that the resinous acid value coming from phthalic anhydride was 6.1, as so planned.

6 /as 25.07.91 ~ii Table 1 Titration midpoint potentials of various carboxylic acids under the state of developing resinous acid value HHPA= hexhydrophthalic anhydride AciA =adipic acid IPHA= isophthalic acid PAn phthalic anhydride TM4An= triinellitic anhydride potential (mV) potential (mV)

HHPA

AdA sebaic acid -400 -390 -420 PAn

IPHA

TM4An -290 -310 -240 4, 4 4 4. 4 444 4 4~t4 4 4.

.4 44 4 Example 2 Composition of polyester resin A-2 isophthalic acid adipic acid trimethylolpropane neopentylglycol 1, 6-hexandiol 97.23 parts 29 .24 42.96 36.99 39.28 (0.585 mole) (0-2) resin weight (Wa) resinous acid value 213.0 parts Calculation of Wb of phthalic anhydride resin weight of polyester A-2 resinou~s acid value based on phthalic anhydIride i. equivalent of phthalic anhydride Wa 213. 0 N E 74.1 6812S/as 25.07.91.

II V.- It~ei i

S.-

II k -16reaction of phthalic anhydride to be reacted with polyester A-2 P 60,0 From the above, Wb 30.56 (0.206 mole) Using the same procedures as stated in Example 1, 213.0 parts by weight of polyester A-2 and 30.56 parts by weight of phthalic anhydride were reacted to obtain varnish M, whose characteristics were as follows: non-volatile content 65.3% viscosity V W resinous acid value 40.5 titration midpoint potential of phthalic anhydride under the state of developing resinous acid value -290 mV resinous acid value based on phthalic anhydride 37.5 Example 3 Composition of polyester resin A-3 isophthalic acid 129.14 parts (0.777 mole) 20 adipic acid 29.24 (0.2) trimethylolpropane 25.05 neopentylglycol 52.77 1,6-hexanediol 56.04 4 *4 4 t 44r 4 41 4 t 4I t 4 resin weight (Wa) resinous acid value 250.6 parts 4444 44 44 1 44 Calculation of Wb of trimellitic anhydride resin weight of polyester A-3 resinous acid va\ue based on trimellitic anhdydride 1 gram equivalent of trimellitic anydride Wa 250.6 64.0 25.07.91 f C) '0 -17- Creaction of trimellitic anhydride to be reacted with polyester A-3 From the above, P 40.0 Wb 2.89 (0.015 mole) Using the same procedures as stated in Example 1, 250.6 parts by weight of polyester A-3 and 2.89 parts by weight of trimellitic anhydride were reacted to obtain varnish N, whose characteristics were as follows: non-volatile content 64.9% viscosity W resinous acid value 8.1 titration midpoint potential of trimellitic anhydride under the state of developing resinous acid value -230 mV resinous acid valua based on trimellitic anhydride 519 Example 4 Composition of polyester resin A-4 00 0 00 a 0 00 00 0

O

00 00 It i isophthalic acid adipic acid trimethylolpropane neopentylglycol 25 1,6-hexanediol 115.37 parts 29.24 46.62 41.78 44.38 (0.694 mole) (0.2) resin weight (Wa) resinous acid value 231.0 parts Calculation of Wb of trimellitic anhydride resin weight of polyester A-4 resinous acid value based on trimellitic anhydride 1 gram equivalent of trimellitic anhydride reaction of trimellitic anhydride to be reacted with polyester A-4 i; j I i, Wa 231.0 N 28.0 E 64.0 P 40.0 S68 /as 25.07.91 -18- From the above, Wb 12.99 (0.068 mole) Using the same procedures as stated in Example 1, 231.0 parts by weight of polyester A-4 and 12.99 parts by weight of trimellitic anhydride were reacted to obtain varnish 0, whose characteristics were as follows: non-volatile content 65.1% viscosity Y resinous acid value 29.4 titration midpoint potential of trimellitic anhydride under the state of developing resinous acid value -230 mV resinous acid value based on trimellitic anhydride 28.1 *at

I

a a at t tr actr S* a Example Composition of polyester resin isophthalic acid 127.31 parts adipic acid 29.24 trimethylolpropane 25.05 neopentylglycol 52.77 1,6-hexanediol 56.04 (0.766 mole) (0.2) resin weight (Wa) resinous acid value 249.2 parts at a a a' Calculation of Wb of pyromellitic anhydride resin weight of polyester A-5 resinous acid value based on pyromellitic anhydride 1 gram equivalent of pyromellitic anhydride reaction of pyromellitic anhydride to be reacted with polyester A-5 Wa 249.2 N= E 54.5 P 60.0 i j ii r i; i i: ii From above Wb 3.69 (0.017 mole) '/as 25.07.91 r U, <A y, u yuLIcane, po-yamlae, polycarbonate resins and the like, which are curable with aminoplast or isocyanate compound. The heat curing may be of any type of the following: 68 S/as 25.07.91 C; *M ii i i 71- -v r m ii-

I

-19- Using the same procedures as stated in Example 1, 249.2 parts by weight of polyester A-5 and 3.69 parts by weight of pyromellitic anhydride were reacted to obtain varnish P, whose characteristics were as follows: non-volatile content 64.6% viscosity X resinous acid value 8.6 titration midpoint potential of pyromellitic anhydride under the state of developing resinous acid value -180 mV resinous acid value based on pyromellitic anhydride 5.8 Ct I C I C Ct r C

CC

C t Example 6 15 Composition of polyester resin A-6 isophthalic acid 116.01 parts adipic acid 29.24 trimethylolpropane 31.94 neopentylglycol 46.71 1,6-hexanediol 49.60 (0.698 mole) (0.2) -i;

CI,

CCI~

resin weight (Wa) resinou. acid value 235.5 parts

~I

rC I 4 Calculation of Wb of pyromellitic anhydride resin weight of polyester A-6 resinous acid value based on pyromellitic anhydride 1 gram equivalent of pyromellitic anhydride reaction of pyromellitic anhydride to be reacted with polyester A-6 Wa 235.5 N 18.0 E 54.5 P 60.0 From above Wb 10.77 (0.049 mole) IAti zN 0 3 72S/aS 25.07.91 1 lFr-L? S aSas 25.07.91 p4t I 11

I

reduced accordingly.

72S/as 25.07.91 ci7S/as 25.07.91 rr 1 8-: T, -1 I0 Lil Using the same procedures as stated in Example 1, 235.5 parts by weight of polyester A-6 and 10.77 parts by weight of pyromellitic anhydride were reacted to obtain varnish Q, whose characteristics were as follows: non-volatile content 64.9% viscosity Z resinous acid value 19.7 titration midpoint potential of pyromellitic anhydride under the state of developing resinous acid, value -180 mV resinous acid value based on pyromellitic anhydride 17.6 o44 .4 4 *49 4 4(14* 4 4 *o 4 *t 4 44 4 Example 7 15 Composition of polyester resin A-7 isophthalic acid 127.31 parts adipic acid 29.24 trimethylolpropane 25.05 neopentylglycol 52.77 1,6-hexanediol 56.04 (0.766 mole) (0.2) resin weight (Wa) resinous acid value 249.2 parts Calculation of Wb of tetrachlorophthalic anhydride 444( a.

4 44 resin weight of polyester A-7 resinous acid value based on tetrachlorophthalic anhydride 1 grai equivalent of tetrachlorophthalic anhydride reaction of tetrachlorophthalic anhydride to be reacted with polyester A-7 Wa 249.2 N E 143.0 P 60.0 From above Wb 9.91 (0.035 mole) rg2 72S/as 25.07.91 1r U;~k311;

I:,

t* -21- Using the same procedures as stated in Example 1, 249.2 parts by weight of polyester A-7 and 9.91 parts by weight of tetrachlorophthalic anhydride were reacted to obtain varnish R, whose characteristics were as follows: non-volatile content 65.2% viscosity V W resinous acid value titration midpoint potential of tetrachlorophthalic anhydride under the state of developing resinous acid value -120 mV resinous acid value based on tetrachlorophthalic anhydride *r 4*I 4 S 44 Example 8 15 Composition of alkyd resin A-8 isophthalic acid 141.8 parts adipic acid 14.62 trimethylolethane 78.56 neopentylglycol 31.55 20 coconut oil 88.58 dehydrated castor oil 22.14 (0.853 mole) resin weight (Wa) resinous acid value 340.1 parts f 4

~~I

4 Calculation of Wb of phthalic anhydride resin weight of alkyd A-8 resinous acid value based on phthalic anhydride 1 gram equivalent of phthalic anhydride reaction of phthalic anhydride to be reacted with alkyd A-8 Wa 340.1 N E 74.1 P 60.0 From above Wb 6.87 (0.046 mole) 672S/as 25.07.91 ,f N t -22- Using the same procedures as stated in Example 1, 340.1 parts by weight of alkyd A-8 and 6.87 parts by weight of phthalic anhydride were reacted to obtain varnish S, whose characteristics were as follows: non-volatile content 60.1% viscosity T U resinous acid value 7.8 titration midpoint potential of phthalic anhydride under the state of developing resinous acid value -290 mV resinous acid value based on phthalic anhydride 5.7 Example 9 15 Composition of alkyd resin A-9 Sisophthalic acid 141.8 parts (0.853 mole) Sadipic acid 14.62 Strimethylolethane 78.56 1 neopentylglycol 31.55 i 20 coconut oil 88.58 dehydrated castor oil 22.14 S' resin weight (Wa) 340.1 parts resinous acid value Calculation of Wb of pyromellitic anhydride *4 44 resin weight of alkyd A-9 Wa 340.1 resinous acid value based on N pyromellitic anhydride N 1 gram equivalent of pyromellitic anhydride E 54.5 reaction of pyromellitic anhydride to be reacted with alkyd A-9 P 60.0 From above Wb 5.03 (0.023 mole) 68( 2S/as 25.07.91 -23- Using the same procedures as stated in Example 1, 340.1 parts by weight of alkyd A-9 and 5.03 parts by weight of pyromellitic anhydride were reacted to obtain varnish T, whose characteristics were as follows: non-volatile content 60.7% viscosity W X resinous acid value 8.1 titration midpoint potential of pyromellitic anhydride under the state of developing resinous acid value -180 mV resinous acid value based on pyromellitic anhydride 6.1 Comparative Example 1 S, 15 Preparation of comparative varnish U 133 Parts by weight of isophthalic acid, 29.2 parts by weight of adipic acid, 25.1 parts by weight of trimethylolethane, 52.8 parts by weight of neopentylgycol and 56 parts by weight of 1,6-hexanediol were placed 4.n a S 20 reaction tank and heated. Stirring was commenced wheli the starting materials were melted to a stirrable condition and I tank temperature was raised to 220*C. At this time, from 160°C to 220°C, the temperature was raised gradually in 3 hours at a constant rate. The formed condensed water was continuously removed out of the system. When reached to 220°C, the same temperature was maintained for 1 hour, and thereafter, 5 parts of xylene were added gradually as a refluxing solvent and the reaction was changed to a condensation in the presence of solvent and kept going. At the time when the resinous acid value reached to 8.0, the reaction was stopped and the mixture was allowed to cool.

After cooling, 118.2 parts of xylene and 13.7 parts of Cellosolve acetate were added to obtain a polyester resin varnish U, whose characteristics were as follows: non-volatile content 65.2% viscosity V resinous acid value 6872S/as 25.07.91

I

-24- Comparative Example 2 Preparation of comparative resin varnish V 88.6 Parts of coconut oil, 22.1 parts of dehydrated castor oil, 39.9 parts of trimethylolethane and 0.1 part of lithium naphthenate were placed in a reaction tank and the mixture was heated to 240'C. Ester-exchange reaction was carried out at 2409C and then 38.6 parts of trimethylolethane, 149.6 parts of isophthalic acid, 14.6 parts of adipic acid, 31.6 parts of neopentylglycol and 7 parts of xylene were added and dehydration reaction was carried out at 220 to 230°C until the resinous acid value reached to 8.0. After cooling, 202 parts of xylene and 23.3 parts of Cellosolve acetate were added to obtain an alkyd resin varnish V, non-volatile content 60.0%, viscosity U and 15 resinous acid value 8.3.

Comparative Example 3 Preparation of comparative resin varnish W Into a reaction vessel fitted with reflux condenser, dropping funnel, thermometer and stirrer, were placed parts of xylene, 20 parts of Cellosolve acetate, 35 parts of methylmethacrylate (IMA), 48 parts of ethyl acrylate (EA), 16 parts of 2-hydroxyethyl methacrylate (HEMA) and I part of methacrylic acid (MAA) and the mixture was heated to 110C.

While maintaining the said temperature, a mixed solution of parts of xylene, 20 parts of Cellosolve acetate, 1 part of azobis isobutyronitrile and 0.25 part of lauryl mercaptane was dropwisely added in 3 hours at a constant speed, and therafter, the mixture was maintained at the same temperature for 2 hours to complete the reaction, The characteristics of thus obtained acrylic resin varnish W are as follows: non-volatile content 50.0%, viscosity Y and resinous acid value 872S/as 25.07,91 [i Example Preparation of resinous composition of acrylic resin whose acid value based on tetrachlorophthalic anhydride is by the reaction of 100 parts (on solid basis) of acrylic resin varnish W obtained in Comparative Example 3, and Wb parts of tetrachlorophthalic anhydride capable of showing a titration midpoint potential of -120 mV in non-aqueous potentiometric titration under the state of developing resinous acid value Calculation of Wb of tetrachlorophthalic anhdyride: resin weight of acrylic resin W Wa 100 resinous acid value derived from tetrachlorophthalic anhydride N= 1 gram equivalent of tetrachlorophthalic anhydride E 143.0 reaction of tetrachlorophthalic anhydride to be reacted with acrylic resin W P 50.0 From the aforesaid equation: o: Wb 3.70 (0.013 mole) Into a reaction vessel, were placed 100 parts of acrylic resin varnish W and 3.7 parts of tetrachlorophthalic anhydride, and the mixture was heated to 140*C. The reaction mixture was maintained at 1400C until the resinous acid value reached to 14.0 and then allowed to cool. Thus obtained acrylic resinous varnish X had non-volatile content of 51.6% and viscosity of Z. Resinous acid value based on tetrachlorophthalic anhydride was Example 11 A pale bluish white colored paint composition was prepared by mixing 35.0 parts (solid) of polyester resin L obtained in Example 1, 15.0 parts (solid) of U-van 20 (melamine resin manufactured by Mitsuitoatsu as crosslinking agent), 8.0 parts of xylene, 4.0 parts of 872/as 25.07.91 6872S/as 25.07.921

IN

-26- Solvesso 100 (an aromatic hydrocarbon solvent) 7.0 parts of n-butanol, 0.015 parts of Silicone KF-69 (a Silicon resin used as a surface control agent manufactured by Shinetsu Kagaku 45.0 parts of Titanium CR-95 (Titanium dioxide manufactured by Ishihara Sangyo and 2.3 parts of Fastgen Blue NK (a phthalocyamine blue pigment manufactured by Dainippon Ink To this, were added a dilution solvent comprising 20.0 parts of Solvesso 100. 50.0 parts of toluene, 10.0 parts of xylene and 20.0 parts of n-butanol to adjust the Ford cup #4 viscosity of 20 sec./25'C. Thus obtained coating composition was applied by spraying onto SPC-1 dull steel plate previously treated with zinc phosphate, and the plate was, after standing for a defined period of time, baked at 100'C for 30 minutes. The film .1 ,5 properties are shown in the following Table 2.

",Examples 12, 13 and 14 e The similar coating compositions were prepared S' t following the procedures of Example 11, but substituting t :equivalent amounts of polyester resin N, polyester resin P S' 20 and polyester resin R obtained in Examples 3, 5 and 7, for the polyester resin L, respectively. These compositions after having adjusted the viscosity, applied on the "similar dull steel plates and baked at 100C' for minutes, The coatings were evaluated as in Example 11 and the test results were shown in the following table 2# EXample 'A coating composition was prepared by using the same proced4res and prescription as given in Example 11, However, in this example, polyester resin LT was replaced by polyester resin R and 45.0 parts (solid) of the resin R and parts (solid of U-van 20 SE-60 were used, respectively.I The composition was diluted to adjust the viscosity, applied Ito the similar dull steel plate and baked at 100°C for minutes, The coating was evaluated as in Example il and the test result we1;- shown in Table 2.

J. i \6 8 6872S/as 25.07. 1 1 alone, respectively. (see Table 1).

S 2S/as 25.07.91 -27- Example 16 Using polyester resin R and U-van 20 SE-60 in solid ratio of 30.0 parts and 20 parts, and repeating the same procedures of Example 11 with the same prescription, a coating compositiort was prepared, which was diluted with a mixed solvent to a(Ajust the viscosity, applied on the c"i similar dull steel plate and baked at 100C for 30 mintures as in Example ll The coating was evaluated and the results were shown in Table 2.

Examples 17, 18 and 19 Using polyester resin M, polyester resin 0 and polyester resin Q obtained in Examples 2, 4 and 6 in place of polyester resin L in :'xample 11 and following the t f. 15 procedures of Example 11 with the same prescription stated therein, three different coating compositions were prepared, which were then diluted with mixed solvent to adjust viscosity, applied on the similar dull steel plates and baked at 1Q0°C for 30 minutes, respectively. Evaluation of these coatings were carried out as in Example 11 and the results were shown in Table 2.

Comparative Examples 4 and A coating composition was prepared as in Example 11, but substituting equivalent amounts of polyester resin U prepare, in comparative Example 1 for the polyester resin L. After diluting with a mixed solvent and applying on the similar dull steel plates, the coatings were bakod at 1400C and at 100, for 30 minutes, respectively. The coatings were then evaluated i4 the same way as in Example 11 and test results were shown in Table 2.

Coiparative Example 6 o the coating composition of Comparative Exariple 4, was added as external catalyst, 1.0 part of p-toluenes!Alfonic acid and mixed well. This was, adjusting viscosity, applied on the sim,.lar dull steel plate and baked at 1009C for 30 minutes. The coating was .872S/as 25.07.91 07.9 1 -28evaluated in the same way as stfted in Example 11 and the test results were shown in Table 2.

Example In Example polyester resin L was replaced by alkyd resin S prepared in Exe'nple 8 and a coating composition was prepared, applied on the similar dull steel plate and baked at the same temperature. Thus obtained coating was evaluated in the same way and the results were shown in Table 2.

Example 21 In Example 11, polyester resin L was replaced by alkyd resin T prepared Example 9 and a coating composition was Or 15 prepared, applied on the similar dull steel plate and baked at lO 0 C for 30 minutes. Thus obtained coating was evaluated in the same way and the results were shown in Table 2.

comparative Examp'le 7 In Example 11, polyesterc resin L was replaced by alkyd -Ott resin V prepared in Comparative Exaiple 2 and a coating composition was prepared, applied or, the similar dull steel plate and baked at l40*C "~or 30 minutes. Thus obtained coating was evaluated in the same way and the results were 'Ott*,shown in Table 2.

Comparative Example 8 Using the same coating composition as, stated il Comparative Example 7, the same procedures of Example 11 were repeated excepting carrying out trie baking atlO 0 C for minutes. The test results are shown in Table 2.

Example 22 In Example 11, polyester resin I, was replaced by Ii acrylic resin X prepared in Example 10 and a coating composition was prepared, applied on the similar dull steel

/Y

0 AyY6872S/as 25.07.91 'Iw -29plate and baked at 100"C for 30 minutes. Thus obtained coating was evaluated in the same way and the results were shown in Table 2.

Comparative Example 9 In Example 11, polyester resin L was replaced by acrylic resin W prepared in Comparative Example 3 and a coating composition was prepared, applied on the similar dull steel plate and baked at 100°C at 30 minutes. Thus obtained coating was evaluated in the same way and the results were shown in Table 2.

Example 23 A coating composition was prepared by mixing 30.0 parts 15 (solid) of alkyd resin T obtained in Example 9, 20.0 parts (solid) of Super Beckamine g 1850 (urea resin, manufactured a 2 by Dainippon Ink crosslinking agent), 1.0 part of S" xylene, 4.0 parts of n-butanol, 0.2 part of Silicone TSA-720 S: (Silicone resin used as a surface control agent, manufactured by Toshiba Silicone 40.0 parts of Titanium CR-95 (manufactured by Ishihara Sangyo and parts of Fastgen Blue NK and diluting the same with a mixed solvent comprising 50.0 parts of methanol and 50.0 parti of xylene to adjust the Ford cup #4 viscosity ato 23 sec./20°C. Thus obtained composition was applied by spraying onto SPC-1 dull steel plate previously treated with zinc phosphate and after standing for a defined period of time, baked at 80sC for 30 minutes. The coating was then evaluated and the test results were shown in Table 2.

s 30 Comparative Example In Example 23, alkyd resin T was replaced by alkyd resin V prepared in Comparative Example 2 and a coating composition was prepared as in Example 23. To this, were added as external catalyst 2.5 parts of p-toluene sulfonic acid and after adjusting the viscosity, thus obtained composition was applied on the similar steel plate and baked at the same temperature as in Example 23. Thus obtained 6V 872S/as 25.07.91 1/ -4162S/as 25.07.91 coating was evaluated in the same way and the results were shown in Table 2.

Example 24 In Example 11, the crosslinking agent was replaced by U-van 125 (melamine resin manufactured by Mitsui toatsu and a simi.ar coating composition was prepared using the same prescription. After diluting to adjust viscosity, said composition was applied on the similar steel plate and baked at 100 0 C for 30 minutes. Thus obtained coating was evaluated as in Example 11 and the results were shown in Table 2.

Example 15 A coating composition was prepared by mixing 50.0 parts (solid) of acrylic resin X used in Example 22, 10.0 parts of Cellosolve acetate, 26.0 parts of Solvesso 100, 70.0 parts of Titanium CR-95 (Ishihara Sangyo 3.5 parts of Fastgen Blue NK, 0.8 part of Modaflow (acrylic resin used as I it 20 a surface control agent manuractured by Monsanto) and parts (solid) of Desmodule TPL-2291 (isocyanate crosslinking agent, manufactured by Sumitomo Bayer The composition was then diluted with a mixed solvent comprising 16.0 parts of butylacetate, 50.0 parts of xylene, 20.0 parts of Sovpsso 100 and 6.0 parts of Cellosolve acetate to adjust Ford cup #4 viscosity to 20 seconds/ 25°C, and applied to SPC-1 dull steel plate previously treated with zinc phosphate by spraying. After standing for a defined period of time, the coating was baked at 80°C for 30 minutes and the film properties were evaluated. The results are shown in Table 3.

Comparative Example 11 In Example 25, acrylic resin x was replaced by alkyd resin W prepared in Comparative Example 9 and a coating composition was prepared, applied on the similar dull steel plate and baked at 80 0 C for 30 minutes as in Example Thus obtained coating was evaluated in the same way and the results were shown in Table 3.

72S 25.07.91 872S/as 25.07.91 -31- Comparative Example 12 The same coating composition as stated in Comparative Example 11 was added with 0.006 part of dibutyl tin dilaurate (DBTDL) as an external catalyst and mixed well.

Thus obtained composition was, after adjusting the viscosity, applied on similar dull steel plate and baked at for 30 minutes. The coating was evaluated and the test results were shown in Table 3.

Examples 26 and 27 In Example 11, polyester resin L was replaced by polyester resin P and by polyester resin R obtained in Example 5 and in Example 7 and U-van 20Se-60 was replaced by Cymel 303 (methyl melamine resin manufactured by Mitsui 15 Toatsu to obtain coating compositions. After applying onto the similar dull steel plates, they are baked at 120°C for 30 minutes and the coatings were evaluated in the same way and the results were shown in Table 4.

1 20 Comparative Example 13 In Example 11, polyester resin L was replaced by polyester resin U prepared in Comparative Example 1 and U-van 20SE-60 was replaced by Cymel 303 (methyl melamine resin manufactured by Mitsui Toatsu, crosslinking agent) to obtain a coating composition. This was, after adjusting the viscosity, applied on the similar dull steel plate and baked at 120°C for 30 minutes. Thus obtained coating was evaluated in the same way and the results were shown in Table 4.

Test methods and evaluation standards: Note 2: Pencil Hardness The coating was scratched by Mitsubishi Uni pencil and pencil hardness was judged by maximum hardness causing no pencil scratches.

Note 3: Gel fraction Sample specimen of baked coating was subjected to a solvent extraction, by using Soxhlet-extractor, with 6872S/as 25.07.91 Wb 3.69 (0.017 mole) -32acetone/methanol=l/l (weight ratio) at 70°C for 5 hours.

The specimen was then dried at 120*C for 30 minutes in decicator, allowed to cool and weighed the final weight.

From the weight difference, gel fraction was calculated.

Note 4: Coat surface condition Coating composition was applied on tinplate by flow coating, and pigment dispersion stability was evaluated by visual observation of finishing apperarance, gloss and on the basis of the following criteria: very good good A slightly inferior X...no good Note 5: Water resistance 15 Baked sample specimen was dipped in wairmed water no abnormality the .partly blistered Note 6: Storage stability Coating composition was kept at 40 0 C and storage stability was evaluated by maximum duration up to gelation.

\Tehb' 6872S/as 25.07.91 pa 1 't t_ 72S/as 25.07.91 -33- Table 2 90 e 9 o* 0 4 e 9 o 0 o «6ft 0 9 9 006 004 0 «H 4 4 *4.0 00 *4 0 Example Number Example 11 Example 12 Example 13 Formulation Note 1 polyester resin L 35.0 N 35.0 P 35.0 alkyd resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin U125 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 Silicone TSA-720 ext. catalyst P-TSA Baking condition 'Cx30' 100 100 100 Film properties pencil hardness Note 2 F F-H H gel fraction Note 3 86 88 92 surface cond. Note 4 water resist. Note 5 0 0 0 Paint properties more than more than more than storage stab. Note 6 3 months OK 3 months OK 3 months OK Note i....resinous weight is by solid weight 6872S/as 25.07.91 Wb 9.91 (0.035 mole) 2S/as 25.07.91 -34- Table 2 (continued) Example Number Example 14 Example 15 Example 16 Formulation Note 1 polyester resin R 35.0 R 45.0 R 30.0 alkyd resin acrylic resin melamine resin U20SE 15.0 5.0 20.0 melamine resin U125 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 Silicone TSA-720 ext. catalyst P-TSA Baking condition °Cx30' 100 100 100 Film properties pencil hardness Note 2 F F-H H-2H gel fraction Note 3 95 86 92 surface cond. Note 4 Q water resist. Note 5 0 0 0 Paint properties more than more than more than storage stab. Note 6 3 months OK 3 months OK 3 months OK Note resinous weight iq by solid weight 1~

I

25.07.91 From above Wb 6.87 (0.046 mole) V 2S/as 25.07.91 6 j1 Table 2 (continued)

I

4i*14 ~*4 14

I,

4 Example Number Example 17 Example 18 Example 19 Formulation Note 1 polyester resin M 35.0 0 35.0 Q 35.0 alkyd resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin U125 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 Silicone TSA-720 ext. catalyst P-TSA Baking condition °Cx30' 100 100 100 Film properties pencil hardness Note 2 H H 2H gel fraction Note 3 92 94 96 surface cond. Note 4 water resist. Note 5 0 0 0 Paint properties storage stab. Note 6 20 days 2 months 2 months gelation gelation gelation Note 1 resinous weight is by solid weight )/as 25.07.91

V

I

From above Wb 5.03 (0.023 mole) A 'm68g2S/as 25.07.91 A '^Y

I

-36- Table 2 (continued) Example Number Comp. Comp. Comp.

Example 4 Example 5 Example 6 Formulation Note 1 polyester resin U 35.0 U 35.0 U 35.0 alkyd resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin U125 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium Cr-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 Silicone TsA-720 ext. catalyst P-TSA Baking condition *Cx30' 140 100 100 Film properties pencil hardness Note 2 H 3B H gel fraction Note 3 94 56 91 surface cond. Note 4 1 X water resist. Note 5 0 X X Paint properties more than more than storage stab. Note 6 3 months OK 3 months OK 20 days gelation Note 1....resinous weight is by solid weight 6872S/as 25.07.91 -37- Table 2 (continued) 4 44 4 4 It 4 444 4 4444 4.

44 44 444 444 4 4 44 *4 4 44 4 *15 Example NumberCmp Example 20 Example 21 Example 7 Formulation Note I.

polyester resin alkyd resin S 35.0 T 35.0 V 35.0 acrylic resin melamine resin U20SE 2.5.0 15.0 15.0 melamine resi~n U2.25 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4,0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 Silicone TSA-720 ext. catalyst P-TSA Baking condition *Cx30' 100 2.00 1,40 Film Pronerties pencil hardness Note 2 HB-F H F gel fraction Note 3 87 93 surface cond. Note 4 water resist. Note 5 0 0 0 Paint properties more than more than more than storage stab. Note 6 3 months OK 3 months OK 3 months OK Note resinous weight is by solid weight 68725/as 25.07.91 1; 4

K)

0 -38- Table 2 (continued) S S €t I I E r i k t t t t t I Example Number Comp. Comp.

Example 8 Example 22 Example 9 Formulation Note 1 polyester resin alkyd resin V 35.0 acrylic resin X 35.0 W 35.0 melamine resiv. U20SE 15.0 15.0 15.0 melamine resin U125 urea resin G-1850 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0,015 0.015 0.015 Silicone TSA-720 ext. catalyst P-TSA Baking condition Cx30' 100 100 100 Film properties pencil hardness Note 2 4B 2H 2B gel fraction Note 3 42 96 63 surface cond. Note 4 X water resist, Note 5 X 0 X Paint properties more than more than more than storage stab. Note 6 3 months OK 3 months OK 3 months OK Note I resinous weight is by solid weight 4

I

I

1872S/as 25.07.91 -39- Table 2 (continued) Example Number Comp.

Example 23 Example 10 Example 24 Formulation Note 1 polyester resin L 35.0 alkyd resin T 30.0 V 30.0 acrylic resin melamine resin U2OSE melamine resin U125 15,0 urea resin G-1850 20.0 20.0 xylene 1.0 1.0 Solvesso 100 n-butanol 4.0 4.0 Titanium CR-95 40.0 40.0 45,0 Fastgen blue NK 2.0 2.0 2,3 Silicone KF-69 0.015 Silicone TSA-720 0.2 0.2 ext. catalyst P-TSA 2.5 Baking condition °CX30' 80 80 100 Film properties pencil hardness Note 2 HB HB H gel fraction Note 3 79 76 92 surface cond. Note 4 0 X water resist. Note 5 6 X O Paint properties more than storage stab. Note 6 2 months 7 days 3 months OK gelation gelation Note resinous weight is by solid Weight r 812S/as 25.07.91 I f I i I ii \i.

it -4 cU Table 3 Example Number Comp. Comp.

R~xcale Example 11 Example 12 Formulation Note 1 acrylic resin X 50.0 W 50.0 W 50.0 isocyanate urosslink (Desmodule TPL-2291) 13.0 13.0 13.0 Cellosolve acetate .0.0 10.0 1010 Solvesso 3.00 26.0 26.0 26.0 fitanium CR-93 70,0 70.0 70.0 Fastqen blue NK 3.5 3.5 Modaflow 0.8 0.8 0.8 4 i S15 ext. catalyst DBTD 4 -0.006 Baking condition 9Cx301 80 80 444444 Film properties pencil hardness Note 2 H 3B H 44 4 gel fraction Note 3 92 65 J surface cond, Note 4 0 'Water resist. Note 5 0 0 So, Paint ropertis pot"-lie (hrs) 5 20 Note rosinois weight is by solid weight e 859I$/aS 25-07.91 Na~(I U 1 i~ k 9, -41- Table 4 Example Number Comp.

le 27 Exa i le 13 Example 26 Examp 49 9I 4 9 9 .9, *9 *4 9 94 4 9*t 9 t4 9 4 99 I Ir 4 9 494 4 49o 1 94 9 4 9* Formulation Note 1 polyester resin melamine resin Cymel 303 xylene Solvesso 100 n-butanol Titanium CR-95 Fastgen blue NK 15 Silicone KF-69 Baking condition 'Cx30' Film properties pencil hardness Note 2 gel fraction Note 3 20 surface cond. Note 4 water resist. Note Paint properties storage stabillty P 35.0 8.0 4.0 7.0 45.0 2.3 0.015 120 R 35.0 15.0 8.0 4.0 7.0 45.0 2.3 0.015 120 U 35.0 15.0 45.0 2.3 0. 015 120 F-H F-H 6B 82 90 39 C S© x more than more than more than 3 months OK 3 months OK 3 months OK Note 1..

resinous weight is by solid weight

A'

Si' 8592S/as 25.07.91 -42- Example 2 Preparation of alkyd resinous varnish I Into a reaction vessel fitted with heating device, stirrer, refluxinq device, water separator, fractionator and thermometer, were placed 88.6 parts of coconut oil, 22.1 parts of dehydrated castor oil, 39.9 parts of trimethylolethane, and 0.1 part of lithium naphthenate and the mixture was heated to 240"C. Ester-exchange reaction was effected at 240*C, and then added with 38.7 parts of trimethylolethane, 141.8 parts of isophthalic acid, 14.6 parts of adipic acid, 31.6 parts of neopentylglycol and 7 parts of xylene. The mixture was heated to 220-230°C, dehydration reaction was effected at the same temperature until the resin value acid reached 2.0 and then the mixture i's? was allowed to cool. Next, 31 parts of Iylene were added at adjust the non-volatile content to 90%,and after adding with 10.0 parts of phthalic anhydride, the mixture was reacted to 150'C for 1 hour. 125 Parts of xylene were added to adjust 't the non-volatile content to 68.2%, 1.66 parts of N-(2-hydroxyethyl)ethyleneimine (HEEI) were added, the Smixture was reacted at 80'C for 1 hour and finally 67 parts of Cellosolve acetate were added to obtain alkyd resin varnish A. The characteristics of this varnish are shown in Table Examples 29 to 34 The same procedures as stated in Example 28 were repeated excepting using the materials shown in Table under the columns of Examples 29 to 34 (In Examples 31 to 34, no ester exchange reaction step was involed). The characteristics of thus obtained varnishes II to VII are shown in Table In these Examples, the used alkyleneimines and basic resins are as follows: i

I

8592S/as 25.07.91 Vu-- u-iu u UM L JV IIIuLl.taU cQi Ln -AdMPle z3.

Thus obtained coating was evaluated in the same way and the results were shown in Table 3.

25,07.91 ;ii Example 29 31 32 33 34 -43alkyleneimine ethyleneimine (EI) N-(2-hydroxyethyl)ethyleneimine(HEEI) N-(2-hydroxyethyl)ethyleneimine(HEEI) 1,2-propyleneimine (PI) N-(2-hydroxyethyl)ethyleneimine(HEEI) N-(2-hydroxyethyl)ethyleneimine (HEEI) basic resin alkyd resin alkyd resin polyester resin polyester resin polyester resin polyester resin I 1I 4* I I I It t -rrr fC I I 11*

*I

ttc

I

ft 6 f t Examples 35 to 39 (Comparative Example) Preparation of acrylic resin varnish VIII and Comparative varnish XII Into a reaction vessel, were placed 80 parts of xylene, parts of Cellosolve acetate, 35 parts of methyl methacrylate (MMA), 48 parts of ethyl acrylate 16 15 parts of 2-hydroxyethyl methacrylate (HEMA) and 1 part of methacrylic acid (MAA), and the mixture was heated to 110°C. While maintaining the same temperature, a mixed solution of 80 parts of xylene, 20 parts of Cellosolve acetate, 1 part of azobisisobutyronitrile and 0.25 parts of laurylmercaptane was dropwisely added at a constant rate in 3 hours, and after standing for 2 hours, 3.7 parts of tetrachlorophthalic anhydride were added and the mixture was heated to 140°C. When the resinous acid value reached to 14.0, the mixture was allowed to cool. The characteristics 25 of thus obtained acrylic resin varnish XII (Comparative resin varnish) are shown in Table To the acrylic resin varnish XII, were added 0.33 part of N-(2-hydroxyethyl)ethyleneimine and the mixture was reacted at 80"C for 1 hour and then allowed to cool. The characteristics of thus obtained acrylic resin varnish VIII are shown in Table 4

I

SI,

C 4 Example 36 (Comparative alkyd resin varnish IX) Alkyd resin varnish IX was prepared in a conventional way, using the materials shown in Table 5. The characteristics of thus obtained varnish are also given in Table 4 s592S/as 25.07.91 .I A! Sample specimen of baked coating was subjected to a solvent extraction, by using Soxhlet-extractor, with A 10.0 6872S/as 25.07.91 -44- Examples 37--38 (Comparative polyester resin varnishes X and

XI)

The materials shown in Table 4 under the column of 1st step reaction (dehydration) were reacted until the resinous acid value of 2.0 was reacted and xylene was added to adjust the non-volatile content of 90.0%. Thereafter, phthalic t anhydride in Example 37 and tetrachlorophthalic anhydride in Example 38 each was added and reacted at 150°C for 1 hour.

After cooling, xylene and Cellosolve acetate (70/30) were added to obtain polyester resin varnishes X and XI, respectively. The characteristics of these varnishes are shown in Table Example 15 A coating composition was prepared by mixing 35.0 parts Sa:s' (solid) of alkyd resin varnish I obtained in Example 28, 15.0 parts (solid) of U-van 20 SE-60 (melamine resin, manufactured by Mitsui Toatsu 8.0 parts of xylene, parts of Solvesso 100, 7.0 parts of n-butanol, 0.015 part of Silicone KF-69 (Shinetsu Kagaku 45.0 parts of Titanium CR-95 (Ishihara Sangyo and 2.3 parts of Fastgen Blue-NK (Dainippon Ink Thus obtained pale bluish white colored paint composition was diluted with a mixed solvent of 20.0 parts of Solvesso 100, 50.0 parts of toluene, 10.0 parts of xylene and 20.0 parts of n-butanol, to adjust the viscosity (Ford cup #4 viscosity) to This was applied by spraying onto SPC-1 dull steel plate previously treated with zinc phosphate and after keeping for a defined period of time, the coated plate was baked at 100°C for 30 minutes. The coating was evaluated and the test results are shown in Table 6. The storage stability and time color stability of said pale bluish white colored coating composition were also evaluated and the test results are shown in Table 6.

S2S/as 25.07.91 *'8§-i2S/as 25.07.91 l Examples 41-49 In Example 40, alkyd resin varnish I was replaced by each of the following and coating composition was prepared according to the prescription of Table 6. The viscosity of the composition was adjusted, and it was applied on the similar dull steel plate and baked at 100 0 C for 30 minutes as in Example 40. The coating was evaluated and results were shown in Table 6. Storage stability and time color stability of the composition were also evaluated and results were given in the same Table.

Example 41 alkyd resin II (Example 29) Example 42 alkyd resin III (Example Example 43 polyester resin IV (Example 31) *t 15 Example 44 polyester resin V (Example 32) SExample 45 polyester resin VI (Example 33) Example 46 polyester resin VII (Example 34) Example 47 polyester re in IV (Example 31) Example 48 polyester re. n IV (Example 31) Example 49 acrylic resin VIII (Example SComparative Examples 14-18 In Example 40, the alkyd resin varnish I was replaced by each of the following resin varnish and the respective coating composition was prepared as in Example 40 (in Comparative Example 16, 1.0 part of p-toluenesulfonic acid was added as external catalyst). After adjusting the viscosity, the composition was appli.ed on the similar dull steel plate and baked at 100°C for 30 minutes. The coating properties were evaluated and shown in Table 6. Storage stability and time color stability of the coating composition were also evaluated and the results were shown in Table 6.

Comparative Example 14 alkyd resin IX (Example 36) Comparative Example 15 alkyd resin X (Example 37) Comparative Example 16 alkyd resin IX (Example 36) Comparative Example 17 polyester resin XI (Example 38) Comparative Example 18 acrylic resin XII (Example 39) 8592S/as 25.07.91 i I _I -46- Example 50-52 In Example 40, the melamine resin U-20 SE-60 was replaced by Cymel 303 (Mitsui Toatsu and alkyd resinous varnish I was by each of the following resinous varnishes to obtain the respective coating compositions.

After adjusting the viscosity, each compositions were applied on the similar dull steel plates and baked at 120°C for 30 minutes. The coatings were evaluated the test results were shown in Table 6. Storage stability and time color stability of the coating compositions were also evaluated and the test results were given in Table 6.

Example 50 alkyd resin III (Example Example 51 polyester resin IV (Example 31) Example 52 polyester resin VII (Exaliple 34) S* Comparative Examples 19-21 In Example 40, melamine resin U-20SE-60 was replaced by Cymel 303 (Mitsui Toatsu and alkyd resinous varnish I was by each of the following varnishes, to obtain the coating compositions (In Comparative Example 34, 1.0 part of p-toluene sulfonic acid was added as external catalyst).

They were, after adjusting the viscosity, applied on the similar dull steel plates and baked at 120°C for minutes. Thus obtained coatings were evaluated and the test results were shown in Table 6. The storage stability and time color stability of the coating composition were also evaluated and test results were given in Table 6.

Comparative Example 19 alkyd resin IX (Example 36) Comparative Example 20 alkyd resin XX (Example 36) Comparative Example 21 polyester resin XI (Example 38) Example 53 The coating composition obtained in Example 52 was, after adjusting viscosity, applied on the similar dull steel plate as used in Example 40 and baked at 100°C for minutes. The coating properties were evaluated and the I

I

1,4 8592S/as 25,07.91

I

-47results were shown in Table 6. Storage stability and time color stability of the coating composition were almost identical with those of Example 52.

Example 54 The coating composition obtained in Example 46 was applied on the similar plate and baked at 80 0 C for minutes. The coating properties were evaluated and the results were shown in Table 6. It was found that storage stability and time color stability of the composition were identical with those of Example 46.

Comparative Example 22 The coating composition obtained in Comparative Example 17 was added with 0.5 part of triethanolamine and coated and baked at 100 C for 30 minutes. The properties of the coating and storage stability and time color stability of the coating composition were evaluated and the test results were given in Table 6.

Test methods and evaluation standards: Note 6, Storage stability Coating composition was kept at 50°C for 30 days and storage stability was evaluated by measuring the viscosity of the composition before and after said storage (measured by Stormer's viscometer), comparing the same and by following the undermentioned criteria: S@ storage stablility is quite excellent and there is no problems in pratical use O storage stability is good and there is no problems in practical use 4 storage stability is slightly inferior and there are problems in practical use X storage stability is no good and it cannot stand for practical use Note 7 Time colour stability The coating composition was kept standing at 20 C for 2 weeks. Thereafter, the composition was stirred well by stirring machine and applied by spraying, and then baked.

2S/as 25..07.91 V2. PP61872S/as 25.07.91 Y_ I -48- Colour difference AE value) between the baked plate and the standard plate (the same composition was applied by spraying immediately after being prepared and baked) was determined and the time colour stability was evaluated from the following criteria: colour difference AE) is less than 0.1, and time colour stability is very good Q colour difference A E) is less than 0.3 and time colour stability is good colour difference A E) is less than 0.5 and time colour stability is slightly inferior X colour difference AE) is more than 0.5 and time colour stability is no good 44 9.4 4 *r 4 #94 9 94*4 4,* 44 9, *444,4 4 4I 4 9, 44 4 9ir 4 4 4 v; i I

V:

8592S/as 25.07.91

J)

L6872S/as 25.07.91 -49- Table Example Example 28 Example 29 Example name of varnish I II III basic resin alkyd resin alkyd resin alkyd resin 1st stage reaction isophthalic acid 141.8 141.8 141.8 adipic acid 14.6 14.6 14.6 trimethylolpropane trimethylolethane 78.6 78.6 78.6 neopentylglycol 31.6 31.6 31.6 1,6-hexanediol coconut oil 88.6 88.6 88.6 dehydrated castor oil 22.1 22.1 22.1 resinous acid value at the end of 1st react. 2.00 2nd stage reaction polycarboxylic acid(a) phthalic anhyd pyromellitic tetrachloro Note 1 anhydride phthalic anhydride amounts 10.0 3,5 18 characteristic of resin resin, acid value of 13.0 9.0 12.0 basic resin resin. acid value based on acid Note 2 11.0 7 0 10.0j titration midpoint potential of -290 -180 -120 alkyleneimine compound name HEEM EI HEEI amounts 1.66 0.05 1.68 R' j -drLU S/as 25.07.91 j -ii B p Table (continued)

C

I I C I C C- C C CO Ct c Ce C: I Example Example 28 Example 29 Example name of varnish I II III basic resin alkyd resin alkyd resin alkyd resin equivalant res.

acid value 3.0 0.2 Varnish character.

non-volatile content% 60.3 60.1 60.0 varnish viscosity U-V X V total resin, acid value 10.3 8.8 resin, acid value based on acid Note 2 8.6 6.8 7.2 Note 1: polycarboxylic acid whose titr, midpoint potent.

is more than -300 mV Note 2: measured by non-aqueous potentiometric titration method ;/as 25.07.91 f 1"; f e i 1L, p -51- Table (continued) a t ra at e I 0g #4

OC

CI C Example Example 31 Example 32 Example 33 name of varnish IV V VI basic resin PE resin PE resin PE resin 1st stagce reaction isophthalic acid 113.0 127.3 127.3 adipic acid 29.2 29.2 29,2 trimethylolpropane 25.1 25.1 25.1 trimethylolethane neopentylglycol 52.8 52.8 52.8 1,6-hexanediol 56.0 56.0 56.0 15 coconut oil dehydrated castor oil resinous acid value at the end of 1st react. 2.0 2,0 2nd stage reaction polycarboxylic acid(a) phthalic anhyd trimellitic tetrachloro Note 1 anhydride phthalic anhydride amounts 45.0 6.0 11,O Characteristics of resin resin. acid value of basic resin resin. acid value based on acid Note 2 titration midpoint potential of (a) alkylneimine compound name amounts 60,0 5840 -290 12. 0 10. 0 -230 10,0 -120 R103 10.3

PT

0.93

HEEX

0.82 859S/as 507.91 -52- Table (continued) Example Example 31 Example 32 Example 33 name of varnish IV V VI basic resin PE resin PE resin PE resin equivalant res.

acid value 23.0 4.0 Varnish character.

non-volatLi-.e content% 60.0 60.0 60.1 varnish viscosity y-z w v-w total resin. acid~ value 36.8 8.3 7.9 resin, acid value based on acid Note 2 35.0 6.5 6.3, Note 1; polycarboxylic acid whose tit Midpoinlt potent, is more than -300 MV Note 2: measLured by non-aqueous potentiometric titration method 8592S/as 25.07.91 j: -53- Table (continued) Example Example 34 Example 35 Example 36

*I

II

II

I I

II

name of varnish basic resin 1st stage reaction isophthalic acid adipic acid trimethylolpropane trimethylolethane neopentylglycol 1,6-hexanediol coconut oil dehydrated castor oil resinous acid value at the end of Ist react.

20 2nd stage reaction polycarboxylic acid(a) Note 1 amounts Characteristic of resin resin, acid value of basic resin resin. acid value based on acid Note 2 titration midpoint potential of (a) alkyiengimine compognd name amounts

VII

PE resin

VIII

acrylic resin 127.3 29.2 25.1

MMA

EA

HEMA

MAA

52 .8 56.0 78.6 31.6 88.6 22.1

IX

alkyd resin 149.6 14.6 2.0 7.0 tetrachloro phthalic anhyd.

25.5 tetrachioro phthalic anhyd.

3.7 20.0 14.0 18.0 -120 -120

HEET

2. 16 0.33 0. 3

CN

1 92S/aS 25, 07.91 85,92S/as 25.07.91 I- F t4 ii -54-.

Table (continued) i Example Example 34 Example 35 Example 36 name of varnish basic Cesin equivalant res.

acid value Varnish character.

non-volatile content% varnish viscosity total resin. acid value resin, acid value based on acid Note 2

VII

PE resin 5.0 VIII IX acrylic resin alkyd resin 59.8

Y

15.5 51.3

Z-Z

60.0

U

12.1 I K t 4 4 13 5 Note 1: polycarboxylic acid whose titr, ridpoint potent.

is more than -300 mV Note 2: measured by non-aqueous potentiometric titration method

F,

8592S/as 25.07.91

I

p Table (r ,tinued) Example Example 37 Example 38 Example 39 name of varnish basic resin ist stage reaction

X

alkyd

XI

PE resin

XII

acrylic resin resin a t 9 P 0 0 0 0P 0 0 *4;

I)

r 00 0~ 0 isophthalic acid 1 adipic acid trimethylolpropane trimethylolethane neopentylglycol 1,6-hexanediol 15 coconut oil dehydrate' castor oil resinous acid value at the end of ist react, 20 2nd stage reaction polycarboxylic acid(a) Note 1 amounts Characteristic of resin resin, acid value of basic resin resin, acid value based on acid Note 2 titration midpoint potential of (a) alkyleneimine compound name amounts 141.8 14.6 78.6 31.6 88.6 22.1 127.3 29.2 25.1 52.8 56.0 MMA EA 48 HEMA 16 MAA 1 2.0 2.0 phthalic tetrachloro tetrachloro anhydride phthalic phthalic anhydride anhydride 10.0 18.4 3.7 IJ .0 15.0 14.0 -120 11,0 13.0 -120 i 8592S/as 25.07.91 41 -56- Table I, (continued) 4 44 4 4 4 4 444 9 '444 4* 4 44 44 44444w 4 4 #4 44 4 444 4 44 4 4 *4 4 44 4 4 '4,44.

4 4444 44 4 44 4, o 44..

44 4 44 4* 44 4 44 4 4* 4 4 Bxample Example 37 Example 38 E-xample 39 name of vn.rnish X XI XII basic resin alkyd resin PE resin acrylic resin eguivalant res.

acid value Y~iiisjh characternon-volatile content% 60.0 60.1 51.2.

varnish viscosity U-V X-YZ 1

Z

total resin, acid 1.5 value 13.0 15.0 14.0 resi.n. acid value based on acid Note 2 11.0 13.0 Note 1: polycarboxylic acid whose titr. midpoint potent.

is more than -300 mV Note 2: measured by non-aqueous potent iometric titration method 8592S/as 25.07.91 characteristics of thus obtained varnish are also given in Table fx 0 8' S. '25,079 f r Ft/4 92S/a 25.07.91 ~,*2ii1 .4 -57- Table 6 *0 0 0 0 0 0t* 0 0*#q 0 00 0*44 tO 0 00 00 0 0 0 $00 I 0$ 4 0 44 o I I Example Number Example 40 Example 41 Example 42 Formulation Note 1 alkyd resin I 35.0 II 35.0 III 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin C-303 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS Baking condition °Cx3G 0 100 100 100 Film properties pencil hardness Note 2 HB-F F H-2H gel fraction Note 3 91 93 surface cond. Note 4 water resist. Note 5 0 0 0 Paint properties storage stab. Note 6 0 time color stability Note 7 0 Note .resinous weight is weight nxpressed by solid

NK

F

8592S/as 25.07.91 1 -58- Table 6 (continued) 4 .4 *r a 44 4 .44r 4 4.44 0O 04 0 44 Example Number Comp. Comp. Comp.

Example 14 Example 15 Example 16 Formulation Note 1 alkyd resin IX 35.0 X 35.0 IX 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 15.0 15,0 melamine resin C-303 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS Baking condition °Cx30' 100 100 100 Film prcoertigA pencil hard'ess Notr 2 3B HB-F i-2H gel fraction Note 3 51 91 surface cond. Note 4

X

water resist. Note 5 X 0 X Paint properties storage stab. Note 6 0 x A time color stability Note 7 X X Note resinous weight is expressed by solid weight o< i I "F -59-- Table 6 (continued) Example Number Example 43 Example 44 Example ii Formulation Note 1 alkyd resin IV 35.0 V 35.0 VI 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin C-303 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 15 Titanium CR-95 45.0 45.0 45.0 4#a 0Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 a triethyl amine aext. catalyst PTS Baking condition OCx30' 100 100 100 Film properties pencil hardness Note 2 H-2H- H H-2H gel fraction Note 3 95 93 surface cond. Note 4 water resist. Note 5 Q 0 0 Paint properties storage stab. Note 6 0© time color stability Note 7 0©© Note l1 .resinous weight is expressed b-y solid weight

AA

minutes. The coating properties were evaluated and the ifC

I>

8592S/as 25.07.91 p mm--- Table 6 (continued) o a *0 *0 a* a; 4

I

*14 a* Example Number Example 46 Example 47 Example 48 Formulation Note 1 alkyd resin VII 35.0 IV 35.0 IV 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 10.0 20.0 melamine resin C-303 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS Baking condition Cx30' 100 100 100 Film properties pencil hardness Note 2H H 2H gel fraction Note 3 96 87 94 surface cond. Note 4 0 0 water resist. Note 5 Q 0 0 Paint properties storage stab. Note 6 0 time color stability Note 7 0 Note resinouq weight is weight expressed by solid 8592S/as 25.07.91

A.

-61- Table 6 (continued) t ~1 4 1 Example Number Comp. Comp.

Example 17 Example 49 Example 18 Formulation Note 1 alkyd resin XI 35.0 VIII 35.0 XII 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 15.0 15.0 melamine resin C-303 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS Baking condition °Cx30' 100 100 100 Film properties pencil hardness Note 2 2H 2H 2H gel fraction Note 3 96 95 surface cond. Note 4 a o (Q water resist.- Note 5 0 0 0 Paint properties storage stab. Note 6 X 0 X time color stability Note 7 X X Note 1 resinous weight weight is expressed by solid t! 8592S/as 25.07.91

I

-62- Table 6 (continued) Example Number Example 50 Example 51 Example 52 9 *9 99 9 999 4 9999 *9 9 99 99 9 99,99.

99 9 9 99 9 994 .9 99 9 4 91 9 #9 9 9 Formulation Note 1 alkyd resin polyester resin acrylic resin melamine resin melamine resin C-303 xylene Solvesso 100 n-butanol 15 Titanium CR-95 Fastgen blue NK Silicone KF-69 triethylamine ext. catalyst PTS Baking condition °Cx30' Film properties pencil hardness Note 2 gel fraction Note 3 surface cond. Note 4 water resist. Note Paint properties storage stab. Note 6 time color stability Note 7 III 35.0 15.0 8.0 4.0 7.0 45.0 2.3 0.015 120

F-H

91, 0 0 IV 35.0 15.0 8.0 4.0 7.0 45.0 2.3 0.015 120

F-H

91 0 VII 35.0 15.0 45.0 2.3 0.015 120 H-2H 0 Note resinous weight is weight expressed by solid 8592S/as 25.07.91 -63- Table 6 (continued) Example Number Comp. Comp. Comp.

Example 19 Example 20 Example 21 Formulation Note 1 alkyd resin IX 35.0 IX 35.0 XI 35.0 polyester resin acrylic resin melamine resin melamine resin C-303 15.0 15.0 15.0 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45.0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS 10 Baking condition OCx30' 120 120 120 Film properties pencil hardness Note 2 6 B F-H H-2H gel fraction Note 3 25 90 surface cond. Note 4 X X water resist. Note 5 X X 0 Paint properties storage stab. Note 6 X X time color stability Note 7 A X X Note 1 resinous weight is expressed by solid weight ~4.

t I St I S S I t 8592S/as 25.07.91 -64- Table 6 (continued) t, t1 t f ei I I t f tt I i I t e4 Example Number Comp.

Example 53 Example 54 Example 22 Formulation Note 1 alkyd resin VII 35.0 VII 35.0 XI 35.0 polyester resin acrylic resin melamine resin U20SE 15.0 15.0 melamine resin C-303 15.0 xylene 8.0 8.0 Solvesso 100 4.0 4.0 n-butanol 7.0 7.0 Titanium CR-95 45.0 45,,0 45.0 Fastgen blue NK 2.3 2.3 2.3 Silicone KF-69 0.015 0.015 0.015 triethylamine ext. catalyst PTS Baking condition *Cx30' 100 80 100 Film properties pencil hardness Note 2 HB-F F-H 2H gel fraction Note 3 84 88 surface cond,. Note 4 water resist. Note 5 0 0 0 Paint properties storage stab. Note 6 0 time color stability Note 7 X Note resinous weight weight is expressed by solid fNT 8592S/as 25.07.91 i

Claims (13)

1. A resin having resinous acid value of M N obtainable by the reaction of a base resin having a functional group reactive with a cross-linking agent selected from an aminoplast or isocyanate compound, and a functional group reactive with a carboxyl group, the base resin having a resinous acid value of M, wherein M is zero or any positive number; and an unsaturated cyclic polycarboxylic acid having a titration midpoint potential in a non-aqueous TBAH (tetrabutylammonium hydroxide) potentiometric titration of greater than -300mV; wherein N is a resinous acid value of from 2 to 50 afforded to the resin by the carboxyl groups derived from the unsaturated polycarboxylic acid

2. A resin as claimed in claim I wherein the base resin is selected from the group consisting of an acrylic resin, an alkyd resin, a polyester resin, an epoxy resin, a polyurethane resin, a polemide resin and a polycarbonate resin. I

3. A resin as claimed in claim i or claim 2 wherein the polyoarboXylic acid is selected from the group consisting of phthalic anhydride, pyromellitic acid, o 25 pyromellitic anhydride, trimellitic acid, trimellitic anhydride, tetrachlorophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic anhydride, tetrabromophthalic acid, HET acid and HET anhydride.

4. A resin as claimed in any one of the preceding claims substantially as herein described with reference to any non-comparative Fample.

A method for preparing a resin having a resinous acid value of M N as claimed in any one of the preceding claims comprising esterifying Wa parts by weight of the base resin having a resinous acid value of M; with '8592S/as 25.07.91 i gr ~I- -66- Wb parts by weight of the polycarboxylic acid wherein N Wa Wb (56100/E) P/100) -N wherein E is 1 gram equivalent of the polycarboxylic acid P is the reaction of the polycarboxylic acid to be reacted with the base resin and N is the desired resinous acid value between 2 and

6. A method as claimed in claim 5 substantially as herein described with reference to any non-comparative Example.

7. A resin prepared by a method as claimed in claim or claim 6.

8. A resin obtainable by the reaction of a resin as claimed in any one of claims I to 4 and 7; and an alkyleneimine compound having at least one alkyleneimine ring of 2 to 3 carbon atoms, in an amount equivalent to a resinous acid value of from 0.01 to 504

9. A resin as claimed in claim 8 wherein the alkyleneimine compound has the general formula: R 2 6 R3 Q -94 wherein R1, R 2 j R 3 R 4 and ,are the same or different and are selected from the group consisting of hydrogen, C-c 20 alkyl, phenyl, totyl, xyyl, benzyl and pheanthyll R6 is hydrogen or CI-C6 alky.

R 1 R2 H 3 R4 R, and Rare optionally substituted with carbonyl, eyano, halogen, amino, hydroxyl, alkoxy, carbalkoxy or nitrile; and n is 0 or 1., 8592S/as 25t07.91 -67- A resin as claimed in claim 8 wherein the alkyleneimine compound is selected from the group consisting of ethyleneimine, 1l 2-propyleneimine, 1, 3-propyloneimine, 1, 2-dodecyleneimine, 1, 1-dimethylethyleneimine, hnltyeemn, oyehlniie penylethyleneimine, toldieylethyleneimine, 2-hydroxyethylethyleneimine, amino-ethylethyleneimine, 2-methyipropyleneimine, 3-chloropropylethyleneimine, p-chlorophenyle-thyleneimine, methoxyethylethyleneimine, carboethoxyethylethyleneimine, N-ethylethyeneimine, N-butylethyleneimine, N- (2-aminoethyl) ethyleneimine, N- (2 -hydroxyethyl) ethyl eneimine N- (cyanoethyl) ethylene imine, N-phenyl ethyl e.-e iine, N-triethyleth,-4e:.-eimine, N- (p-chlorophenyl) ethyl.eneimine, N- (2-carbethoxy-1-ethyl) ethyleneimine, ethylene-l,2-bisaziridine and 1, 2,4-tris 1-azirLdinylethyl) -tri-iiallitate.

11. A resin as claimed in claim 8 substantially as herein described with reference to any non-comparative Example.

12. A resinous composition comprising 45 to 95% b~y weight (solid) of~ a rosin as claimed in aniy one of cla)'als I to 4 and 7 to 10, and 5 to 55t by weight (solid) of a cross-lin}king agent selected from, an amitioplast, or isocyanate comnpound.

13. A resinous Pomposition as claimed in claim 12 substantially as herein described with reference to any non-comparative Example. DATED this 25th day of July 1991 NTPPN PtNTCO,, T,) By ita Patent Attorneys GRIFFITH HACK CO. s 25.07.91