CA1318075C - Resinous composition for coating use - Google Patents
Resinous composition for coating useInfo
- Publication number
- CA1318075C CA1318075C CA000573666A CA573666A CA1318075C CA 1318075 C CA1318075 C CA 1318075C CA 000573666 A CA000573666 A CA 000573666A CA 573666 A CA573666 A CA 573666A CA 1318075 C CA1318075 C CA 1318075C
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- Prior art keywords
- coating
- melamine
- trademark
- composition
- resinous
- Prior art date
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Mo-3158 LeA 25,530 A PROCESS FOR THE PRODUCTION OF
POLYNUCLEAR AROMATIC POLYAMINES
ABSTRACT OF THE INVENTION
This invention relates to an improved process for the preparation of polynuclear aromatic polyamines, in which the reaction product is prepared by condensing aniline with fonmaldehyde in the presence of water and acjdic catalysts and is worked up by extraction with a hydrophobic solvent. The acid catalyst that accumulates in the aqueous phase during the extraction process is reused.
Le A 25 530
POLYNUCLEAR AROMATIC POLYAMINES
ABSTRACT OF THE INVENTION
This invention relates to an improved process for the preparation of polynuclear aromatic polyamines, in which the reaction product is prepared by condensing aniline with fonmaldehyde in the presence of water and acjdic catalysts and is worked up by extraction with a hydrophobic solvent. The acid catalyst that accumulates in the aqueous phase during the extraction process is reused.
Le A 25 530
Description
~31~7~
A resinous composition for coating use Field oE the invention ~he present invention relates to a resinous composition for coating use, which is excellent in resistance to abrasion and is specifically useful as resinous vehicle in a top coat paint, including a solid colored paint and a clear coat paint, for automobile body, electric appliance and the iike.
Backgroung of the invention In a top coat paint for automobile body, electric appliance and the like, various combination of resins have - been used as, for example, melamine/alkyd resins, melamine/polyester resins, melamine/acrylic resins, melamine/acrylic/epoxy resins, acrylic/urethane resins, polyester/urethane resins and the like. However, in a deep color paint containing relatively smaller quantity of pigment, there are problems that the coating resulted is liable to be injured and coating scratches show up conspicuously.
Since an automobile is often subjected to an auto-washing machine, and recently, a vivid deep color is in much request in the coating of automobile body and the like, resistance to abrasion of a coating is getting more and more important for paint industries and longing for a good solution for the same. What are wished for are not only the 131~7~
improvement in abrasion resistance, but also the improvement in initial coating qualities and especially prevention of rapid loss in glamourous appearance.
Employment of resinous mat.erial having a lower glass transition temperature (Tg) and various other proposals for hardening a coating have all failed in obtaining the abovesaid improvements.
It is, therefore, an object of the invention to provide a resinous composition which can be used as a top coat or a clear coat for automobile body or the like and capable of resulting a coating with excellent resistance in abrasion and chipping resistance, whose glamorous appearance and gloss would not be disappeared in a short period of time.
Summary of the invention According to the invention, the aforesaid object can be attained with a resinous composition for coating use comprising (A) a melamine resin having a monomeric content of 50 or more and a degree of etherification of 5 or more, 80 or more of the ether groups contained being methylated me-thylol groups, and (B) an aliphatic or alicyclic linear-structured compound having an average molecular weight of 100 to 1000 and bearing end hydroxyl groups, which may include ether or ester bonds, the solid weight ratio of said (A) to(B) being 3/7 to 7/3.
1 3 ~
Preferred embodiments of the invention ~ lelamine resin is a thermosetting resin prepared by reacting 2,4,6-triamino-1,3,5-triazine (a common name of melamine) and formaldehyde to give a methylolated melamine and subjecting the latter to the reaction with a lower alcohol. Since the melamine resin can aEford, when baked, a coating with excellent properties in respects of hardness, gloss, rub resistance, weather resistance and chemical resistance, it has widely been used as the coating for 10 automobile body, electric appliance and the like.
Such a resin is usually employed in the form of resinous varnish.
Generally accepted melamine resins are mainly composed of polynuclear structure, in which 2 or more melamine 15 molecules are condensed together, and etherification is mainly of butylation type. Degree of etherification is commonly 3 or less.
The present inventors, as the results of a series of studies for improving abrasion resistance of melamine resin 20 while maintaining the desired properties thereof, have succeeded in finding a resinous composition comprising a particular melamine resin as a hard component and a particular linear aliphatic or alicyclic compound as a soft component in a specific weight ratio, which can result a 25 baked coating having excellent abrasion resistance, gloss and glamorous appearance, and on the basis these findings, have succeeded in establishing the present invention.
~ 31~7~
The melamine resin as used in the present invention as a hard component i5 a etherified melamine resin, majority, i.e. 50% or more, preferably 80~ or more, of which are composed of monomeric melamine. Degree of etherification must be 5 or more and 80~ or more of said etherification must be of methylation type.
Thus, the present melamine resin is mainly composed o monomeric, methylated methylol melamine. Examples of such melamine resins are Cymel 303, (trademark, ~litsui Toatsu lO Chem. Co.), Sumimal ~1100 (trademark, Sumitomo Chem. Co.) and -the like.
In the present invention, to the abovementioned melamine resin, is compounded as a soft component a linear-structured aliphatic or alicyclic compound having end 15 hydroxyl groups and a number average molecular weight of 100 to 1000.
Such compound may include in its main chain ether or ester bonds. Examples of such compounds are bi-functional compounds as polyethylene glycol, polypropylene glycol, 20 polybutylene glycol, K-Flex 188 and IC-Flex 148 (trademarks of polyester polyols HocH2~CE~200C COOCH2~CH20EI
molecular weights 490 and 478, viscosities 10000 cps and 4000 cps, hydroxyl values 230 and 235, respectively, 25 manufactured by King Co.), reaction products of bi-functional aliphatic or alicyclic acids and glycol: decane l,10-diol, dodecane 1,12-diol, polycarbonate diol D-1000 13~7~
(trademark, HO-(ROCO ~ RO~I, manufaetured by Toha Gosei K.K.), bi-functional polycaprolaetones of the formula EIO ~ (C~l2)5C- ~ R--~--O Cll (CH2)5~0~.1 O O
like Plaecel 205 (polycaprolactone molecular weight 500), Placcel 208 (molecular weight 800), Placcel 210~(molecular weight 1000), all trademarks of Daieel K.K.), and X-22-160AS
(end reaetive silicone oil, molecular weight 1000, manufactured by Shinetsu Kagaku), and tri-funetional compounds as tri-functional polyeaprolactones of the formula:
HO~ (CH2)5-1C-O ~ R ~O-ICl(cH2)5-]n OH
O O
~[ O-C-(CH2)5 ]n OEI
like Plaeeel 303 (moleeular weight 310), Placeel 305 (molecular weight 550), Plaecel 308 (molecular weight 860), all trademarks of Daieel K.K.).
The abovesaia melamine resin and the abovementioned soft component eompound are blended in a weight ratio (on solid basis) of 3/7 to 7/3.
When the present resinous eomposition is applied on a substrate and bakea at a higher temperature as, for example 160DC or more, the melamine resin (hard eomponent) and the - soft eomponent eompound are reaeted together in sueeessive order, to give a network struetural, erosslinked resin, ~ 3 ~
which is speciEically excellent in abrasion resistance and still maintains desired properties of melamine resin.
To attain the object of the invention, the following are essential.
(l) ~1elamine resin must be mainly composecl of mono-meric structure. If it is of conventional type, i.e.
mainly composed of trimeric structure, there only results an excessively hard coating.
A resinous composition for coating use Field oE the invention ~he present invention relates to a resinous composition for coating use, which is excellent in resistance to abrasion and is specifically useful as resinous vehicle in a top coat paint, including a solid colored paint and a clear coat paint, for automobile body, electric appliance and the iike.
Backgroung of the invention In a top coat paint for automobile body, electric appliance and the like, various combination of resins have - been used as, for example, melamine/alkyd resins, melamine/polyester resins, melamine/acrylic resins, melamine/acrylic/epoxy resins, acrylic/urethane resins, polyester/urethane resins and the like. However, in a deep color paint containing relatively smaller quantity of pigment, there are problems that the coating resulted is liable to be injured and coating scratches show up conspicuously.
Since an automobile is often subjected to an auto-washing machine, and recently, a vivid deep color is in much request in the coating of automobile body and the like, resistance to abrasion of a coating is getting more and more important for paint industries and longing for a good solution for the same. What are wished for are not only the 131~7~
improvement in abrasion resistance, but also the improvement in initial coating qualities and especially prevention of rapid loss in glamourous appearance.
Employment of resinous mat.erial having a lower glass transition temperature (Tg) and various other proposals for hardening a coating have all failed in obtaining the abovesaid improvements.
It is, therefore, an object of the invention to provide a resinous composition which can be used as a top coat or a clear coat for automobile body or the like and capable of resulting a coating with excellent resistance in abrasion and chipping resistance, whose glamorous appearance and gloss would not be disappeared in a short period of time.
Summary of the invention According to the invention, the aforesaid object can be attained with a resinous composition for coating use comprising (A) a melamine resin having a monomeric content of 50 or more and a degree of etherification of 5 or more, 80 or more of the ether groups contained being methylated me-thylol groups, and (B) an aliphatic or alicyclic linear-structured compound having an average molecular weight of 100 to 1000 and bearing end hydroxyl groups, which may include ether or ester bonds, the solid weight ratio of said (A) to(B) being 3/7 to 7/3.
1 3 ~
Preferred embodiments of the invention ~ lelamine resin is a thermosetting resin prepared by reacting 2,4,6-triamino-1,3,5-triazine (a common name of melamine) and formaldehyde to give a methylolated melamine and subjecting the latter to the reaction with a lower alcohol. Since the melamine resin can aEford, when baked, a coating with excellent properties in respects of hardness, gloss, rub resistance, weather resistance and chemical resistance, it has widely been used as the coating for 10 automobile body, electric appliance and the like.
Such a resin is usually employed in the form of resinous varnish.
Generally accepted melamine resins are mainly composed of polynuclear structure, in which 2 or more melamine 15 molecules are condensed together, and etherification is mainly of butylation type. Degree of etherification is commonly 3 or less.
The present inventors, as the results of a series of studies for improving abrasion resistance of melamine resin 20 while maintaining the desired properties thereof, have succeeded in finding a resinous composition comprising a particular melamine resin as a hard component and a particular linear aliphatic or alicyclic compound as a soft component in a specific weight ratio, which can result a 25 baked coating having excellent abrasion resistance, gloss and glamorous appearance, and on the basis these findings, have succeeded in establishing the present invention.
~ 31~7~
The melamine resin as used in the present invention as a hard component i5 a etherified melamine resin, majority, i.e. 50% or more, preferably 80~ or more, of which are composed of monomeric melamine. Degree of etherification must be 5 or more and 80~ or more of said etherification must be of methylation type.
Thus, the present melamine resin is mainly composed o monomeric, methylated methylol melamine. Examples of such melamine resins are Cymel 303, (trademark, ~litsui Toatsu lO Chem. Co.), Sumimal ~1100 (trademark, Sumitomo Chem. Co.) and -the like.
In the present invention, to the abovementioned melamine resin, is compounded as a soft component a linear-structured aliphatic or alicyclic compound having end 15 hydroxyl groups and a number average molecular weight of 100 to 1000.
Such compound may include in its main chain ether or ester bonds. Examples of such compounds are bi-functional compounds as polyethylene glycol, polypropylene glycol, 20 polybutylene glycol, K-Flex 188 and IC-Flex 148 (trademarks of polyester polyols HocH2~CE~200C COOCH2~CH20EI
molecular weights 490 and 478, viscosities 10000 cps and 4000 cps, hydroxyl values 230 and 235, respectively, 25 manufactured by King Co.), reaction products of bi-functional aliphatic or alicyclic acids and glycol: decane l,10-diol, dodecane 1,12-diol, polycarbonate diol D-1000 13~7~
(trademark, HO-(ROCO ~ RO~I, manufaetured by Toha Gosei K.K.), bi-functional polycaprolaetones of the formula EIO ~ (C~l2)5C- ~ R--~--O Cll (CH2)5~0~.1 O O
like Plaecel 205 (polycaprolactone molecular weight 500), Placcel 208 (molecular weight 800), Placcel 210~(molecular weight 1000), all trademarks of Daieel K.K.), and X-22-160AS
(end reaetive silicone oil, molecular weight 1000, manufactured by Shinetsu Kagaku), and tri-funetional compounds as tri-functional polyeaprolactones of the formula:
HO~ (CH2)5-1C-O ~ R ~O-ICl(cH2)5-]n OH
O O
~[ O-C-(CH2)5 ]n OEI
like Plaeeel 303 (moleeular weight 310), Placeel 305 (molecular weight 550), Plaecel 308 (molecular weight 860), all trademarks of Daieel K.K.).
The abovesaia melamine resin and the abovementioned soft component eompound are blended in a weight ratio (on solid basis) of 3/7 to 7/3.
When the present resinous eomposition is applied on a substrate and bakea at a higher temperature as, for example 160DC or more, the melamine resin (hard eomponent) and the - soft eomponent eompound are reaeted together in sueeessive order, to give a network struetural, erosslinked resin, ~ 3 ~
which is speciEically excellent in abrasion resistance and still maintains desired properties of melamine resin.
To attain the object of the invention, the following are essential.
(l) ~1elamine resin must be mainly composecl of mono-meric structure. If it is of conventional type, i.e.
mainly composed of trimeric structure, there only results an excessively hard coating.
(2) ~lonomeric melamine and soft component compound must be reacted in successive order so as to give a network s-tructure product, otherwise the desired abrasion resistance cannot be obtained.
(3) In order to attain a defined level of hardness of the coating, etherification of said melamine must be mainly of lS methylation type.
(4) Degree of etherification of melamine must be 5 or more to prevent possible reaction of mutual melamine resins themselves.
(5) ~lolecular weight of the soft component compound must be in a range of lO0 to lO00, preferably 300 to 600. If the molecular weight is outside the abovementioned range, the desired sprlng-like action of the soft component compound cannot be expected.
(6) The maximum quantity of either soft component or hard component must be limited to 70~ by weight. If the former exceeds over the upper limit of 70~ by weight, there results a deEicient crosslinking, and if the latter, an 7~
excessively progressed hardening. In either case, the desired abrasion resistance can hardly be obtaine-l.
The inventors have also Eound that though it is not essential in the present invention, a strong acidic catalyst as p-toluene sulfonic acid, dinonyl naphthalene disulfonic acid, dodecyl benzene sulfonic acid and the like may advantageously be added to the present resinous composition in an amount corresponding to 0.2 to 3~ by weight of the total solid, thereby reducing the baking temperature to 10 160C or less. Therfore, in a particularly preferred embodiment, a strong acidic catalyst is present in the present resinous composition. If desired, pigment and other paint additives may be successfully added to the present resinous composition. Thus, the present resinous composition is useful as a resinous vehicle in a top coat composition including both solid color paint and clear coating composition, to be applied on automobile body, electric appliance and the like. The clear coating composition may be applied on both solid color paint and metallic coating. In either case, the abrasion resistance of such coating is excellent.
The invention shall be now more fully explained in the following Examples. Unless otherwise being stated, all parts and percentages are by weight.
7.~
Example l K-Flex 188 (trademark, polyester polyol, molecular weight 490, manuEactured by King Co.) as a soft component and Cymel 303 (trademark, melamine resin: monomeric 5 structure content 60% by weight, ~egree of etheriEication about 5.5, degree of methoxylation about 5.5, manufactured by Mitsui Tohatsu K.K.) as a hard component were blended in a solid weight ratio of 5:5, and the mixture was treated in a disper for 30 minutes to obtain a uniform solution. To 10 this solution, N~CURE 155 (trademark, King Co.) was added as a catalyst in an amount of l~ of the total weight of the composition and stirred well to obtain a resinous composition for coating use.
Examples 2 to 4 Resinous compositions were prepared by repeating the procedures of Example l, excepting revising the weight ratio of soft component/hard component as follows. That is, in Example 2, said ratio was changed to 4/6, in Example 3, to 3/7 and in Example 4, to 7/3.
Example 5 2.0 parts of carbon black and 50 parts on K-Flex 188 were mixed together. To this, were added equal quantities of glass beads (2mm diameter) and the combined mixture was treated in a disper for 60 minutes. Thereafter, 50 parts 25 Cymel 303 were added and mixed well in the disper for additional 30 minutes. Nacure 155 (catalyst) was then added in an amount of l~ of the total weight of the composition ~3~7.5 and mixed well to obtain a coating composition.
Example 6 The same procedures as stated in Example 1 were repeated, excepting substituting polye-thylene glycol 400 (trademark, polyethylene glyco:l manufactured by Aldrich Co.) for K-Flex 188 and Sumimal ~llO0 (trademark, melamine resin, monomeric structure content 80~ by weight, degree of etherification about 5.5, degree of methoxylation about 5.5, manufactured by Sumitomo Chem. Co.) for Cymel 303, to obtain 10 a coating composition.
Example 7 The same procedures as stated in Example 1 were repeated, excepting substituting polyethylene glycol 600 (trademark, polyethylene glycol manufactured by Aldrich Co.) for K-Flex 188 to obtain a coating compositon.
Example 8 The same procedures as stated in Example 1 were repeated, excepting substituting polypropylene glycol 425 (trademarX, polypropylene glycol manufactured by Aldrich Co.) for K-Flex 188 to obtain a coating composition.
Example 9 The same procedures as stated in Example 1 were repeated, excepting substituting Sumimal ~llO0 for Cymel 303 to obtain a coating composition.
Example 10 The same procedures as stated in Example 3 were repeated, excepting substituting K-Flex 1~8 (trademark, ~3~7~3' polyester polyol, molecular weight 47~, manufactured by King Co.) for l<-Flex 1~8 and Sumimal 11100 for Cymel 303 to obtain a coating composition.
Example 11 K-Flex 14~ as a soft component and Cymel 303 as a hard component were blended in a solid weight ~atio of 5:5 and stirred and mixed well in a disper for 30 minutes.
~hereafter, p-toluene sulfonic acid, diethanolamine and xylene were added each in the amounts corresponding to 1%, 0.92% and 40~ of the total weight of the resulted coating composition, and the combined mixture was stirred well until a uniform solution was obtained, heated under stirring to 100C and reacted at the same temperature for 2 hours to obtain a resinous composition comprising a polymer having a number average molecular weight of 5000.
Preparaion of coated test panels (A) To a series of test steel panels (each 300x500xO.Bmm size) previously treated with Granodine SD5000 (zinc phosphate pre-treating agent, trademark of Nippon Paint Co., Ltd.), was applied Power top U-30 (Epoxy urethane cationic electrodepositing coating composition, trademark of Nippon Paint Co., Ltd.) in a dry film thickness of 30~, baked at 170C for 20 minutes, was applied an intercoat of Orga P-2 (trademark, gray intercoat composition based on polyester resin, Nippon Paint Co., Ltd.) in a dry film thickness oE
35~ and baked at 140C for 20 minutes. Onto thus coated panels, coating compositions obtained in Examples 1 to 6 and 1 3 ~ 7 ~
Orga S-20 clear coating composition tEor comparison salce) (trademark, polyester resin base clear coating composition, Nippon Paint Co., Ltd.) each was applied in a dry film thickness oE 30~ and then baked at 140C for 20 minutes.
Thus obtained test panels were subjected to the following tests and their abrasion resistance, pencil hardness, gloss, accelerated weather resistance and water resistance properties were examined. The test results are shown in Table 1.
Preparation of coated test panels (B) To a series of test steel panels (each 300x500xO.8mm size) previously treated with Granodine SD5000 (zinc phosphate pre-treating agent, trademark of Nippon Paing Co., L,td.), was applied Power top U-30 (trademark, epoxy urethane cationic electrodeposition coa-ting composition, Nippon Paint Co., Ltd.) in a dry film thickness on 30J~, baked at 170C
for 20 minutes, was applied an intercoat of Orga P-2 in a dry film thickness of 35~ and baked at 1~0C for 20 minutes. Onto thus prepared plates, was applied Superlack ~I-90 Silver (trademark, acryl-melamine resin base silver colored coating composition, Nippon Paint Co., Ltd.) to a dry film thickness of 15~ and then, on wet-on-wet basis, each clear coating composition obtained in F.xample 1, Examples 7 -to 11 and Superlack 0-128 (trademark, acryl-melamine base clear coating composition, Nippon Paing Co.,Ltd.) in a dry film thickness of 15~ . Finally, they were baked at 140C for 20 minutes.
7 ~
Thus obtained test panels were subjected to the following tests and their abrasion resistance, pencil hardness, gloss, accelerated weather resistance and water resistance properties were examined. The test results are shown in Table 2.
The test methods and evaluation standards used are as follows.
l. Abrasion resistance Test plate is fixed on the roof of an automobile and 10subjected to an auto-washer 20 times. Thereafter, the coating conditions are visually examined.
O ....... no scratch O ....... faint scratch ~ ....... slight scratch X ....... scratches X X ........ quite many scratches 2. Pencil hardness JIS K 500 6.14 method 3. Gloss 20JIS K 5400 6.7 method 4. impact resis-tance JIS K 5400 6.13 method 5. ~ccelerated weather resistance JIS K 5400 6.17 me-thod 256. Water resistance JIS IC 5400 7.2 method 13.~7~
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excessively progressed hardening. In either case, the desired abrasion resistance can hardly be obtaine-l.
The inventors have also Eound that though it is not essential in the present invention, a strong acidic catalyst as p-toluene sulfonic acid, dinonyl naphthalene disulfonic acid, dodecyl benzene sulfonic acid and the like may advantageously be added to the present resinous composition in an amount corresponding to 0.2 to 3~ by weight of the total solid, thereby reducing the baking temperature to 10 160C or less. Therfore, in a particularly preferred embodiment, a strong acidic catalyst is present in the present resinous composition. If desired, pigment and other paint additives may be successfully added to the present resinous composition. Thus, the present resinous composition is useful as a resinous vehicle in a top coat composition including both solid color paint and clear coating composition, to be applied on automobile body, electric appliance and the like. The clear coating composition may be applied on both solid color paint and metallic coating. In either case, the abrasion resistance of such coating is excellent.
The invention shall be now more fully explained in the following Examples. Unless otherwise being stated, all parts and percentages are by weight.
7.~
Example l K-Flex 188 (trademark, polyester polyol, molecular weight 490, manuEactured by King Co.) as a soft component and Cymel 303 (trademark, melamine resin: monomeric 5 structure content 60% by weight, ~egree of etheriEication about 5.5, degree of methoxylation about 5.5, manufactured by Mitsui Tohatsu K.K.) as a hard component were blended in a solid weight ratio of 5:5, and the mixture was treated in a disper for 30 minutes to obtain a uniform solution. To 10 this solution, N~CURE 155 (trademark, King Co.) was added as a catalyst in an amount of l~ of the total weight of the composition and stirred well to obtain a resinous composition for coating use.
Examples 2 to 4 Resinous compositions were prepared by repeating the procedures of Example l, excepting revising the weight ratio of soft component/hard component as follows. That is, in Example 2, said ratio was changed to 4/6, in Example 3, to 3/7 and in Example 4, to 7/3.
Example 5 2.0 parts of carbon black and 50 parts on K-Flex 188 were mixed together. To this, were added equal quantities of glass beads (2mm diameter) and the combined mixture was treated in a disper for 60 minutes. Thereafter, 50 parts 25 Cymel 303 were added and mixed well in the disper for additional 30 minutes. Nacure 155 (catalyst) was then added in an amount of l~ of the total weight of the composition ~3~7.5 and mixed well to obtain a coating composition.
Example 6 The same procedures as stated in Example 1 were repeated, excepting substituting polye-thylene glycol 400 (trademark, polyethylene glyco:l manufactured by Aldrich Co.) for K-Flex 188 and Sumimal ~llO0 (trademark, melamine resin, monomeric structure content 80~ by weight, degree of etherification about 5.5, degree of methoxylation about 5.5, manufactured by Sumitomo Chem. Co.) for Cymel 303, to obtain 10 a coating composition.
Example 7 The same procedures as stated in Example 1 were repeated, excepting substituting polyethylene glycol 600 (trademark, polyethylene glycol manufactured by Aldrich Co.) for K-Flex 188 to obtain a coating compositon.
Example 8 The same procedures as stated in Example 1 were repeated, excepting substituting polypropylene glycol 425 (trademarX, polypropylene glycol manufactured by Aldrich Co.) for K-Flex 188 to obtain a coating composition.
Example 9 The same procedures as stated in Example 1 were repeated, excepting substituting Sumimal ~llO0 for Cymel 303 to obtain a coating composition.
Example 10 The same procedures as stated in Example 3 were repeated, excepting substituting K-Flex 1~8 (trademark, ~3~7~3' polyester polyol, molecular weight 47~, manufactured by King Co.) for l<-Flex 1~8 and Sumimal 11100 for Cymel 303 to obtain a coating composition.
Example 11 K-Flex 14~ as a soft component and Cymel 303 as a hard component were blended in a solid weight ~atio of 5:5 and stirred and mixed well in a disper for 30 minutes.
~hereafter, p-toluene sulfonic acid, diethanolamine and xylene were added each in the amounts corresponding to 1%, 0.92% and 40~ of the total weight of the resulted coating composition, and the combined mixture was stirred well until a uniform solution was obtained, heated under stirring to 100C and reacted at the same temperature for 2 hours to obtain a resinous composition comprising a polymer having a number average molecular weight of 5000.
Preparaion of coated test panels (A) To a series of test steel panels (each 300x500xO.Bmm size) previously treated with Granodine SD5000 (zinc phosphate pre-treating agent, trademark of Nippon Paint Co., Ltd.), was applied Power top U-30 (Epoxy urethane cationic electrodepositing coating composition, trademark of Nippon Paint Co., Ltd.) in a dry film thickness of 30~, baked at 170C for 20 minutes, was applied an intercoat of Orga P-2 (trademark, gray intercoat composition based on polyester resin, Nippon Paint Co., Ltd.) in a dry film thickness oE
35~ and baked at 140C for 20 minutes. Onto thus coated panels, coating compositions obtained in Examples 1 to 6 and 1 3 ~ 7 ~
Orga S-20 clear coating composition tEor comparison salce) (trademark, polyester resin base clear coating composition, Nippon Paint Co., Ltd.) each was applied in a dry film thickness oE 30~ and then baked at 140C for 20 minutes.
Thus obtained test panels were subjected to the following tests and their abrasion resistance, pencil hardness, gloss, accelerated weather resistance and water resistance properties were examined. The test results are shown in Table 1.
Preparation of coated test panels (B) To a series of test steel panels (each 300x500xO.8mm size) previously treated with Granodine SD5000 (zinc phosphate pre-treating agent, trademark of Nippon Paing Co., L,td.), was applied Power top U-30 (trademark, epoxy urethane cationic electrodeposition coa-ting composition, Nippon Paint Co., Ltd.) in a dry film thickness on 30J~, baked at 170C
for 20 minutes, was applied an intercoat of Orga P-2 in a dry film thickness of 35~ and baked at 1~0C for 20 minutes. Onto thus prepared plates, was applied Superlack ~I-90 Silver (trademark, acryl-melamine resin base silver colored coating composition, Nippon Paint Co., Ltd.) to a dry film thickness of 15~ and then, on wet-on-wet basis, each clear coating composition obtained in F.xample 1, Examples 7 -to 11 and Superlack 0-128 (trademark, acryl-melamine base clear coating composition, Nippon Paing Co.,Ltd.) in a dry film thickness of 15~ . Finally, they were baked at 140C for 20 minutes.
7 ~
Thus obtained test panels were subjected to the following tests and their abrasion resistance, pencil hardness, gloss, accelerated weather resistance and water resistance properties were examined. The test results are shown in Table 2.
The test methods and evaluation standards used are as follows.
l. Abrasion resistance Test plate is fixed on the roof of an automobile and 10subjected to an auto-washer 20 times. Thereafter, the coating conditions are visually examined.
O ....... no scratch O ....... faint scratch ~ ....... slight scratch X ....... scratches X X ........ quite many scratches 2. Pencil hardness JIS K 500 6.14 method 3. Gloss 20JIS K 5400 6.7 method 4. impact resis-tance JIS K 5400 6.13 method 5. ~ccelerated weather resistance JIS K 5400 6.17 me-thod 256. Water resistance JIS IC 5400 7.2 method 13.~7~
_ _ .~ ~
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rn ~r~ U ,~ rn w rd U r ~ U h _ _ rrJ P~ ... -,1 rd 13~7~
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Claims
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A resin composition for coating use comprising (A) a melamine resin having a monomeric content of 50%
or more and a degree of etherification of 5 or more, 80%
or more of the ether groups contained being methylated methylol groups, and (B) an aliphatic or alicyclic, linear-structured compound having an average molecular weight of 100 to 1000 and bearing end hydroxyl groups, which may include ether or ester bonds, the solid weight ratio of said (A) to (B) being 3/7 to 7/3.
or more and a degree of etherification of 5 or more, 80%
or more of the ether groups contained being methylated methylol groups, and (B) an aliphatic or alicyclic, linear-structured compound having an average molecular weight of 100 to 1000 and bearing end hydroxyl groups, which may include ether or ester bonds, the solid weight ratio of said (A) to (B) being 3/7 to 7/3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62196132A JPS6440571A (en) | 1987-08-05 | 1987-08-05 | Coating resin composition |
| JP196132/87 | 1987-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1318075C true CA1318075C (en) | 1993-05-18 |
Family
ID=16352772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000573666A Expired - Fee Related CA1318075C (en) | 1987-08-05 | 1988-08-03 | Resinous composition for coating use |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6440571A (en) |
| KR (1) | KR960014757B1 (en) |
| CA (1) | CA1318075C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3870635A4 (en) * | 2018-11-21 | 2022-07-13 | Entrotech, Inc. | Polymeric sheet useful for application to concave surface topographies of articles and related methods |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0737747B2 (en) * | 1990-12-18 | 1995-04-26 | 株式会社総合駐車場コンサルタント | Multistory parking lot |
| KR20160081370A (en) * | 2014-12-31 | 2016-07-08 | 현대자동차주식회사 | High elasticity primer composition |
| JP6299829B2 (en) * | 2015-10-20 | 2018-03-28 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and release polyethylene terephthalate film |
-
1987
- 1987-08-05 JP JP62196132A patent/JPS6440571A/en active Pending
-
1988
- 1988-08-03 CA CA000573666A patent/CA1318075C/en not_active Expired - Fee Related
- 1988-08-04 KR KR1019880009955A patent/KR960014757B1/en active IP Right Grant
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3870635A4 (en) * | 2018-11-21 | 2022-07-13 | Entrotech, Inc. | Polymeric sheet useful for application to concave surface topographies of articles and related methods |
| US12065549B2 (en) | 2018-11-21 | 2024-08-20 | Ppg Advanced Surface Technologies, Llc | Polymeric sheet useful for application to concave surface topographies of articles and related methods |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960014757B1 (en) | 1996-10-19 |
| JPS6440571A (en) | 1989-02-10 |
| KR890003897A (en) | 1989-04-18 |
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