WO1979000732A1 - Water soluble epoxy ester copolymers for sanitary can use - Google Patents

Water soluble epoxy ester copolymers for sanitary can use Download PDF

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Publication number
WO1979000732A1
WO1979000732A1 PCT/US1979/000110 US7900110W WO7900732A1 WO 1979000732 A1 WO1979000732 A1 WO 1979000732A1 US 7900110 W US7900110 W US 7900110W WO 7900732 A1 WO7900732 A1 WO 7900732A1
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WO
WIPO (PCT)
Prior art keywords
epoxy ester
acid
recited
copolymer
ester copolymer
Prior art date
Application number
PCT/US1979/000110
Other languages
French (fr)
Inventor
K Sekmakas
R Shah
Original Assignee
K Sekmakas
R Shah
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by K Sekmakas, R Shah filed Critical K Sekmakas
Publication of WO1979000732A1 publication Critical patent/WO1979000732A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to water soluble epoxy ester copolymers which are particularly adapted to sanitary can use where good resistance to extraction by hot water and good odor and flavor characteristics are essential.
  • Background Art Water solution coating compositions have been employed for diverse purposes, but it has been difficult to obtain the good resistance to extraction by hot water and good odor and flavor characteristics which are important to enable application of the coatings to sanitary cans.
  • a relatively low molecular. weight polyepoxide having an average molecular weight of about 300 to about 1100 (by calculation) and a 1, 2-epoxy equivalency of about 1.4 to about 2.0 is esterified with an at least approximately stoichio-metric proportion, based on epoxide functionality, of monocarboxylic acid selected from benzoic acid, a C 1 -C 8 alkyl substituted benzoic acid, or a C 6 -C 10 alkanoic acid to produce an ester derivative substantially free of epoxy functionality.
  • This esterification reaction is continued to an acid number of less than 20.
  • the resulting hydroxy functional epoxy ester is then polyesterified with a monoethylenic dicarboxylic acid which resists homopolymerization, preferably fumaric acid.
  • polyesterification reaction From 1.5-8% of the diacid is used in the polyesterification reaction, based on the weight, of the epoxy ester, so the hydroxy groups in the epoxy ester are present in stoichiometric excess, and the polyesterification is continued to an acid number of less than 20 to provide an ethylenically unsaturated hydroxy functional poly- ester.
  • This unsaturated polyester is then copolymerized with from 15% to 70% of monoethylenic monomers, based on the weight of the copolymer, to provide a copolymer product.
  • These monomers include monoethylenic carboxylic acid, such as methacrylic acid or fumaric acid, to provide an acid number of from 20-100 in the final copolymer so that amine and water can be added to provide a water dispersion which is either a solution or a colloidal dispersion.
  • Reactive monomers such as hydroxyethyl acrylate or N-methylol acrylamide or its ether, such as the butyl ether, may be used.
  • an aminoplast such as hexamethoxy methyl melamine, or a water soluble or dispersible phenoplast, or a mixture thereof, may be used for cure.
  • the polyepoxides preferably have a 1, 2-epoxy equivalency of about 1.4 to about 2.0 and the best properties are obtained using diglycidyl ethers of a bisphenol, such as bisphenol A.
  • the preferred molecular weight of the polyepoxides which may be provided by the use of mixtures, is from 350 to 800.
  • the saturated monocarboxylie acid used to consume the epoxy functionality may be benzoic acid or a C 1 -C 8 alkyl substituted benzoic acid or a C 6 -C 10 alkanoic acid, but para tertiary butyl benzoic acid is particularly preferred.
  • the C 6 -C 10 alkanoic acids are less preferred and are illustrated by hexoic acid or pelar- gonic acid.
  • These saturated monocarboxylic acids uniquely provide maximum impermeability in the combination of this invention.
  • the esterification reaction is wholly conventional, simple heating to a hot melt, desirably in the presence of a trace of amine catalyst, being all that is needed.
  • the acid is used in at least approximately stoichiometric proportion and the reaction is continued to consume most of the acid, an acid number of less than about 20, preferably less than 10, being contemplated.
  • Significant residual epoxy functionality yields instability and should be avoided. Some excess acid will simply react with the hydroxy functionality on the epoxy ester. It is here noted that polyepoxides frequently contain hydroxy groups, and even if they do not, the carboxy-epoxy reaction produces hydroxy groups, so the epoxy ester which is formed is hydroxy functional. Substantially stoichiometric proportions are preferred.
  • the monoethylenically unsaturated dicarboxylic acid should resist homopolymerization so that its acidity can be substantially consumbed in the production of a polyester with the hydroxyl functional epoxy ester without consuming the unsaturation.
  • the preferred dicarboxylic acid is fumaric acid, but maleic acid or maleic anhydride can also be used.
  • This polyester now contains polymerizable unsaturation and it is copolymerized with monoethylenic monomers, the bulk of which (at least about 50% by weight) are nonreactive. This means that, aside from their polymerizable unsaturation, they do not react under the conditions of polymerization and use which are contemplated. A similar statement is that there are no functional groups except the polymerizable ethylenic group. Styrene and vinyl toluene are particularly contemplated, though methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile and vinyl acetate will further illustrate the useful materials. Styrene and vinyl toluene are especially important for two reasons.
  • a monoethylenic carboxylic acid of any desired type should be employed to provide an acid number of from 20-100 in the final copolymer. Fumaric acid and maleic acid are preferred because these are F.D.A. approved, but acrylic acid, methacrylic acid, crotonic acid and itaconic acid are all useful, and one cannot know which acids will be a-proved for sanitary can use in the future. Maleic anhydride is useful at the smaller proportion of use.
  • the preferred acidity should not exceed 60. While more acid polymers can be used, sanitary can use requires maximum water resistance and good resistance to water extraction, and these are best at low acid value.
  • the copolymers herein are well adapted to disperse in water at low acid value.
  • Other reactive monoethylenic monomers may be included in an amount up to about 20% of the total polymerizable monomers. These are illustrated by hydroxy monomers, such as 2-hydroxyethyl acrylate, amide monomers, such as acrylamide, N-methylol functional monomers, such as N-methylol acrylamide or ethers thereof like the butyl ether.
  • the copolymerization is itself conventional being carried out in organic solvent solution using a free radical generating polymerization catalyst. These are well known and are illustrated in the Example.
  • aminoplast and phenoplast resins which may be used for cure are also well known and will be illustrated by hexamethoxymethyl melamine.
  • This class of water soluble and water dispersible materials useful for curing hydroxy functional resins is a matter of common knowledge in the art. They are used in an amount of 5-40% of total resin solids.
  • An amine including ammonia, is added to allow the acidic copolymer to be dispersed in water. This is again conventional, and is illustrated using dimethyl ethanol amine.
  • the resulting aqueous solutions cure to provide films characterized by superior resistance to extraction and they resist absorbing odor and flavor components of the foods and beverages which are packaged. They can be applied to any metal can interior, such as aluminum, steel and tin plated steel. Spray appication and cure by baking at 400°F. for 3 minutes are particularly contemplated. Films of about 0.2-0.3 mil are formed. Good adhesion is obtained on all of these surfaces.
  • the final product is a milky dispersion having the following characteristics: Nonvolatile solids 30.1%; Acid value of solids - 33.5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

Water soluble epoxy ester copolymers adapted for sanitary can use comprise an hydroxy functional epoxy ester of a polyepoxide having an average molecular weight of about 300 to about 1100 and a 1,2-epoxy equivalency of about 1, 4 to about 2.0, esterified with an at least approximately stoichiometric proportion, based on epoxide functionality, of monocarboxylic acid selected from benzoic acid, C1-C8 alkyl substituted benzoic acid, and C6-C10 alkanoic acid, the esterification reaction being continued to provide an acid number of less than 20, this hydroxy functional epoxy ester is polyesterified with from 1.5-8%, based on the weight of the epoxy ester, of a monoethylenically unsaturated dicarboxylic acid which resists homopolymerization to an acid number of less than 20, and the polyester so obtained is copolymerized with from 15% to 70% of monoethylenic monomers, based on the copolymer, these monoethylenic monomers including carboxyl functional monomer providing an acid number of from 20-100 in the copolymer. The copolymers are dispersed in water by salt formation with an amine and aminoplast or phenoplast resin is incorporated to provide curing reactivity.

Description

WATER SOLUBLE EPOXY ESTER COPOLYMERS FOR SANITARY CAN USE Technical Field
The present invention relates to water soluble epoxy ester copolymers which are particularly adapted to sanitary can use where good resistance to extraction by hot water and good odor and flavor characteristics are essential. Background Art Water solution coating compositions have been employed for diverse purposes, but it has been difficult to obtain the good resistance to extraction by hot water and good odor and flavor characteristics which are important to enable application of the coatings to sanitary cans.
Disclosure of Invention
In this invention, a relatively low molecular. weight polyepoxide having an average molecular weight of about 300 to about 1100 (by calculation) and a 1, 2-epoxy equivalency of about 1.4 to about 2.0 is esterified with an at least approximately stoichio-metric proportion, based on epoxide functionality, of monocarboxylic acid selected from benzoic acid, a C1-C8 alkyl substituted benzoic acid, or a C6-C10 alkanoic acid to produce an ester derivative substantially free of epoxy functionality. This esterification reaction is continued to an acid number of less than 20. The resulting hydroxy functional epoxy ester is then polyesterified with a monoethylenic dicarboxylic acid which resists homopolymerization, preferably fumaric acid.
From 1.5-8% of the diacid is used in the polyesterification reaction, based on the weight, of the epoxy ester, so the hydroxy groups in the epoxy ester are present in stoichiometric excess, and the polyesterification is continued to an acid number of less than 20 to provide an ethylenically unsaturated hydroxy functional poly- ester. This unsaturated polyester is then copolymerized with from 15% to 70% of monoethylenic monomers, based on the weight of the copolymer, to provide a copolymer product. These monomers include monoethylenic carboxylic acid, such as methacrylic acid or fumaric acid, to provide an acid number of from 20-100 in the final copolymer so that amine and water can be added to provide a water dispersion which is either a solution or a colloidal dispersion. Reactive monomers, such as hydroxyethyl acrylate or N-methylol acrylamide or its ether, such as the butyl ether, may be used. Alternatively, an aminoplast, such as hexamethoxy methyl melamine, or a water soluble or dispersible phenoplast, or a mixture thereof, may be used for cure. The polyepoxides preferably have a 1, 2-epoxy equivalency of about 1.4 to about 2.0 and the best properties are obtained using diglycidyl ethers of a bisphenol, such as bisphenol A. The preferred molecular weight of the polyepoxides, which may be provided by the use of mixtures, is from 350 to 800.
The saturated monocarboxylie acid used to consume the epoxy functionality may be benzoic acid or a C1-C8 alkyl substituted benzoic acid or a C6-C10 alkanoic acid, but para tertiary butyl benzoic acid is particularly preferred. The C6-C10 alkanoic acids are less preferred and are illustrated by hexoic acid or pelar- gonic acid. These saturated monocarboxylic acids uniquely provide maximum impermeability in the combination of this invention. The esterification reaction is wholly conventional, simple heating to a hot melt, desirably in the presence of a trace of amine catalyst, being all that is needed. The acid is used in at least approximately stoichiometric proportion and the reaction is continued to consume most of the acid, an acid number of less than about 20, preferably less than 10, being contemplated. Significant residual epoxy functionality yields instability and should be avoided. Some excess acid will simply react with the hydroxy functionality on the epoxy ester. It is here noted that polyepoxides frequently contain hydroxy groups, and even if they do not, the carboxy-epoxy reaction produces hydroxy groups, so the epoxy ester which is formed is hydroxy functional. Substantially stoichiometric proportions are preferred. The monoethylenically unsaturated dicarboxylic acid should resist homopolymerization so that its acidity can be substantially consumbed in the production of a polyester with the hydroxyl functional epoxy ester without consuming the unsaturation. The preferred dicarboxylic acid is fumaric acid, but maleic acid or maleic anhydride can also be used. An acid number of less than 20, preferably less than 10, indicates the desired complete reaction.
This polyester now contains polymerizable unsaturation and it is copolymerized with monoethylenic monomers, the bulk of which (at least about 50% by weight) are nonreactive. This means that, aside from their polymerizable unsaturation, they do not react under the conditions of polymerization and use which are contemplated. A similar statement is that there are no functional groups except the polymerizable ethylenic group. Styrene and vinyl toluene are particularly contemplated, though methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile and vinyl acetate will further illustrate the useful materials. Styrene and vinyl toluene are especially important for two reasons. First, they copolymerize better with the dicarboxylic acids used for polyesterification. Second, they produce higher molecular weight copolymers which provide higher viscosity aqueous solutions at low solids content, and this provides spray solutions which better resist the formation of bubbles, blisters and foams. A monoethylenic carboxylic acid of any desired type should be employed to provide an acid number of from 20-100 in the final copolymer. Fumaric acid and maleic acid are preferred because these are F.D.A. approved, but acrylic acid, methacrylic acid, crotonic acid and itaconic acid are all useful, and one cannot know which acids will be a-proved for sanitary can use in the future. Maleic anhydride is useful at the smaller proportion of use. The preferred acidity should not exceed 60. While more acid polymers can be used, sanitary can use requires maximum water resistance and good resistance to water extraction, and these are best at low acid value. The copolymers herein are well adapted to disperse in water at low acid value. Other reactive monoethylenic monomers may be included in an amount up to about 20% of the total polymerizable monomers. These are illustrated by hydroxy monomers, such as 2-hydroxyethyl acrylate, amide monomers, such as acrylamide, N-methylol functional monomers, such as N-methylol acrylamide or ethers thereof like the butyl ether.
The copolymerization is itself conventional being carried out in organic solvent solution using a free radical generating polymerization catalyst. These are well known and are illustrated in the Example.
The aminoplast and phenoplast resins which may be used for cure are also well known and will be illustrated by hexamethoxymethyl melamine. This class of water soluble and water dispersible materials useful for curing hydroxy functional resins is a matter of common knowledge in the art. They are used in an amount of 5-40% of total resin solids.
An amine, including ammonia, is added to allow the acidic copolymer to be dispersed in water. This is again conventional, and is illustrated using dimethyl ethanol amine. The resulting aqueous solutions cure to provide films characterized by superior resistance to extraction and they resist absorbing odor and flavor components of the foods and beverages which are packaged. They can be applied to any metal can interior, such as aluminum, steel and tin plated steel. Spray appication and cure by baking at 400°F. for 3 minutes are particularly contemplated. Films of about 0.2-0.3 mil are formed. Good adhesion is obtained on all of these surfaces.
Best Mode for Carrying Out the Invention
The invention is illustrated in the following example of preferred operation, all parts herein being by weight except where otherwise noted. Example 1
(1) Para tertiary butyl benzoic acid) 210 . CIBA 6010 ) 230
Heat to 100°C. to melt.
(2) Dimethyl ethanol amine 1 Add (2). Watch for exotherm which heats the mixture to 225°C. and hold for acid value less than 5. Then cool to 180°C.
(3) Fumaric acid ) 15 Xylol ) 30
Add (3). Heat to 225°C. and remove water of esteri fication and hold for acid value less than 7. Cool to 170°C.
(4) Butyl cellosolve ) 460
(5) Fumaric acid ) 40 Add (4) and (5). Hold 30 minutes to dissolve the fumaric acid and then cool to 125°C.
(6) Styrene ) 160
Cumene Hydroperoxide ) 25
Premix (6) and add over 2 hrs at 125°C. and hold 1 hr. (7) Cumene hydroperoxide
Add (7) and hold 1 hr. (8) Cumene hydroperoxide ) 5 Add (8) hold 1 hr., and cool to 70°C.
(9) Dimethyl ethanol amine ) 75
(10) Hexamethoxymethyl melamine )165 Add (9) and (10)
(11) Deionized water )1400 Add (11) slowly over 30 minutes.
The final product is a milky dispersion having the following characteristics: Nonvolatile solids 30.1%; Acid value of solids - 33.5.
This dispersion has been successfully sprayed on aluminum and steel can interiors and cured by baking at 400°F. for 3 minutes. Extractables are low and good flavor and color properties are obtained.

Claims

1. Epoxy ester copolymer soluble in water with the aid of an amine comprising the hydroxy functional epoxy ester of a polyepoxide having an average molecular weight of about 300 to about 1100 and a 1, 2- epoxy equivalency of about 1.4 to about 2.0, esterified with an at least approximately stoichiometric proportion, based on epoxide functionality, of monocarboxylie acid selected from benzoic acid, C1 - C8 alkyl substituted benzoic acid, and C6 - C10 alkanoic acid, the esterification reaction being continued to provide an acid number of less than 20, said hydroxy functional epoxy ester being polyesterified with from 1.5-8%, based on the weight of the epoxy ester, of a monoethylenically unsaturated dicarboxylic acid which resists homopolymerization to an acid number of less .than 20, and said polyester being copolymerized with from 15% to 70% of monoethylenic monomers, based on the copolymer, said monoethylenic monomers including carboxyl functional monomer providing an acid number of from 20-100 in the copolymer.
2. Epoxy ester copolymer as recited in claim 1 in which said polyepoxide has an average molecular weight of from 350 to 800.
3. Epoxy ester copolymer as recited in claim 2 in which said polyepoxide is a diglycidyl ether of a bisphenol.
4. Epoxy ester copolymer as recited in claim 1 in which said monocarboxylie acid is para tertiary butyl benzoic acid.
5. Epoxy ester copolymer as recited in claim 1 in which said hydroxy functional epoxy ester is polyesterified with from 2.5-5%, based on the weight of the epoxy ester, of said unsaturated dicarboxylic acid.
6. Epoxy ester copolymer as recited in claim 1 in which said polyepoxide and said monocarboxylic acid are used in substantially stoichiometric proportions.
7. Epoxy ester copolymer as recited in claim 1 in which said unsaturated dicarboxylic acid is fumaric acid.
8. Epoxy ester copolymer as recited in claim 7 in which said carboxyl functional monomer is also fumaric acid.
9. Epoxy ester copolymer as recited in claim 1 in which at least 50% of said monomers are nonreaetive.
10. Epoxy ester copolymer as recited in claim 9 in which said nonreaetive monomers consist of styrene and vinyl toluene.
11. Epoxy ester copolymer as recited in claim 9 in which the functionality of any nonacidic reactive monomer is selected from the group consisting of hydroxy, amide and N-methylol amide.
12. Epoxy ester copolymer as recited in claim 1 in which said copolymer is present in admixture with from 5-40%, based on total resin solids, of an aminoplast or phenoplast resin.
13. Epoxy ester copolymer as recited in claim 1 in which said copolymer has an acid number of up to about 60.
14. An aqueous dispersion comprising water having the acidic epoxy ester copolymer of any of claim 1-13 dispersed therein in the form of a salt with an amine.
PCT/US1979/000110 1978-03-09 1979-03-09 Water soluble epoxy ester copolymers for sanitary can use WO1979000732A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88503678A 1978-03-09 1978-03-09
US885036 1978-03-09

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EP (1) EP0015917A1 (en)
JP (1) JPS55500154A (en)
CA (1) CA1117690A (en)
WO (1) WO1979000732A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042426A1 (en) * 1979-12-28 1981-12-30 DeSOTO, INC. Water soluble epoxy ester copolymers for interior can use
WO1990010677A1 (en) * 1987-04-10 1990-09-20 Lowell Cummings Water-based coating compositions
WO2002083801A2 (en) * 2001-04-06 2002-10-24 Kansai Paint Co., Ltd. Water-based coating composition for inner surface of can and method of coating inner surface of can

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5318462B2 (en) * 2008-05-23 2013-10-16 互応化学工業株式会社 Carboxyl group-containing resin and cured product thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3564074A (en) * 1966-11-28 1971-02-16 Dow Chemical Co Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides
US4101398A (en) * 1971-04-01 1978-07-18 Hoechst Aktiengesellschaft Process for hardening a resin which is the reaction product of an epoxy resin, an olefinically unsaturated monocarboxylic acid and a polycarboxylic acid anhydride unit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773856A (en) * 1971-11-11 1973-11-20 E Takiyama Process for the preparation of unsaturated epoxy ester compositions
JPS5296690A (en) * 1976-02-10 1977-08-13 Dainippon Ink & Chem Inc Rapidly curable photo-setting resin composition
US4098735A (en) * 1977-02-14 1978-07-04 Mobil Oil Corporation Water reducible epoxy ester using monocarboxylic acid to control molecular weight

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3564074A (en) * 1966-11-28 1971-02-16 Dow Chemical Co Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides
US4101398A (en) * 1971-04-01 1978-07-18 Hoechst Aktiengesellschaft Process for hardening a resin which is the reaction product of an epoxy resin, an olefinically unsaturated monocarboxylic acid and a polycarboxylic acid anhydride unit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0015917A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042426A1 (en) * 1979-12-28 1981-12-30 DeSOTO, INC. Water soluble epoxy ester copolymers for interior can use
EP0042426A4 (en) * 1979-12-28 1982-05-10 Desoto Inc Water soluble epoxy ester copolymers for interior can use.
WO1990010677A1 (en) * 1987-04-10 1990-09-20 Lowell Cummings Water-based coating compositions
WO2002083801A2 (en) * 2001-04-06 2002-10-24 Kansai Paint Co., Ltd. Water-based coating composition for inner surface of can and method of coating inner surface of can
WO2002083801A3 (en) * 2001-04-06 2003-03-13 Kansai Paint Co Ltd Water-based coating composition for inner surface of can and method of coating inner surface of can
US6893678B2 (en) 2001-04-06 2005-05-17 Kansai Paint Co., Ltd. Water-based coating composition for inner surface of can and method of coating inner surface of can
CN100343351C (en) * 2001-04-06 2007-10-17 关西涂料株式会社 Water-based coating composition for inner surface of can and method of coating inner surface of can

Also Published As

Publication number Publication date
EP0015917A4 (en) 1980-07-17
CA1117690A (en) 1982-02-02
JPS55500154A (en) 1980-03-21
EP0015917A1 (en) 1980-10-01

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