WO1998040443A1 - Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers - Google Patents
Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers Download PDFInfo
- Publication number
- WO1998040443A1 WO1998040443A1 PCT/EP1998/001572 EP9801572W WO9840443A1 WO 1998040443 A1 WO1998040443 A1 WO 1998040443A1 EP 9801572 W EP9801572 W EP 9801572W WO 9840443 A1 WO9840443 A1 WO 9840443A1
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- WO
- WIPO (PCT)
- Prior art keywords
- aqueous coating
- stable aqueous
- ethylene oxide
- poly
- coating dispersions
- Prior art date
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- 0 C*(OC1CCC(CC(CC2)CCC2OC)CC1)=C Chemical compound C*(OC1CCC(CC(CC2)CCC2OC)CC1)=C 0.000 description 1
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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Definitions
- the invention is relating to aqueous epoxy/phenolic codispersions, usable for interior food can coating lacquers .
- the invention is relating to aqueous codispersions of an epoxy resin as curing resin and a phenolic resin as co-curing resin, both of which have dispersed during the same processing step, and showing a reduced Volatile Organic Compounds (VOC) content .
- VOC Volatile Organic Compounds
- Polymer coating compositions designed for use in the interior for food containers have to meet very stringent requirements .
- High molecular weight epoxy resins are suitable for internal protective lacquers for tinplate and aluminium packaging .
- the cross-linking agents used are phenol formaldehyde, melamine formaldehyde and urea formaldehyde resins. Due to the prespecified application viscosity, can lacquers were based on organic solvents with a typical solvent content between 55 and 70 %wt . With reference to the hereinbeforementioned aims, the use of such organic solvents must be avoided as much as possible .
- a currently desired volatile organic content (VOC) level is lower than 200 g/kg solids.
- Possible routes to reduce the use of solvents are, for example, those of powder coatings, high solids binders, or water based systems.
- an object of the present invention is to provide said stable aqueous epoxy resin lacquer systems, showing the required physical properties in the final can coating layer and manufactured in cheap equipment and by using cheap, environmentally acceptable starting materials and auxiliaries.
- Another object of the present invention is to provide an effective process for the manufacture of said stable lacquer systems.
- the invention relates to stable aqueous coating dispersions, comprising a codispersion of at least a curable epoxy resin and a co-curable phenolic resin, and a combination of a non-ionic surfactant, comprising at least a reaction product of poly (ethylene oxide) polymers and a diglycidylether of a dihydric phenol having an epoxy group content in the range of from 1000 to 6000 mmol/kg, or a block copolymer of ethylene oxide and propylene oxide, and an anionic surfactant, comprising a random copolymer of at least one monovinyl arene, an alkyl acrylate, containing from 2 to 6 and preferably from 2 to 4 carbon atoms in the alkyl group, and acrylic acid, the copolymer having a weight average molecular weight in the range of from 3000 to 30.000, and preferably 4500 to 7000 and more preferably from 5500 to 6500, said composition partly neutralized by an amine, and preferably
- the non-ionic surfactant is a reaction product of poly (ethylene oxide) alcohol having an apparent molecular weight of from 5000 to 10.000 and more preferably from 6000 to 9000 and a diglycidyl ether of dihydric phenol.
- the diglycidyl ether of dihydric phenol reactant more preferably has a viscosity of from 5 to 7 mPa . s at 25 °C in a MEK solution (40% by weight) .
- the epoxy resins to be dispersed in the practice of this invention comprise one or more polyglycidyl ethers of polyhydric phenols having two or more epoxide groups and one or more six carbon aromatic rings present in the molecule, as represented by the structural formula
- R]_ represents a "g" valent Cg-C5 Q organic radical comprising at least one six carbon aromatic ring and g is equal to or greater than 2, but less than or equal to 6. More in particular R]_ may represent a group
- Suitable epoxy resins are commercially available from a variety of sources and include EPIKOTE or EPON epoxy resins (EPIKOTE and EPON are trade marks) from Shell
- suitable epoxy resins are: I) Polyglycidyl and poly (beta-methylglycidyl) esters obtainable by reacting a compound having at least two carboxy groups in the molecule with epichlorohydrin or beta-methyl-epichlorohydrin respectively. The reaction is advantageously carried out in the presence of bases.
- aromatic polycarboxylic acids which may be used include, for example, phthalic acid, isophthalic acid or terephthalic acid.
- Polyglycidyl or poly (beta-methylglycidyl) ethers obtainable by reacting a compound having at least two free phenolic hydroxy groups with epichlorohydrin or beta-methyl-epichlorohydrin, respectively, under alkaline conditions, or in the presence of an acid catalyst and with subsequent alkali treatment.
- the epoxy compounds of this type may be derived from mononuclear phenols, such as for example, resorcinol or hydroquinone; or they are based on polynuclear phenols, such as, for example, bis (4-hydroxyphenyl ) methane, , ' -dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis ( 4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl) propane, 2, 2-bis (3, 5-dibromo- 4-hydroxyphenyl) propane, and from novolacs obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols that are substituted in the nucleus by halide atoms or C]_-C ⁇ _g (preferably C ⁇ -Cg) alkyl groups, such as, for
- epoxy resins that have an epoxy content of from 2 to 10 equivalents/mole and that are glycidyl ethers or glycidyl esters of aromatic or alkylaromatic compounds.
- Especially preferred epoxy resins are polyglycidyl ethers of bisphenols, such as, for example, of 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) or bis ( 4-hydroxyphenyl) methane (bisphenol F) , or novolacs formed by reacting formaldehyde with a phenol .
- bisphenols 2, 2-bis (4-hydroxyphenyl) propane
- bisphenol F bis ( 4-hydroxyphenyl) methane
- epoxy resins are polyglycidyl ethers based on bisphenol A.
- epoxy resins are used, having an epoxide equivalent weight of at least 700 and more preferably at least 1500.
- aromatic polyglycidylethers which are commercially available under the trade names EPIKOTE 1001, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1008, EPIKOTE 1055 and EPIKOTE 1009.
- co-curable phenolic resins can be used those which were disclosed in e.g. U.S. patent No. 5,491,031,
- the phenolic resin utilized in the present composition is a condensation product, resulting from a reaction between a phenol and formaldehyde, and has a low molecular weight of 1,000 to 8,000 and preferably 3,000 to 5,000.
- Phenol or essentially any other compound including a hydroxyphenyl moiety, like cresols acid, can be used as the phenol component of the phenolic resin.
- suitable phenol compounds include phenol, o-cresol, p-cresol, m-cresol and bisphenol A.
- Bisphenol A is the preferred phenol component of the phenolic resin.
- bisphenol A and formaldehyde are used as the components of the phenolic resin.
- the combination of bisphenol A and formaldehyde provides a phenolic resin that, when incorporated into a coating composition of the present invention, imparts excellent adhesion of the coating composition both to the primer coating and to a variety of plastisol gaskets that can be applied over the cured composition coating.
- Cresol cresylic acid
- An exemplary phenolic resin utilized in the present coating composition includes about 24% by weight bisphenol A, and about 7% by weight formaldehyde. This phenolic resin is incorporated into a present coating composition as a solution containing about 50% by weight of the phenolic resin.
- Suitable examples of phenolic resins are those, which are commercially available under the trade names EPIKURE DX-200-MN-70 or DX-200-N-60, or PHENODUR 217.
- the weight ratio between the epoxy resin and the cocurable phenolic resins to be dispersed may be in the range of from 90/10 to 20/80 and preferably from 85/15 to 65/35.
- the non-ionic surfactant may be derived from poly (ethoxy) polymers of the formula
- G represents the residue of a dihydric alcohol and more preferably polyalkylene glycol, has and wherein X has a value from 100 to 250 and preferably from 150 to 200, which is prereacted with diglycidylether, and is a more preferred surfactant, or
- dihydric alcohols which can be used for the preparation of the non-ionic surfactant component derived from ethylene oxide and propyleneoxide are polyethylene glycol, polypropylene glycols, or a mixture thereof. The use of polyethylene glycol is most preferred.
- the epoxy resin reactant is preferably selected from diglycidyl ethers derived from dihydric phenols, having one or more six carbon aromatic rings present in the molecule, represented by the structural formula
- R]_ and g are as defined hereinbefore.
- R ⁇ represents a group
- More preferably epoxy resins are used for the preparation of the non-ionic surfactants, having an epoxide equivalent weight of at least 700 and most preferably of at least 1500.
- epoxy resins are aromatic polyglycidyl ethers, which are commercially available under the trade name EPIKOTE 1001, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1008, EPIKOTE 1009, EPIKOTE 1055, of which EPIKOTE 1001 is the most preferred.
- the non-ionic surfactant is generally included in amounts in the range of from 1 to 15 wt% and preferably from 4 to 10 wt% relative to the total weight of solids. More preferably the amounts are in the range of from 6 to 8 wt%.
- the anionic co-surfactant is preferably a terpolymer of styrene, ethyl acrylate and acrylic acid in a weight ratio of from 40 to 50 wt% styrene, from 15 to 25 wt% ethylacetate, and from 30 to 35 wt% acrylic acid, the sum of the percentages of the three comonomer components being 100%. More preferably co-surfactant terpolymers are used, derived from 44 to 46 wt% styrene, from 20 to 22 wt% ethyl acetate and from 33 to 34 wt% acrylic acid, the sum of the percentages of the three comonomer components being 100%. Said terpolymers and their preparation are known from
- the anionic terpolymer surfactant is generally included in amounts of from 2 to 15 wt%, relative to the total weight of the solids, and preferably from 5 to 10 wt% and more preferably from 6 to 8 wt%.
- neutralizing amines are preferably used dimethyl- ethanol amine (DMEA) and/or N-ethyl-morpholine (NEM) .
- DMEA dimethyl- ethanol amine
- NEM N-ethyl-morpholine
- the codispersions are physically stable, if as far as the neutralization degree is in the range of from 25 to 95.
- this neutralization degree will be in the range from 30 to 60% for optimum results.
- Another aspect of the present invention is formed by a process for the manufacture of the hereinbefore specified aqueous lacquers.
- the invention relates to a process for the manufacture of stable aqueous coating dispersions comprising heating of the hereinbefore specified starting materials to be dispersed and surfactants and stirring until a homogeneous liquid mixture at a stirring speed in the range of from 50 to 150 RPM, adjusting the temperature to the desired Phase Inversion Temperature (PIT) and adding water dropwise and an aqueous solution of the neutralizing amine just before inversion occurs, continuation of adding water dropwise to avoid back inversion and stirring the obtained aqueous dispersion at a few degrees below the PIT for an extra one to four hours and preferably from two to three hours, optionally further dilution of the obtained aqueous dispersion and cooling .
- PIT Phase Inversion Temperature
- inversion occurs between 68% and 77% weight of non-volatile compounds.
- the maximum PIT is between 60 and 83 °C.
- aqueous coating dispersions are stable over a long storage period and have average particle sizes DW ⁇ 2 ⁇ m and D n ⁇ 1 ⁇ m of at least 90% of the particles.
- the quality of the codispersion is very good: homogeneous, small particles and sharp particle size distribution (see Fig. 3). As previously explained, the distribution increases during storage and reaches and equilibrium (Fig. 3). The resulting codispersion is physically stable for months at room temperature (R.T.); there is no or very little settling after 6 months.
- Anionic Anionic surfactant A surfactant B water 36.90 g 36.90 g n-butanol 236.47 g 236.47 g butylOXITOL 144.02 g 144.02 g
- Codispersions made of a E 1055/DX 200 blend have been prepared (code: Ex. 2) in the presence of 7% on solids of non- ionic surfactant Q and of 6% on solids of anionic surfactant A.
- the resulting codispersion is physically stable for months at R.T.; there is no or very little settling after six months. No indication about chemical stability.
- EPIKOTE/resole codispersions containing binary blends of phenolic resins (DX 200 + another resol) have also been prepared.
- Codispersions have been prepared via the process described in Example 2 with various amounts of non-ionic surfactants Q with the aim of optimising the level to the minimum required (Table 2) .
- compositions of co-dispersions with various amounts of non-ionic surfactants Q are Compositions of co-dispersions with various amounts of non-ionic surfactants Q
- the anionic-surfactant A (AIS-A) level was slightly increased when the amount of non-ionic surfactant Q (NIS-Q) was lowered.
- the neutralization degree was raised as well in Ex. 5 and Ex. 6 in order to increase the chance of success. From Table 2, it is clear that the more non-ionic surfactant Q (NIS-Q) which is present, the higher the viscosity is.
- the final solids content was subsequently lowered to keep a suitable viscosity.
- the inversion point is similar for Ex. 5 and Ex. 6; the difference is not significant.
- the NVC could be expected to be lower which is in agreement with what was observed when preparing Ex. 2 (Fig. 6) .
- the inversion point of Comp. Ex. A is far away from the expected area. Inversion could only occur at a much lower NVC, i.e. with more water, showing therefore that this blend is more difficult to invert.
- the acrylic copolymer was neutralized by another frequently used amine species, DMEA, at a neutralization level of 60%. Therefore, the DMEA was replaced by N-ethyl-morpholine (NEM) , which has also been used for Glidden type products .
- NEM N-ethyl-morpholine
- Nonionic surfactant Q 7 parts solids Anionic surfactant B 6 parts solids ButylOXITOL 10 parts ( additional solvent added to the other chemicals) .
- VOC 250 gr/kg solids .
- D n 0.75 nm .
- D w 1.05 nm
- Example 8 Exactly the same as Example 8 but E 1055 is replaced by E 1007 and N-ethyl-Morpholine is replaced with dimethylethanol amine.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002283384A CA2283384A1 (en) | 1997-03-12 | 1998-03-11 | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
JP53924098A JP2001514694A (en) | 1997-03-12 | 1998-03-11 | Aqueous epoxy / phenolic resin co-dispersible for use in coating lacquers inside food cans |
AU67303/98A AU6730398A (en) | 1998-03-11 | 1998-03-11 | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
PCT/EP1998/001572 WO1998040443A1 (en) | 1997-03-12 | 1998-03-11 | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
BR9807994-8A BR9807994A (en) | 1997-03-12 | 1998-03-11 | Stable aqueous dispersions and coating compositions, and, process for the manufacture of stable aqueous coating dispersions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97200740.5 | 1997-03-12 | ||
PCT/EP1998/001572 WO1998040443A1 (en) | 1997-03-12 | 1998-03-11 | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998040443A1 true WO1998040443A1 (en) | 1998-09-17 |
Family
ID=8166906
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/001572 WO1998040443A1 (en) | 1997-03-12 | 1998-03-11 | Aqueous epoxy/phenolic codispersions usable for interior food can coating lacquers |
Country Status (2)
Country | Link |
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AU (1) | AU6730398A (en) |
WO (1) | WO1998040443A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020499A1 (en) * | 1998-10-02 | 2000-04-13 | The Dow Chemical Company | Epoxy resins and stable aqueous dispersions thereof |
US8337967B2 (en) | 2010-09-22 | 2012-12-25 | Empire Technology Development Llc | Can with bisphenol A capture system |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4029620A (en) * | 1975-08-13 | 1977-06-14 | Mobil Oil Corporation | Blends of partially neutralized carboxyl functional copolymers and epoxy resins in aqueous emulsion |
US4059550A (en) * | 1976-07-06 | 1977-11-22 | Celanese Polymer Specialties Company | Aqueous dispersions of polyhydroxy polyether resins and aminoplast resins |
US4233197A (en) * | 1978-06-26 | 1980-11-11 | Oxy Metal Industries Corporation | Water-borne coating for metal surfaces |
US4623680A (en) * | 1985-06-03 | 1986-11-18 | Celanese Corporation | Aqueous epoxy resin dispersions for can coating use |
EP0491550A2 (en) * | 1990-12-17 | 1992-06-24 | The Dow Chemical Company | Water-emulsifiable epoxy resin composition |
WO1997001609A1 (en) * | 1995-06-26 | 1997-01-16 | Basf Coatings Aktiengesellschaft | Aqueous powder coating dispersion for packing containers |
-
1998
- 1998-03-11 WO PCT/EP1998/001572 patent/WO1998040443A1/en not_active Application Discontinuation
- 1998-03-11 AU AU67303/98A patent/AU6730398A/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4029620A (en) * | 1975-08-13 | 1977-06-14 | Mobil Oil Corporation | Blends of partially neutralized carboxyl functional copolymers and epoxy resins in aqueous emulsion |
US4059550A (en) * | 1976-07-06 | 1977-11-22 | Celanese Polymer Specialties Company | Aqueous dispersions of polyhydroxy polyether resins and aminoplast resins |
US4233197A (en) * | 1978-06-26 | 1980-11-11 | Oxy Metal Industries Corporation | Water-borne coating for metal surfaces |
US4623680A (en) * | 1985-06-03 | 1986-11-18 | Celanese Corporation | Aqueous epoxy resin dispersions for can coating use |
EP0204511A2 (en) * | 1985-06-03 | 1986-12-10 | INTEREZ, Inc. (a Georgia corporation) | Aqueous epoxy resin dispersions for can coating use |
EP0491550A2 (en) * | 1990-12-17 | 1992-06-24 | The Dow Chemical Company | Water-emulsifiable epoxy resin composition |
WO1997001609A1 (en) * | 1995-06-26 | 1997-01-16 | Basf Coatings Aktiengesellschaft | Aqueous powder coating dispersion for packing containers |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020499A1 (en) * | 1998-10-02 | 2000-04-13 | The Dow Chemical Company | Epoxy resins and stable aqueous dispersions thereof |
US8337967B2 (en) | 2010-09-22 | 2012-12-25 | Empire Technology Development Llc | Can with bisphenol A capture system |
US9221583B2 (en) | 2010-09-22 | 2015-12-29 | Empire Technology Development Llc | Can with bisphenol A capture system |
Also Published As
Publication number | Publication date |
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AU6730398A (en) | 1998-09-29 |
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