US 4,490,417 AGrant
Coating Composition
Issue Date:1984-12-25
•19 Claims
Abstract
A coating composition which comprises (A) a vinylic monomer-copolymerized resin having a hydroxyl group and a carboxyl group and (B) an alkoxylated amine-formaldehyde condensate as a curing agent for the resin (A). When the coating composition is used as a base coating composition and/or as a clear coating composition in the two coat-one bake coating system, the resulting coating film shows excellent weather resistance with good appearance.
Metadata
Assignee
- Nippon Paint Co., Ltd.
Inventors
- Kenji Shindow
- Akimitsu Uenaka
- Takaharu Izumo
- Teruyoshi Fujishima
- Satoshi Yamamoto
Application Information
Application Number:US 4957318
Filing Date:1983-05-20
Priority Date:1980-08-29
Art Unit:151
Classifications
IPC:
B05D 302C08L 6128
Field of Search:
525427428524162;163385.5;407.1;409;327;388.3460;463100;512
Patent Drawings
This patent does not have any drawings.
Description
Example 1
Preparation of a base coating composition:
Component (A):
Into a 2 liter volume flask equipped with a reflux cooler, a dropping funnel, a thermometer and an agitator, xylene (320 g), n-butanol (80 g), methyl methacrylate (400 g), n-butyl acrylate (264 g), 2-hydroxyethyl methacrylate (120 g) and methacrylic acid (16 g) were charged, and the resultant mixture was heated up to 110.degree. C. A mixture of xylene (320 g), n-butanol (80 g), azobisisobutyronitrile (8 g) and laurylmercaptan (2 g) was dropwise added thereto in 3 hours. After the dropwise addition was completed, the resultant mixture was agitated at about 110.degree. C. for 2 hours to give a resinous composition (solid content, 50%).
Component (B):
n-Butoxylated methylolmelamine ("Uban 20SE60" manufactured by Mitsui Toatsu Co., Ltd.; solid content, 60%).
The component (A) (140 parts), the component (B) (50 parts), an aluminum pigment ("Alpaste No. 1123N" manufactured by Toyo Aluminum Co., Ltd.) (22 parts) and xylene (30 parts) were mixed together. The resultant mixture (242 parts) was diluted with a mixture of toluene, isobutanol and ethylene glycol monoethyl acetate (60:20:20 by weight) to make a base coating composition showing a value of 13 seconds (20.degree. C.) with No. 4 Ford Cup.
Example 2
Preparation of a clear coating composition:
Component (A"):
Into a 2 liter volume flask equipped with a reflux cooler, a dropping funnel, a thermometer and an agitator, xylene (440 g) and n-butanol (160 g) were charged, and the resultant mixture was heated up to 120.degree. C. A mixture of styrene (240 g), 2-ethylhexyl methacrylate (160 g), methyl methacrylate (85.6 g), n-butyl methacrylate (76.8 g), n-butyl acrylate (120 g), hydroxyethyl methacrylate (111.2 g), methacrylic acid (6.4 g) and azobisisobutyronitrile (16 g) was dropwise added thereto in 3 hours. After aging for 30 minutes, a mixture of xylene (50 parts) and benzoyl peroxide (1 g) was dropwise added thereto. Then, the resultant mixture was aged for 2 hours and diluted with xylene (150 parts) to give a resinous composition (solid content, 50%).
In the same procedure as above but using the monomeric composition as shown in Table 1, there was prepared a resinous composition as the component (A").
In the above table, the abbreviations have the following meanings: ST, sytrene; EHMA, 2-ethylhexyl methacrylate; EHA, 2-ethylhexyl acrylate; MMA, methyl methacrylate; nBMA, n-butyl methacrylate; nBA, n-butyl acrylate; HEMA, 2-hydroxyethyl methacrylate; MAA, methacrylic acid; Tg, glass transition temperature as calculated.
Component (B'):
n-Butoxylated methylolmelamine ("Uban 20SE60" manufactured by Mitsui Toatsu Co., Ltd.).
The components (A") and (B') were mixed together in a weight proportion of 70:30 (in terms of the solid components), and the resultant mixture was diluted with xylene to make a clear coating composition showing a value of 25 seconds (20.degree. C.) with No. 4 Ford Cup.
Example 3
Two coat-one bake coating system:
Onto the steel plate obtained by degreasing and phosphating a polished mild steel plate and applying subsequently an electro-deposition coating composition and an intermediary coating composition thereto, the base coating composition prepared in Example 1 was sprayed twice with an interval of 2 minutes in a water washing booth at a temperature of 23.degree. C. under a humidity of 85%, and after 3 minutes, the clear coating composition prepared in Example 2 was sprayed thereon so as to make a coating film having a thickness of 20.mu. for the base coating composition and a thickness of 30.mu. for the clear coating composition. Then, the coated plate was baked at 140.degree. C. for 30 minutes to make a test piece.
The test piece was subjected to test by the use of a sunshine weatherometer (manufactured by Suga Testing Machine Mfg. Co., Ltd.) (irradiated, 600 hours) and of a wetting tester (50.degree. C., 98% relative humidity, 96 hours) taken as one cycle, and the test was repeatedly carried out to evaluate the abnormality (e.g. cracks, peeling, luster depression) on the appearance of the coating film. The results are shown in Table 2. Evaluation of peeling was made on the state of the coating film after the test piece was taken out from the wetting tester, wiped off to eliminate the water drops attached thereon, dried at room temperature for 30 minutes and cross-cut at the surface, followed by attaching an adhesive tape and peeling off the same; O, no abnormality, X, coating film peeled off. Cracks were observed macroscopically; O, no abnormality; X, cracks produced. Evaluation of luster was effected macroscopically; O, no remarkable luster depression; X, remarkable luster depression.
Example 4
Two coat-one bake coating system:
The component (A") (Run No. 1) prepared in Example 2 and n-butoxylated methylolmelamine ("Uban 20SE60" manufactured by Mitsui Toatsu Co., Ltd.) as the component (B') were mixed together in the weight proportion as shown in Table 3, and a clear coating composition was prepared in the same manner as in Example 2 . In the same manner as in Example 3 but using the above prepared clear coating composition, there was prepared a test piece, which was subjected to test for promoted weather resistance. The results are shown in Table 4.
Example 5
Preparation of a clear coating composition:
The component (A") (Run Nos. 1 to 11) prepared in Example 2 and the component (B') were mixed together in a weight proportion of 70:30 (in terms of solid components), and epoxylated soybean oil ("Epocizer W-100EL" manufactured by Dainippon Ink K.K.) as the component (C) and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate ("Tinubin 770" manufactured by Ciba-Geigy A.G.) as the component (D) were added thereto respectively in amounts of 0.5 part and 1 part to 100 parts of the mixture of the components (A") and (B') (in terms of the solid components). The resultant mixture was diluted with xylene to make a clear coating composition showing a value of 25 seconds (20.degree. C.) with No. 4 Ford Cup.
Example 6
Two coat-one bake coating system:
A test piece was prepared in the same manner as in Example 3 but using the clear coating composition prepared in Example 5 and subjected to test for promoted weather resistance. The results are shown in Table 5.
Example 7
Two coat-one bake coating system:
A clear coating composition was prepared in the same manner as in Example 5 but adjusting the mixing weight proportion of the components (C) and (D) as shown in Table 6. A test piece was prepared in the same manner as in Example 3 but using the clear coating composition as prepared above and subjected to test for promoted weather resistance. The results are shown in Table 7.
Example 8
Preparation of a base coating composition:
Component (A'):
Into a 2 liter volume flask equipped with a reflux cooler, a dropping funnel, a thermometer and an agitator, xylene (320 g), n-butanol (80 g), methyl methacrylate (280 g), ethyl acrylate (384 g), 2-hydroxyethyl methacrylate (128 g) and methacrylic acid (8 g) were charged, and the mixture was heated up to 110.degree. C. A mixture of xylene (320 g), n-butanol (80 g), azobisisobutyronitrile (8 g) and laurylmercaptan (2 g) was dropwise added thereto in 3 hours. After the dropwise addition was completed, the resultant mixture was agitated at about 110.degree. C. for 2 hours to obtain a resinous composition having a solid content of 50%.
In the same manner as above but adopting the monomeric composition as shown in Table 8, there was prepared a resinous composition as the component (A').
In the above table, the abbreviations have the following meanings: EA, ethyl acrylate; LMA, lauryl methacrylate.
Component (B'):
n-Butoxylated methylolmelamine ("Uban 20SE60" manufactured by Mitsui Toatsu Co., Ltd.).
The component (A') (140 parts), the component (B') (50 parts), an aluminum pigment ("Alpaste No. 1123N" manufactured by Toyo Aluminum Co., Ltd.) (22 parts) and xylene (30 parts) were mixed together and diluted with a mixture of toluene, isobutanol and ethylene glycol monoethyl acetate in a weight proportion of 60:20:20 to make a base coating composition showing a value of 13 seconds (20.degree. C.) with No. 4 Ford Cup.
Example 9
Two coat-one bake coating system:
In the same manner as in Example 3 but using the base coating composition prepared in Example 8 and the clear coating composition prepared in Example 2, two coat-one bake coating was carried out to make a test piece.
The finishing appearance of the test piece was observed, and the results are shown in Table 9 wherein the case giving 90 or more in 60.degree. gloss was indicated as O and the case giving less than 90 was indicated as X.
Also, the test piece was subjected to test for promoted weather resistance as in Example 3. The results are shown in Table 9.
Example 10
Two coat-one bake coating system:
In the same manner as in Example 9 but using the base coating composition (Run No. 32) as the component (A') and the clear coating composition (Run No. 1) as the component (A") in the weight proportion as shown in Table 10, there was prepared a test piece.
The finishing appearance of the test piece was observed. Also, the test piece was subjected to test for promoted weather resistance. The results are shown in Table 11.
Claims
What is claimed is:
1. A coating composition which consists essentially of (A') a vinylic monomer-copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group and (3) at least one other ethylenically unsaturated monomer copolymerizable therewith; the monomer (1) being used in an amount which can provide the thus produced solid resin with a hydroxyl value of 40 to 80 and the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25, and having a glass transition temperature of 20 to 50.degree. C. and a solubility parameter of 10.3 to 11.5, and (B') an alkoxylated melamine-formaldehyde condensate, the weight proportion of the components (A') and (B') being from 85:15 to 60:40.
2. The coating composition according to claim 1, which further comprises (C) a compound comprising no reactive group, having a number average molecular weight of 300 to 5,000 and being in a non-crystalline state at room temperature and (D) a piperidine compound of the formula: ##STR2## wherein n is an integer of 1 to 3, R.sub.1 is hydrogen or alkyl and R.sub.2 is monoacyl, N-substituted carbamoyl, N-substituted thiocarbamoyl, a monovalent group derived from an oxygen acid excluding one hydroxyl therefrom, alkyl, cycloalkyl, aralkyl or aryl when n is 1, diacyl, dicarbamoyl, bisthiocarbamoyl, carbonyl, a divalent group derived from an oxygen acid excluding two hydroxyls therefrom, alkylene, arylene or arylenedialkyl when n is 2 or triacyl, tricarbamoyl, tristhiocarbamoyl, a trivalent group derived from an oxygen acid excluding three hydroxyls therefrom, alkanetriyl, arenetriyl or arenetriylalkylene.
3. The coating composition according to claim 2 wherein the amounts of the compounds (C) and (D) are from 0.1 to 5 parts by weight and 0.05 to 3 parts by weight respectively based on 100 parts by weight of the components (A') and (B').
4. The coating composition according to claim 1, which further comprises an ultraviolet ray absorber.
5. The coating composition according to claim 1, which further comprises a metal powder.
6. A coating composition which consists essentially of (A") a vinylic monomer-copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group, (3) at least one other copolymerizable ethylenically unsaturated monomer as an optical monomer; and (4) at least one of aromatic vinyl monomers and alkyl acrylates or methacrylates wherein the alkyl moeity has not less than 8 carbon atoms; the monomer (4) being used in an amount of from 40 to 80% by weight based on the total weight of the monomers (1), (2), (3) and (4); the monomer (1) being used in an amount which can provide the produced solid resin with a hydroxyl value of 50 to 90; the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25 and the monomer (3) when present being used in an amount of not more than 50% by weight based on the total weight of the monomers (1), (2), (3) and (4), said resin having a glass transition temperature of 10 to 45.degree. C., and (B') an alkoxylated melamine -formaldehyde condensate; the weight proportion of the components (A") and (B') being from 80:20 to 60:40.
7. The coating composition according to claim 6, which further comprises (C) a compound comprising no reactive group, having a number average molecular weight of 300 to 5,000 and being in a non-crystalline state at room temperature and (D) a piperidine compound of the formula: ##STR3## wherein n is an integer of 1 to 3, R.sub.1 is hydrogen or alkyl and R.sub.2 is monoacyl, N-substituted carbamoyl, N-substituted thiocarbamoyl, a monovalent group derived from an oxygen acid excluding one hydroxyl therefrom, alkyl, cycloalkyl, aralkyl or aryl when n is 1, diacyl, dicarbamoyl, bisthiocarbamoyl, carbonyl, a divalent group derived from an oxygen acid excluding two hydroxyls therefrom, alkylene, arylene or arylenedialkyl when n is 2 or triacyl, tricarbamoyl, tristhiocarbamoyl, a trivalent group derived from an oxygen acid excluding three hydroxyls therefrom, alkanetriyl, arenetriyl or arenetriylalkylene.
8. The coating composition according to claim 7 wherein the amounts of the compounds (C) and (D) are from 0.1 to 5 parts by weight and 0.05 to 3 parts by weight respectively based on 100 parts by weight of the components (A") and (B').
9. The coating composition according to claim 6, which further comprises an ultraviolet ray absorber.
10. A two coat-one bake coating system wherein the coating composition according to claim 1 is used as a base coating composition.
11. A two coat-one bake coating system wherein the coating composition according to claim 6 is used as a clear coating composition.
12. A two coat composition applied to at least one surface of a substrate wherein the base coating is a composition consisting essentially of (A') a vinylic monomer-copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group and (3) at least one other ethylenically unsaturated monomer copolymerizable therewith; the monomer (1) being used in an amount which can provide the thus produced solid resin with a hydroxyl value of 40 to 80 and the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25, and having a glass transition temperature of 20 to 50.degree. C. and a solubility parameter of 10.3 to 11.5, and (B') an alkoxylated melamine-formaldehyde condensate, the weight proportion of the components (A') and (B') being from 85:15 to 60:40; and a clear coating consisting essentially of (A") a vinylic monomer copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group, (3) at least one other copolymerizable ethylenically unsaturated monomer as an optional monomer; and (4) at least one of aromatic vinyl monomers and alkyl acrylates or methacrylates wherein the alkyl moeity has not less than 8 carbon atoms; the monomer (4) being used in an amount of from 40 to 80% by weight based on the total weight of the monomers (1), (2), (3) and (4); the monomer (1) being used in an amount which can provide the produced solid resin with a hydroxyl value of 50 to 90; the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25 and the monomer (3) when present being used in an amount of not more than 50% by weight based on the total weight of the monomers (1), (2), (3) and (4), said resin having a glass transition temperature of 10.degree. to 45.degree. C., and (B') an alkoxylated melamine-formaldehyde condensate; the weight proportion of the components (A") and (B') being from 80:20 to 60:40.
13. A method for coating a substrate with two coatings which comprises applying to at least one surface of a substrate a first coating composition, optionally diluted with a solvent, said composition consisting essentially of (A') a vinylic monomer-copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group and (3) at least one other ethylenically unsaturated monomer copolymerizable therewith; the monomer (1) being used in an amount which can provide the thus produced solid resin with a hydroxyl value of 40 to 80 and the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25, and having a glass transition temperature of 20.degree. to 50.degree. C. and a solubility parameter of 10.3 to 11.5, and (B') an alkoxylated melamine-formaldehyde condensate, the weight proportion of the components (A') and (B') being from 85:15 to 60:40; and then applying a second coating composition, optionally diluted with a solvent, onto the first coating, said second coating composition consisting essentially of (A") a vinylic monomer-copolymerized resin having hydroxyl groups and carboxyl groups prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group, (3) at least one other copolymerizable ethylenically unsaturated monomer as an optional monomer; and (4) at least one of aromatic vinyl monomers and alkyl acrylates or methacrylates wherein the alkyl moeity has not less than 8 carbon atoms; the monomer (4) being used in an amount of from 40 to 80% by weight based on the total weight of the monomers (1), (2), (3) and (4); the monomer (1) being used in an amount which can provide the produced solid resin with a hydroxyl value of 50 to 90; the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25 and the monomer (3) when present being used in an amount of not more than 50% by weight based on the total weight of the monomers (1), (2), (3), (4), said resin having a glass transition temperature of 10.degree. to 45.degree. C., and (B') an alkoxylated melamine-formaldehyde condensate; the weight proportion of the components (A") and (B') being from 80:20 to 60:40; and then baking the resulting coating compositions on the substrate.
14. A base coating composition for a two coat-one bake coating system which comprises (A) a vinylic monomer-copolymerized resin containing a hydroxyl group and a carboxyl group and having a glass transition temperature of 20.degree. to 50.degree. C. and a solubility parameter of 10.3 to 11.5, the resin (A) being one prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group and (3) at least one other ethylenically unsaturated monomer copolymerizable therewith, the monomer (1) being used in an amount which can provide the produced solid resin with a hydroxyl value of 40 to 80, the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25 and the monomer (3) comprising an alkyl methacrylate, and (B) an alkoxylated melamineformaldehyde condensate, the weight proportion of the component (A) and the component (B) being from 85:15 to 60:40.
15. The composition according to claim 14, wherein the monomer (3) comprises at least one alkyl methacrylate and at least one other ethylenically unsaturated monomer.
16. A clear coating composition for a two coat-one bake coating system which comprises (A) a vinylic monomer-copolymerized resin containing a hydroxyl group and a carboxyl group and having a glass transition temperature of 10.degree. to 45.degree. C., the resin (A) being the one prepared by polymerizing (1) an ethylenically unsaturated monomer having a hydroxyl group, (2) an ethylenically unsaturated monomer having a carboxyl group and (3) at least one ethylenically unsaturated monomer copolymerizable therewith, the monomer (1) being used in an amount which can provide the produced solid resin with a hydroxyl value of 50 to 90, the monomer (2) being used in an amount which can provide the produced solid resin with an acid value of 5 to 25 and the monomer (3) comprising styrene, and (B) an alkoxylated melamineformaldehyde condensate, the weight proportion of the component (A) and the component (B) being from 80:20 to 60:40.
17. The composition according to claim 16, wherein the monomer (3) comprises styrene and at least one other ethylenically unsaturated monomer.
18. The composition according to claim 16, wherein the amount of styrene is from 40 to 80% by weight based on the total weights of the monomers (1), (2) and (3).
19. The composition according to claim 17, wherein the amount of styrene is from 40 to 80% by weight based on the total weights of the monomers (1), (2) and (3).