CA1117690A - Water soluble epoxy ester copolymers for sanitary can use - Google Patents
Water soluble epoxy ester copolymers for sanitary can useInfo
- Publication number
- CA1117690A CA1117690A CA000323074A CA323074A CA1117690A CA 1117690 A CA1117690 A CA 1117690A CA 000323074 A CA000323074 A CA 000323074A CA 323074 A CA323074 A CA 323074A CA 1117690 A CA1117690 A CA 1117690A
- Authority
- CA
- Canada
- Prior art keywords
- epoxy ester
- acid
- recited
- copolymer
- ester copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
Abstract
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-Cl0 alkanoic acid, the esterifica-tion reaction being continued to provide an arid 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 homopoly-merization 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 function-al 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 pheno-plast resin is incorporated to provide curing reactivity.
Description
~7~ 0 WATER SOLUBLE EPOXY ESTER COPOLYMERS FOR
~ S~NITARY CAN USE
Technical Field The present invention relates to water soluble epoxy ester copolymers which are particulaxly adapted to sanitary can use where good resistance to extraction by hot water and good odor and flavor characteristics are essential.
Backgro~und Art 1~ 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 15 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 20 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 Cl-C8 alkyl substituted benzoic acld, or a C6-Cl~ alkanoic 25 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 poly-esterified with a monoethylenic dicarboxylic acid which - 30 resists homopolymerization, preferably fumaric acid.
From 1.5-8% of the diacid is used in the polyesterifica-tion reaction, based on the weight of the epoxy ester, so the hydroxy groups in the epoxy ester are present l.n stoichiometric excess, and the polyesterification is 35 continued to an acid number of less than 20 to provide an ethylenically unsaturated hydroxy functional poly-,'' ~
ester. This unsaturated polyester is then copolymerizedwith from 15~/, to 70% of monoethylenic monomers, based on the weight of the copolymer, to provide a copolymer product. These monomers include monoethylenic carhoxyl-ic acid, such as methacrylic acid or fumaric acid, toprovide an acid number of from 20-100 in the final copolymer so that amine and water can be added to pro-vide a water dispersion which is either a solution or a colloidal dispersion. Reactive monomers, such as 10 hydroxyèthyl acrylate or N-methylol acrylamide or its ether, such as the butyl ether, may be used. Alterna-tively, 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 l,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 20 the use of mixtures, is from 350 to 800.
The saturated monocarboxylic acid used to consume the epoxy functionality may be benzoic acid or a Cl-C8 . alkyl substituted benzoic acid or a C6-C10 alkanoic acid, but para tertiary butyl benzoic acid is particu-25 larly 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 combina-tion 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 stoichiomet-- ric proportion and the reaction is continued to consume 35 most of the acid, an acid number of less than about 20, . preferably less than 10, being contemplated.
~ ~17 ~ ~
Significant residual epoxy functionality yields instability and should be avolded. Some excess acid will simply react with the hydroxy functionality on the epoxy ester. It is here noted that polyepoxides fre-quently 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 10 acid should resist homopolymerization so that its acid-ity 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 15 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 unsat-uration and it is copolymerized with monoethylenic 20 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 25 functional groups except the polymerizable ethylenic group. Styrene and vinyl toluene are particularly contemplated, though methyl methacrylate, methyl acryl-ate, ethyl acrylate, acrylonitrile and vinyl acetate will further illustrate the useful materials. Styrene 30 and vinyl toluene are especially i~portant for two - reasons. First, they copolymerize better with the di-carboxylic acids used fur polyesterification. Second, they produce higher molecular weight copolymers which provide higher viscosity aqueous solutions at low solids 3~-content, and this provides spray solutions which better resist the formation of bubbles, blisters and foams.
~7~;~0 A monoethylenic carboxylic acid of any desired type should be employed to provide an ac-id 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 t~e future. Maleic anhydride is useful at the small~r proportion of use. The preferred acidity should 10 not exceed 60. While more acid polymers can be used, sanitary can use requires maximum water resis~ance and good resistance to water extraction, and these are best at low acid value. The copolyme~s herein are well adapted to disperse in water at low acid value.
` 15 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, ~-methylol function-; 20 al monorners, 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 25 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 illus-trated by hexamethoxymethyl melamine. This class of water soluble and water dispersible materials useful 30 for curing hydroxy functional resins is a ma-tter 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 copol~mer to be dispersed in water. This is 35 again conventional, and is illustrated using dimethyl ethanol amine.
The resulting aqueous solutions cure to provide films characterized by superior resistance to extrac-tion and they resist absorbing odor and flavor compo-nents of the foods and beverages which are packaged.
- 5 They can be applied to any metal can interior, such as aluminum, steel and tin plated steel. Spray appication and cure by baking at 400F. or 3 minutes are particu-- larly contemplated. Films of about 0.2-0.3 mil are formed~. Good adhesion is obtained on all of these 10 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 100C. to melt.
: (2) Dimethyl ethanol amine Add (2). Watch for exotherm which heats the mixture to 225C. and hold for acid value less than 5. Then cool to 1~0C.
(3) Fumaric acid ) 15 Xylol ~ 30 Add (3). Heat to 225C. and remove water of esteri-- 25 fication and hold for acid value less than 7. ~ol - to 170C.
- (4) Butyl cellosolve ) 460 - (5) Fumaric acid ) 40 ~dd (4) and (5). Hold 30 minutes to dissolve the fumaric acid and then cool to 125C.
(6) Styrene ) 160 Cumene Hydroperoxide ) 25 Premix (6) and add over 2 hrs. at 125C. and hold 1 hr.
35 (7) Cumene hydroperoxide ) 5 Add (7) and hold 1 hr.
7~i~V
(8) Cumene hydroperoxide ) 5 Add (8) hold 1 hr., and cool to 70C.
(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 -10 30. l~/o~ Acid value of solids - 33.5.
This dispersion has been successfully sprayed on aluminum and steel can interiors and cured by baking at 400F. for 3 minutes. Extractables are low and good flavor and color properties are obtained.
, .
.
~ S~NITARY CAN USE
Technical Field The present invention relates to water soluble epoxy ester copolymers which are particulaxly adapted to sanitary can use where good resistance to extraction by hot water and good odor and flavor characteristics are essential.
Backgro~und Art 1~ 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 15 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 20 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 Cl-C8 alkyl substituted benzoic acld, or a C6-Cl~ alkanoic 25 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 poly-esterified with a monoethylenic dicarboxylic acid which - 30 resists homopolymerization, preferably fumaric acid.
From 1.5-8% of the diacid is used in the polyesterifica-tion reaction, based on the weight of the epoxy ester, so the hydroxy groups in the epoxy ester are present l.n stoichiometric excess, and the polyesterification is 35 continued to an acid number of less than 20 to provide an ethylenically unsaturated hydroxy functional poly-,'' ~
ester. This unsaturated polyester is then copolymerizedwith from 15~/, to 70% of monoethylenic monomers, based on the weight of the copolymer, to provide a copolymer product. These monomers include monoethylenic carhoxyl-ic acid, such as methacrylic acid or fumaric acid, toprovide an acid number of from 20-100 in the final copolymer so that amine and water can be added to pro-vide a water dispersion which is either a solution or a colloidal dispersion. Reactive monomers, such as 10 hydroxyèthyl acrylate or N-methylol acrylamide or its ether, such as the butyl ether, may be used. Alterna-tively, 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 l,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 20 the use of mixtures, is from 350 to 800.
The saturated monocarboxylic acid used to consume the epoxy functionality may be benzoic acid or a Cl-C8 . alkyl substituted benzoic acid or a C6-C10 alkanoic acid, but para tertiary butyl benzoic acid is particu-25 larly 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 combina-tion 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 stoichiomet-- ric proportion and the reaction is continued to consume 35 most of the acid, an acid number of less than about 20, . preferably less than 10, being contemplated.
~ ~17 ~ ~
Significant residual epoxy functionality yields instability and should be avolded. Some excess acid will simply react with the hydroxy functionality on the epoxy ester. It is here noted that polyepoxides fre-quently 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 10 acid should resist homopolymerization so that its acid-ity 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 15 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 unsat-uration and it is copolymerized with monoethylenic 20 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 25 functional groups except the polymerizable ethylenic group. Styrene and vinyl toluene are particularly contemplated, though methyl methacrylate, methyl acryl-ate, ethyl acrylate, acrylonitrile and vinyl acetate will further illustrate the useful materials. Styrene 30 and vinyl toluene are especially i~portant for two - reasons. First, they copolymerize better with the di-carboxylic acids used fur polyesterification. Second, they produce higher molecular weight copolymers which provide higher viscosity aqueous solutions at low solids 3~-content, and this provides spray solutions which better resist the formation of bubbles, blisters and foams.
~7~;~0 A monoethylenic carboxylic acid of any desired type should be employed to provide an ac-id 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 t~e future. Maleic anhydride is useful at the small~r proportion of use. The preferred acidity should 10 not exceed 60. While more acid polymers can be used, sanitary can use requires maximum water resis~ance and good resistance to water extraction, and these are best at low acid value. The copolyme~s herein are well adapted to disperse in water at low acid value.
` 15 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, ~-methylol function-; 20 al monorners, 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 25 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 illus-trated by hexamethoxymethyl melamine. This class of water soluble and water dispersible materials useful 30 for curing hydroxy functional resins is a ma-tter 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 copol~mer to be dispersed in water. This is 35 again conventional, and is illustrated using dimethyl ethanol amine.
The resulting aqueous solutions cure to provide films characterized by superior resistance to extrac-tion and they resist absorbing odor and flavor compo-nents of the foods and beverages which are packaged.
- 5 They can be applied to any metal can interior, such as aluminum, steel and tin plated steel. Spray appication and cure by baking at 400F. or 3 minutes are particu-- larly contemplated. Films of about 0.2-0.3 mil are formed~. Good adhesion is obtained on all of these 10 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 100C. to melt.
: (2) Dimethyl ethanol amine Add (2). Watch for exotherm which heats the mixture to 225C. and hold for acid value less than 5. Then cool to 1~0C.
(3) Fumaric acid ) 15 Xylol ~ 30 Add (3). Heat to 225C. and remove water of esteri-- 25 fication and hold for acid value less than 7. ~ol - to 170C.
- (4) Butyl cellosolve ) 460 - (5) Fumaric acid ) 40 ~dd (4) and (5). Hold 30 minutes to dissolve the fumaric acid and then cool to 125C.
(6) Styrene ) 160 Cumene Hydroperoxide ) 25 Premix (6) and add over 2 hrs. at 125C. and hold 1 hr.
35 (7) Cumene hydroperoxide ) 5 Add (7) and hold 1 hr.
7~i~V
(8) Cumene hydroperoxide ) 5 Add (8) hold 1 hr., and cool to 70C.
(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 -10 30. l~/o~ Acid value of solids - 33.5.
This dispersion has been successfully sprayed on aluminum and steel can interiors and cured by baking at 400F. for 3 minutes. Extractables are low and good flavor and color properties are obtained.
, .
.
Claims (14)
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 molecu-lar 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 esterifi-cation reaction being continued to provide an acid num-ber 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 di-carboxylic acid which resists homopolymerization to an acid number of less than 20, and said polyester being copolymerized with from 15% to 70% of monoethylenic mono-mers, 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 monocarboxylic acid is para tertiary butyl benzoic acid.
5. Epoxy ester copolymer as recited in claim 1 in which said hydroxy functional epoxy ester is poly-esterified 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 nonreactive.
10. Epoxy ester copolymer as recited in claim 9 in which said nonreactive 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 amino-plast 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, 4 and 12 dispersed therein in the form of a salt with an amine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88503678A | 1978-03-09 | 1978-03-09 | |
| US885,036 | 1978-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117690A true CA1117690A (en) | 1982-02-02 |
Family
ID=25385977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000323074A Expired CA1117690A (en) | 1978-03-09 | 1979-03-09 | Water soluble epoxy ester copolymers for sanitary can use |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0015917A1 (en) |
| JP (1) | JPS55500154A (en) |
| CA (1) | CA1117690A (en) |
| WO (1) | WO1979000732A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294737A (en) * | 1979-12-28 | 1981-10-13 | Desoto, Inc. | Water soluble epoxy ester copolymers for interior can use |
| US4812493A (en) * | 1987-04-10 | 1989-03-14 | Adhesive Coatings Co. | Dual cure rate water-based coating compositions |
| JP2002302639A (en) | 2001-04-06 | 2002-10-18 | Kansai Paint Co Ltd | Aqueous coating composition for inner surface of can |
| 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 |
Family Cites Families (5)
| 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 |
| DE2115918C3 (en) * | 1971-04-01 | 1980-04-24 | Hoechst Ag, 6000 Frankfurt | Process for the production of epoxy polyadducts |
| 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 |
-
1979
- 1979-03-09 JP JP50051479A patent/JPS55500154A/ja active Pending
- 1979-03-09 CA CA000323074A patent/CA1117690A/en not_active Expired
- 1979-03-09 WO PCT/US1979/000110 patent/WO1979000732A1/en unknown
- 1979-10-09 EP EP79900275A patent/EP0015917A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55500154A (en) | 1980-03-21 |
| WO1979000732A1 (en) | 1979-10-04 |
| EP0015917A1 (en) | 1980-10-01 |
| EP0015917A4 (en) | 1980-07-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |