WO2000000533A1 - Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve - Google Patents

Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve Download PDF

Info

Publication number
WO2000000533A1
WO2000000533A1 PCT/EP1999/004118 EP9904118W WO0000533A1 WO 2000000533 A1 WO2000000533 A1 WO 2000000533A1 EP 9904118 W EP9904118 W EP 9904118W WO 0000533 A1 WO0000533 A1 WO 0000533A1
Authority
WO
WIPO (PCT)
Prior art keywords
bisphenol
coating
coating lacquer
lacquer according
adduct
Prior art date
Application number
PCT/EP1999/004118
Other languages
English (en)
Inventor
Isabelle Frischinger
Michael Vogel
Jürgen Finter
Original Assignee
Vantico Ag
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 Vantico Ag filed Critical Vantico Ag
Priority to KR1020007014822A priority Critical patent/KR20010053217A/ko
Priority to BR9911571-9A priority patent/BR9911571A/pt
Priority to EP99927985A priority patent/EP1095086A1/fr
Priority to JP2000557292A priority patent/JP2002519455A/ja
Publication of WO2000000533A1 publication Critical patent/WO2000000533A1/fr

Links

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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings

Definitions

  • the present invention relates to a heat-curable can-coating lacquer and to a process for the production of a coating for a food container by means of said can-coating lacquer.
  • can-coating lacquers One field of application for heat-curable epoxy compositions are can-coating lacquers.
  • heat-curable can-coating lacquers it is possible to coat materials which are resistant against the necessary curing temperatures and which come into contact with foodstuffs, and which materials, if not correspondingly coated, either have an adverse effect on the quality of these foodstuffs or are themselves attacked by the foodstuff's components.
  • Can-coating lacquers are used in particular for coating the interior of metallic cans.
  • a widely used formulation component for standard can-coating lacquers are the so-called advanced epoxy resins which are obtainable by reacting one or several difunctional phe- nol(s) with one or several bisphenol diglycidyl ether(s) in the presence of a suitable catalyst, the bisphenol diglycidyl ethers needing to be present in stoichiometric excess over the difunctional phenols.
  • the advancement proceeds, for example, according to the following known reaction scheme:
  • BLR is a virtually monomeric diglycidyl ether based on bisphenol HO-[BPh] 1 -OH, wherein BLR is a group of the following chemical formula:
  • n is a number from 0 to 0.3 corresponding to the average number of the structural repeating units -[BPh] 1 OCH 2 CH(OH)CH 2 O- in the diglycidyl ether molecules, so that such a diglycidyl ether consists to about 99.7 % or more of monomers of the formula:
  • a is a number higher than 1 , for example 1.1 and higher.
  • the upper limit of a is preferably 2.
  • Both the quotient [1/(a-1)] and the index n are an average value for the sum of all molecules of the respective resin and can therefore also be fractional numbers if a polydisperse resin, i.e. a mixture of molecules of different chain lengths, is present.
  • Such advanced epoxy resins are often produced e.g. from bisphenol A and liquid, virtually monomeric diglycidyl ether of bisphenol A.
  • This invention provides another solution for the above problem.
  • the invention is based on the insight that the production of an advanced epoxy resin from one or several monomeric bisphenol diglycidyl ether(s) and from one or several bisphenol(s) gives an advanced epoxy resin containing a markedly reduced proportion of unreacted monomeric bisphenol diglycidyl ethers if, in addition to the bisphenol diglycidyl ether, an adduct of epoxidised soybean oil with a monocarboxylic acid takes part in the advancement reaction, which adduct has an epoxy equivalent weight of about 350 to 650.
  • Epoxy resins advanced in this manner which are based on adducts of vernonia oil, a naturally occurring epoxidised vegetable oil, and of a monocarboxylic acid, and also heat-curable compositions based on these advanced epoxy resins and on certain crosslinking agents for epoxy resins, for example polyphenols, have been known for some time and are mentioned, inter alia, in EP-A-0555 589. The state of the art, however, does not describe the amount of unreacted bisphenol diglycidyl ether monomers in these advancement resins.
  • the reduction of the percentage by weight of the undesirable monomeric bisphenol diglycidyl ethers in the advancement resins brought about by a modification of the advancement reaction using a certain portion of an adduct of epoxidised soybean oil and benzoic acid is, surprisingly, substantially higher than the reduction of the percentage by weight of monomeric bisphenol diglycidyl ethers which are used for the production of the modified advancement resin caused by that modification.
  • this invention relates to a heat-curable can-coating lacquer, which comprises an advanced epoxy resin which is the reaction product of one or several bisphenol diglycidyl ether(s), one or several bisphenol(s) and of an adduct of epoxidised soybean oil with a monocarboxylic acid, which has an epoxy equivalent weight of 350 to 600, and a crosslinking agent for epoxy resins.
  • an advanced epoxy resin which is the reaction product of one or several bisphenol diglycidyl ether(s), one or several bisphenol(s) and of an adduct of epoxidised soybean oil with a monocarboxylic acid, which has an epoxy equivalent weight of 350 to 600, and a crosslinking agent for epoxy resins.
  • This invention also relates to a process for the production of a food container, one or several sides of which are coated entirely or partly with such a can-coating lacquer, which coating is heat-cured.
  • the novel can-coating lacquer preferably contains an advanced epoxy resin having an epoxy equivalent weight of 1000 (corresponding to 1 equivalent of epoxide per kilogramme of resin) to 4000 (about 0.25 equivalent of epoxide per kilogramme of resin), preferably of 1400 (about 0.7 equivalents of epoxide per kilogramme of resin) to 2000 (0.5 equivalents of epoxide per kilogramme of resin).
  • the advanced epoxy resin may be produced by reacting e.g. epoxidised soybean oil first with the monocarboxylic acid.
  • Suitable monocarboxylic acids are, for example, monocarboxylic acids containing 1 to 20, preferably 7 to 20, carbon atoms. Particularly preferred is the use of aromatic and cycloaliphatic carboxylic acids, for example benzoic acid or abietic acid. Owing to its good availability, benzoic acid is very particularly preferred.
  • the reaction of the epoxidised soybean oil with the monocarboxylic acid reduces the epoxy functionality of the epoxidised soybean oil, which is in practice at about 4, to a value from about 2 to 3, preferably from 2 to 2.5.
  • the epoxy equivalent weight of the epoxidised soybean oil which is normally in the range from 230 to 250, is raised to the range from about 350 to 600 by the reaction with the monocarboxylic acid.
  • the epoxy equivalent weight of the adduct is preferably in the range from about 450 to 600.
  • the monocarboxylic acid In order to achieve the desired reduction of the functionality of the epoxidised soybean oil, the monocarboxylic acid must be used in an amount of about 1 to 2 mol per 4 epoxy equivalents of the epoxidised soybean oil.
  • the reaction can, for example, take place at a temperature from 120 to 160°C and is usefully carried out in the presence of a suitable catalyst, for example a tertiary amine, such as tributylamine, or N,N-ethylmethylpiperidinium iodide, which is used in customary catalytic amounts, for example from 0.0001 to 10 % by weight, based on the epoxy resin.
  • a suitable catalyst for example a tertiary amine, such as tributylamine, or N,N-ethylmethylpiperidinium iodide, which is used in customary catalytic amounts, for example from 0.0001 to 10 % by weight, based on the epoxy resin.
  • the reaction is usually carried out under protective gas (e.g. nitrogen) and/or under a slight vacuum, preferably in the range from 0.01 to 0.07 MPa (100 to 700 mbar).
  • protective gas e.g. nitrogen
  • a slight vacuum preferably in the range from
  • the adduct obtained from the epoxidised soybean oil and the monocarboxylic acid can then be further reacted with one or several different bisphenol diglycidyl ether(s) and one or several different difunctional phenol(s) to give the finished advanced epoxy resin.
  • This reaction is preferably carried out immediately after the preparation of the reaction product in the same reaction vessel. ln this application, bisphenol diglycidyl ethers will be taken to generally mean diglycidyl ethers of difunctional phenols.
  • the difunctional phenols, on which the cited diglycidyl ethers are based can, for example, be mononuclear, such as resorcinol or hydroquinone, but are preferably polynuclear, in particular binuclear, such as biphenol(4,4'-dihydroxybiphenyl), bisphenol F, bisphenol A ; 4,4'-dihydroxydiphenylsulfone or 4,4'-dihydroxybenzophenone or bis(4-hydroxyphenyl)ether. It is also possible to use mixtures of one or several diglycidyl ether(s), such as the ones mentioned above.
  • the diglycidyl ethers used conveniently have an epoxy equivalent weight in the range from 110 to 250.
  • Diglycidyl ethers which are particularly preferred for use in this invention are diglycidyl ethers of bisphenol A, diglycidyl ethers of bisphenol F, mixed diglycidyl ethers of bisphenol A/bis- phenol F and mixtures of the cited diglycidyl ethers, most preferably diglycidyl ether of bisphenol A.
  • the bisphenols which are preferably used for the production of the advanced epoxy resins, are likewise mononuclear or, preferably, polynuclear, particularly preferably binuclear.
  • suitable bisphenols are, in particular, the bisphenols cited above in the description of the bisphenol diglycidyl ethers.
  • the bisphenols it is also possible to use mixtures of two or more bisphenols.
  • Particularly preferred bisphenols are bisphenol F and, most preferably, bisphenol A.
  • the participating epoxy components When reacting the adduct of epoxidised soybean oil and the monocarboxylic acid with the bisphenol and the bisphenol diglycidyl ether, the participating epoxy components must, as is usual in the case of advancements, be present in such an amount that epoxy groups are present in the reaction mixture in an excess over the hydroxyl groups of the bisphenol, as the epoxy resin of higher molecular weight is obtainable only then.
  • the proportion of the reaction mixture in the adduct of epoxidised soybean oil and monocarboxylic acid can vary within wide limits and is conveniently from at least 5 up to 50 % by weight, based on the total weight of the adduct and of the bisphenols and bisphenol diglycidyl ethers participating in the advancement. If the adduct proportion is too small, the resulting reduction of the content of free bisphenol diglycidyl ether monomers is relatively small, whereas a very high adduct proportion can lower the softening point of the resin and may, depending on the circumstances, already adversely affect the curability of a can-coating lac- quer produced with such advanced epoxy resins, which is crucial e.g.
  • the adduct proportion is in the range from 5 to 35 % by weight, more preferably from 10 to 35 % by weight, very particularly preferably from 15 to 25 % by weight.
  • the adduct proportion should usefully be in the upper range if the desired advanced epoxy resin has a relatively low epoxy equivalent weight.
  • catalysts are described, inter alia, in US patent (US-A-)5,095,050, which disclosure is explicitly referred to here.
  • Preferred examples of catalysts are tertiary amines, such as tri- ethylamine, tripropylamine, tributylamine, 2-methylimidazole, 2-phenylimidazole, N-methyl- morpholine, N,N-ethylmethylpiperidinium iodide, quarternary ammonium compounds, tetra- alkylphosphonium compounds, such as tetrabutylphosphonium bromide, and alkali metal hydroxides.
  • catalysts are used in customary catalytic amounts, for example in amounts from 0.0001 to 10 % by weight, based on the epoxy resin.
  • Particularly preferred catalysts are tetrabutylphosphonium bromide, tributylamine and N,N-ethylmethylpiperidinium iodide and mixtures thereof.
  • the reaction temperatures during the advancement are preferably in the range from 80 to 250°C, more preferably from 130 to 210°C.
  • the completion of the reaction can be determined in simple manner, for example by checking the epoxy value of the reaction mixture.
  • Crosslinking agents suitable for the epoxy resin material of this invention are, in principle, all crosslinking agents for epoxy resins suitable for food purposes.
  • the hardeners are used in the customary amounts, which are known to the skilled person, preferably in an about stoi- chiometric ratio of the epoxy groups of the advanced epoxy to the epoxy-reactive groups (e.g. amino, hydroxyl, carboxyl, or ⁇ , ⁇ -dicarboxylic acid anhydride groups) of the crosslinking agent.
  • the epoxy groups can, for example, also be present in up to 30 % stoichiometric excess over the epoxy-reactive groups, and vice versa.
  • Crosslinking agents preferably used for the novel can-coating lacquers are acid anhydrides, for example trimellitic anhydride, and polyphenols, preferably phenolformaldehyde condensates.
  • acid anhydrides for example trimellitic anhydride
  • polyphenols preferably phenolformaldehyde condensates.
  • epoxy hardeners are known to the skilled person and are commercially available in a multitude of embodiments.
  • crosslinking agents preferably used for the novel can-coating lacquers are those reaction products which can be obtained by heating trimellitic anhydride together with at least one polyol at a molar ratio of 2 to 1.25 to a temperature from 190 to 250°C for at least four hours at a pressure from 0.666 to 4 kPa.
  • Crosslinking agents of this type are described, inter alia, in US patent (US-A-)4,226,755.
  • the hardener is preferably used in an amount from 10 to 30 % by weight, based on the advanced epoxy resin.
  • a very particularly preferred cross- linking agent is the corresponding reaction product of trimellitic anhydride with ethylene gly- col and glycerol, which reaction product has an acid number from 520 to 560 mg KOH per gramme of crosslinking agent and an anhydride content of about 2 to 3 equivalents per kilogramme of crosslinking agent.
  • the novel can-coating lacquer can contain other additives customarily used in this field of application in the respective customary amounts.
  • additives are light stabilisers, colourants, pigments, e.g. titanium dioxide, adhesives, thixotropic agents, flow control agents and suitable solvents, preferably methoxypropyl acetate, where appropriate in admixture with another solvent, such as cyclohexanone.
  • the novel can-coating lacquer is used for entirely or partly coating one or several sides of a food container, e.g. of a tin or a tube, in customary manner.
  • the lacquer is dried after being applied to the substrate.
  • the lacquer is preferably cured by heating to a temperature in the range from 160 to 240°C.
  • the curing time is preferably from about 10 to 30 minutes.
  • the novel can-coating lacquers are particularly suitable for coating the interior sides of food containers, in particular of metallic food containers.
  • Example 1 (Production of an adduct of epoxidised soybean oil and benzoic acid and of an advanced epoxy resin based on 10 % by weight of the adduct:
  • the reactor is charged with 591.4 g (3.16 epoxy equivalents) of a diglycidyl ether of bisphenol A (epoxy value 5.35 equivalents/kg), with 308.5 g (2.71 hydroxyl equivalents) of bisphenol A (8.77 hydroxyl equivalents/kg) and with 1.99g (1.56mmoles) of the catalyst N,N'-methylethylpiperidinium iodide (as a solution of c. 20 % by weight in ethanol).
  • the temperature is continuously raised over 2 hours and 30 minutes to 205°C (measured externally) and is then kept constant for another 28 minutes.
  • the pressure in the reaction vessel rises to about 300 mbar during the reaction.
  • the advanced epoxy resin so obtained has an epoxy value of 0.67 equivalents/kg, a softening point of 112°C (measured by means of a Mettler thermosystem FP 800) and a viscosity according to H ⁇ ppler (40% in butylcarbitol according to DIN 53015) at 25°C of 1386 mPa-s.
  • the proportion of unreacted monomeric diglycidyl ether of bisphenol A in the advanced resin is 1 % by weight (lOOOOppm).
  • Example 2 (Production of an adduct of epoxidised soybean oil and benzoic acid according to Example 1 and of an advanced epoxy resin based on 20 % by weight of the adduct:
  • the reactor is charged with 515.4 g (2.75 epoxy equivalents) of a diglycidyl ether of bisphenol A (epoxy value 5.35 equivalents/kg), with 284.6 g (2.5 hydroxyl equivalents) of bisphenol A (8.77 hydroxyl equivalents/kg) and with 1.04g (4.08mmoles) of the catalyst N.N'-methylethylpiperidinium iodide (as a solution of c. 20 % by weight in ethanol).
  • the temperature is continuously raised over 1 hour and 45 minutes to 205°C and is then kept constant for another 15 minutes.
  • the pressure in the reaction vessel rises to about 200 mbar during the reaction.
  • the advanced epoxy resin so obtained has an epoxy value of 0.60 equivalents/kg, a softening point of 106°C (measured by means of a Mettler thermosystem FP 800) and a viscosity according to H ⁇ ppler (40% in butylcarbitol according to DIN 53015) at 25°C of 1409 mPa-s.
  • the proportion of unreacted monomeric diglycidyl ether of bisphenol A in the advanced resin is about 0.2 % by weight (2100 ppm).
  • Example 3 (Production of an adduct of epoxidised soybean oil and benzoic acid according to Example 1 and of an advanced epoxy resin based on 30 % by weight of the adduct:
  • the reactor is charged with 438.9 g (2.35 epoxy equivalents) of diglycidyl ether of bisphenol A (epoxy value 5.35 equivalents/kg), with 261.1 g (2.3 hydroxyl equivalents) of bisphenol A (8.77 hydroxyl equivalents/kg) and with 1.28g (5.02mmoles) of the catalyst N.N'-methylethylpiperidinium iodide (as a solution of c. 20 % by weight in ethanol).
  • the temperature is continuously raised over 1 hour and 45 minutes to 205°C and is then kept constant for another 15 minutes.
  • the pressure in the reaction vessel rises to about 400 mbar during the reaction.
  • the advanced epoxy resin so obtained has an epoxy value of 0.60 equivalents/kg, a softening point of 88°C (measured by means of a Mettler thermosystem FP 800) and a viscosity according to H ⁇ ppler (40% in butylcarbitol according to DIN 53015) at 25°C of 693 mPa-s.
  • the proportion of unreacted monomeric diglycidyl ether of bisphenol A in the advanced resin is about 0.1 % by weight (1300 ppm).
  • Example 4 (Production of an adduct of epoxidised soybean oil and benzoic acid and of an advanced epoxy resin based on 20 % by weight of the adduct:
  • the reactor is charged with 525.30 g (2.805 epoxy equivalents) of a diglycidyl ether of bisphenol A having an epoxy equivalent weight of 187, with 274.7g (2.409 hydroxyl equivalents) of bisphenol A and with 1.054g (4.133 mmol) of N.N'-methylethylpiperidinium iodide (solution of 20 % by weight of N,N'-methylethylpiperidi- nium iodide in ethanol).
  • the temperature is continuously raised over 1 hour and 55 minutes to 205°C (external reactor temperature) and is then kept constant for another 22 minutes (internal reactor temperature about 199°C).
  • the resulting advanced epoxy resin has an epoxy equivalent weight of 1538, a softening point of 105°C (measured by means of a Mettler thermosystem FP 800) and a viscosity according to H ⁇ ppler (40% in butylcarbitol according to DIN 53015) at 25°C of 1586 mPa-s.
  • the proportion of free monomeric diglycidyl ether of bisphenol A in the advanced resin is 2300 ppm, and the proportion of free bisphenol A is 202 ppm.
  • the can-coating lacquers listed in the following Table are produced by first preparing the solution of the crosslinking agent indicated in the Table and then mixing that with a solution of 50 % by weight of the respective advanced epoxy resin in methoxypropyl acetate (MPA) and adding the indicated amount of additional methoxypropyl acetate. Using a roll coater, the curable compositions are then applied to aluminium sheets (to determine the mechanical properties of the coatings) and to tin sheets (to carry out the sterilisation tests and to determine the resistance to acetic acid).
  • MPA methoxypropyl acetate
  • the impact strength; r( reverse side) is determined by dropping a 2 kg die, on the bottom side of which is a ball 20 mm in diameter, bottom first from a specific height from the reverse side on to the coated area.
  • the value indicated is the product of the weight of the die in kg and of the test height in cm at which no damage of the coating is found yet, i.e. the coating remains uncracked.
  • the acetone rubbing test is carried out by drenching a wool cloth with acetone and rubbing it twenty times back and forth over the coating.
  • trimellitic anhydride and an ester of CAS-No. 43011-20-7 (acid number 500-540 mgKOH/g; anhydride content 3.00 - 4.00 equ./kg; softening point according to Mettler, DIN 51920 95 to 110°C)
  • the can-coating lacquer listed in the following Table is produced and applied according to the description of Example 5, the properties indicated in the Table being found.

Landscapes

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

Abstract

L'invention se rapporte à un vernis-laque thermodurcissable, conçu pour la formation de revêtements sur des boites de conserve. Ce vernis-laque comporte d'une part une résine époxy perfectionnée qui est le produit de réaction d'un ou de plusieurs éthers de bisphénol et de diglycidyle et d'un produit d'addition d'huile de soja époxydée avec un acide monocarboxylique, l'huile de soja époxydée possédant un poids équivalent en époxy compris entre 350 et 600, et d'autre part un agent de réticulation pour résines époxy.
PCT/EP1999/004118 1998-06-26 1999-06-15 Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve WO2000000533A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020007014822A KR20010053217A (ko) 1998-06-26 1999-06-15 열경화성 캔-코팅 래커
BR9911571-9A BR9911571A (pt) 1998-06-26 1999-06-15 Verniz para revestimento de latas curável pelo calor
EP99927985A EP1095086A1 (fr) 1998-06-26 1999-06-15 Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve
JP2000557292A JP2002519455A (ja) 1998-06-26 1999-06-15 熱硬化性缶塗装ラッカー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1368/98 1998-06-26
CH136898 1998-06-26

Publications (1)

Publication Number Publication Date
WO2000000533A1 true WO2000000533A1 (fr) 2000-01-06

Family

ID=4208787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004118 WO2000000533A1 (fr) 1998-06-26 1999-06-15 Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve

Country Status (6)

Country Link
EP (1) EP1095086A1 (fr)
JP (1) JP2002519455A (fr)
KR (1) KR20010053217A (fr)
CN (1) CN1307606A (fr)
BR (1) BR9911571A (fr)
WO (1) WO2000000533A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013063753A1 (fr) * 2011-11-01 2013-05-10 Dow Global Technologies Llc Formulations de résine époxy liquide
US10703920B2 (en) 2016-09-28 2020-07-07 Ppg Industries Ohio, Inc. Corrosion-resistant epoxidized vegetable oil can interior coating

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101386673B (zh) * 2008-09-25 2011-09-07 中国海洋石油总公司 油改性环氧树脂及含该树脂的预涂卷材涂料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160622A2 (fr) * 1984-05-02 1985-11-06 Ciba-Geigy Ag Compositions contenant des esters de résines époxydes allongées
US4786666A (en) * 1987-11-18 1988-11-22 Interez, Inc. Epoxy compositions containing glycidyl ethers of fatty esters
US5095050A (en) * 1990-11-21 1992-03-10 The Dow Chemical Company Advanced epoxy compositions, curable compositions and cured products
EP0610987A1 (fr) * 1993-02-01 1994-08-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de résines glycidyliques contenant des groupes alpha-glycols
WO1994022954A1 (fr) * 1993-03-30 1994-10-13 Shell Internationale Research Maatschappij B.V. Modification d'esters epoxy a l'aide d'huile vegetale epoxydee

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160622A2 (fr) * 1984-05-02 1985-11-06 Ciba-Geigy Ag Compositions contenant des esters de résines époxydes allongées
US4786666A (en) * 1987-11-18 1988-11-22 Interez, Inc. Epoxy compositions containing glycidyl ethers of fatty esters
US5095050A (en) * 1990-11-21 1992-03-10 The Dow Chemical Company Advanced epoxy compositions, curable compositions and cured products
EP0610987A1 (fr) * 1993-02-01 1994-08-17 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de résines glycidyliques contenant des groupes alpha-glycols
WO1994022954A1 (fr) * 1993-03-30 1994-10-13 Shell Internationale Research Maatschappij B.V. Modification d'esters epoxy a l'aide d'huile vegetale epoxydee

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013063753A1 (fr) * 2011-11-01 2013-05-10 Dow Global Technologies Llc Formulations de résine époxy liquide
CN104066765A (zh) * 2011-11-01 2014-09-24 陶氏环球技术有限责任公司 液体环氧树脂制剂
CN104066765B (zh) * 2011-11-01 2016-05-18 蓝立方知识产权有限责任公司 液体环氧树脂制剂
US9745409B2 (en) 2011-11-01 2017-08-29 Blue Cube Ip Llc Liquid epoxy resin formulations
US10703920B2 (en) 2016-09-28 2020-07-07 Ppg Industries Ohio, Inc. Corrosion-resistant epoxidized vegetable oil can interior coating
US11332303B2 (en) 2016-09-28 2022-05-17 Ppg Industries Ohio, Inc. Corrosion-resistant epoxidized vegetable oil can interior coating

Also Published As

Publication number Publication date
BR9911571A (pt) 2001-03-20
KR20010053217A (ko) 2001-06-25
JP2002519455A (ja) 2002-07-02
EP1095086A1 (fr) 2001-05-02
CN1307606A (zh) 2001-08-08

Similar Documents

Publication Publication Date Title
KR101918787B1 (ko) 코팅 조성물
EP3371241B1 (fr) Composition liquide de résine époxyde utile pour fabriquer des polymères
JP5797759B2 (ja) コーティング組成物
WO2008045894A1 (fr) Polymères solubles avec une faible conversion d'acides à partir de résines époxy aromatiques et de diacides et revêtements réticulés préparés à partir de ceux-ci
JP2014173090A (ja) エポキシ樹脂組成物、同組成物を製造する方法、およびその物品
WO2008045889A1 (fr) Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères
CN110408013A (zh) 一种粉末涂料用聚酯树脂及其制备方法
WO2008045884A1 (fr) Procédé d'élaboration de polymères solubles avec taux de conversion élevé de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères
US6555628B2 (en) Epoxy resins and process for making the same
EP4089131A1 (fr) Résine durcissable, composition de résine durcissable, produit durci, dispositif électronique, matériau de carte stratifiée, agent d'encapsulation de composant électronique et procédé de production de résine durcissable
WO2000000533A1 (fr) Vernis-laque thermodurcissable pour la formation de revetements sur des boites de conserve
JP2782467B2 (ja) 先駆エポキシ樹脂
TWI515224B (zh) 羥基官能聚醚及其製備方法
US5420227A (en) Modified acid polyesters and their use as curing agents in heat-curable binders
US20220380622A1 (en) Method for manufacturing ultra-low-temperature, fast-curable epoxy resin, and powder coating composition comprising resin manufactured thereby
JP7337874B2 (ja) 多価フェノール樹脂、多価フェノール樹脂のグリシジルエーテル、及びその使用
JP3517933B2 (ja) エポキシ基含有ポリヒドロキシポリエ−テル樹脂及びその樹脂組成物
JPH0710968A (ja) アドバンスメント触媒を含むエポキシ樹脂混合物
JPH10310683A (ja) エポキシ樹脂およびその塗料組成物
JPH08325512A (ja) 官能基としてカルボキシル基を持つアルキリデンポリフェノールを含むエポキシ樹脂を基材とする焼付エナメル
JPH0410492B2 (fr)
JP2003137980A (ja) フェノール樹脂、エポキシ樹脂、その製造方法及び半導体封止材用樹脂組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99807883.2

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): BR CN JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999927985

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09720439

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1020007014822

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1999927985

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020007014822

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1999927985

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020007014822

Country of ref document: KR