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EP1268693A2 - Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol - Google Patents

Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol

Info

Publication number
EP1268693A2
EP1268693A2 EP01919392A EP01919392A EP1268693A2 EP 1268693 A2 EP1268693 A2 EP 1268693A2 EP 01919392 A EP01919392 A EP 01919392A EP 01919392 A EP01919392 A EP 01919392A EP 1268693 A2 EP1268693 A2 EP 1268693A2
Authority
EP
European Patent Office
Prior art keywords
glycol
polyester
coating composition
powder coating
propanediol
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.)
Withdrawn
Application number
EP01919392A
Other languages
German (de)
English (en)
French (fr)
Inventor
Oliver Wendell Smith
Shelby Freland Thames
Lichang Zhou
Thomas Clayton Forschner
Wyndham Henry Boon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP1268693A2 publication Critical patent/EP1268693A2/en
Withdrawn legal-status Critical Current

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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints

Definitions

  • powder coatings release no harmful solvents during application, may be applied in a highly efficient manner with little waste, and, thus, are considered particularly environmentally friendly and economical .
  • Usable powder coatings may be obtained using curable epoxy resin powder coatings.
  • Many epoxy resin powder coatings currently commercially available contain solid polyester polyols which are cured with epoxy resins .
  • thermosetting coatings when compared to coatings derived from thermoplastic compositions, generally are tougher, more resistant to solvents and detergents, have better adhesion to metal substrates, and do not soften when exposed to elevated temperatures .
  • the curing of thermosetting coatings has created problems in obtaining coatings which have, in addition to the above-stated desirable characteristics, good smoothness, and flexibility.
  • Coatings derived from thermosetting coating compositions should possess good impact strength, hardness, flexibility, and resistance to solvents and chemicals. For example, good flexibility is essential for powder coating compositions used to coat sheet (coil) steel which is destined to be formed or shaped into articles used in the manufacture of various household appliances and automobiles where the sheet metal is flexed or bent at various angles.
  • Powder coating systems based on carboxyl polyesters such as neopentyl glycol based carboxyl polyesters and melamine-, benzoguanamine- , and urea-formaldehyde cross- linking agents have been used in the coatings industry. See, for example, those described in US-A-5739204.
  • EP-A-0008344 discloses a similar system and mentions the use of 1,3-PDO.
  • Neopentyl glycol is often used in formulations for polyester powder coatings along with a mixture of terephthalic and isophthalic acids either by themselves or as mixtures and optionally branched with small amounts of trimethylol propane.
  • polyester used in this type of powder coating is modified for improved flexibility, impact, and toughness, then other properties of significance to the coating are compromised.
  • Other potential modifiers include adipic acid, 1 , 4-butanediol , and 2 -methyl -1, 3-propanediol .
  • 1 , 3-propanediol is incorporated into a carboxyl functional polyester epoxy resin powder coating composition for increased impact resistance and flexibility without the loss of other critical properties and also where the 1,3-PDO modified polyester has lower melt viscosity than polyesters made with 100% neopentyl glycol .
  • the present invention comprises a polyester powder coating composition formed by reacting: a) a polyester resin formed by reacting one or more aliphatic glycols and one or more polycarboxylic acids and/or anhydrides, wherein the aliphatic glycol is comprised of 5 to 90% 1, 3-propanediol on a molar basis, in the presence of an esterification catalyst and then endcapping the polyester with an endcapping agent to ensure that the polyester has carboxyl chain ends ; and b) an epoxy resin crosslinking agent.
  • a polyester powder coating composition formed by reacting: a) a polyester resin formed by reacting a mixture of neopentyl glycol and 1, 3-propanediol , wherein the 1, 3-propanediol comprises from 5 to 90% of the mixture on a molar basis, with a mixture of terephthalic acid and isophthalic acid, wherein the ratio of terephthalic acid to isophthalic acid is in the range of 90/10 to 50/50, in the presence of dibutyl tin oxide, and adding trimellitic anhydride to endcap the polyester; and b) an epoxy resin crosslinking agent which is a diglycidyl ether of 2 , 2-bis (4-hydroxy phenyl) propane which has been reacted with bisphenol-A and has a weight per epoxy of 450 to 900.
  • any coated product made using the powder coating composition of the present invention.
  • FIG 3 is a graph showing the Differential Scanning Calorimetry (DSC) curves of polyester/epoxy hybrid powder coatings; and Figure 4 is a graph showing the gloss of clear and pigmented polyester/epoxy powder coatings.
  • DSC Differential Scanning Calorimetry
  • carboxyl capped polyesters that were examined were carboxy equivalent, acid number, colour before grinding, glass transition temperature (Tg) , processability, storage stability, front/reverse impact, powder flow properties, powder reactivity, hardness, adhesion, MEK double rub, and chemical and stain resistance.
  • the preferred carboxyl capped polyesters are characterized by an acid number of 30 to 120 mg KOH/g, preferably 40 to 110 mg KOH/g, and a Tg of greater than
  • the acid number 56, 100/equivalent weight (56,100 is the weight in mg per mole KOH) .
  • Low equivalent or high acid number results in high crosslinking density and brittleness, while high equivalent or low acid number results in low crosslinking density, and thus poor performance such as low methylethylketone and solvent resistance, etc.
  • the Tg range is generally a requirement for good storage stability.
  • the starting materials for the polyester of the present invention are aliphatic glycols including 1,3- PDO, aromatic polycarboxylic acids or anhydrides, an esterification catalyst, and optionally a branching agent.
  • the starting materials for the cured coatings of the present invention are the 1,3-PDO containing polyester, one or more epoxy resins, a crosslinking catalyst and optionally conditioning agents, auxiliary agents, and additives.
  • Suitable aliphatic glycols have a number average molecular weight of 62 to 500 and may optionally contain ether groups, ester groups, and/or carbonate groups.
  • Suitable aliphatic glycols include, but are not limited to, ethylene glycol, 1, 2-propanediol , 2 -methyl -1, 3- propanediol , 1,3- and 1, 4-butanediol , 1, 6-hexanediol , diethylene glycol, dipropylene glycol, neopentyl glycol and mixtures of these diols.
  • Other suitable diols include triethylene glycol, tetraethylene glycol, tripropylene glycol, tetrapropylene glycol, polycarbonate diols having hydroxyl numbers of about 56 to 168, dimeric fatty alcohols and mixtures of these diols.
  • a branching agent is also useful, such as, for example, a small amount of a triol or higher alcohol.
  • Suitable branching agents include, but are not limited to trimethylolethane, trimethylolpropane, or pentaerythritol . The preferred was trimethylolpropane.
  • the carboxyl functional polyesters of the present invention may be synthesized by a two stage process. This is an esterification reaction.
  • dibasic acid such as terephthalic acid (TPA) , isophthalic acid (IPA) , polyols such as NPG and PDO diols, and optional branching agents like trimethylolpropane are reacted at a temperature in the range of 150 to 250°C, preferably 170 to 230°C, to form a hydroxyl-terminated prepolymer .
  • TPA terephthalic acid
  • IPA isophthalic acid
  • polyols such as NPG and PDO diols
  • optional branching agents like trimethylolpropane are reacted at a temperature in the range of 150 to 250°C, preferably 170 to 230°C, to form a hydroxyl-terminated prepolymer .
  • the hydroxyl groups are endcapped with carboxylic acids or their anhydrides to form an acid polyester.
  • the amount of endcapping agent used is determined by the hydroxyl number of the polyester. From 80 to 100% of the stoichiometric amount required to cap all of the chain ends of the polyester is generally added.
  • the endcapping agents which can be utilized are generally acids or anhydrides containing a plurality of carboxylic acid groups, that is two or more carboxylic groups per molecule.
  • Suitable acids include saturated, unsaturated, aliphatic, or aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, sebacic, maleic, fumaric, succinic, adipic, azelaic, malonic, dodecanoic, trimellitic, pyromellitic, or mixtures thereof.
  • Terephthalic acid is preferred with isophthalic acid being highly preferred.
  • Anhydrides of these acids can also be used as endcapping agents and are preferred, including the anhydrides of the acids described above, and especially including phthalic anhydride, trimellitic anhydride and succinic anhydride, wherein trimellitic anhydride is preferred.
  • the endcapping agent is added to the prepolymer and the esterification is continued until a desired acid number is obtained.
  • the total reaction time is approximately 10 to 15 hours.
  • a conventional catalyst for promotion of an esterification reaction such as dibutyltin oxide, can be used in catalytic amounts of 0.01 to 1 wt%.
  • the catalyst can be added in either Stage 1 or Stage 2.
  • Catalysts which can be for the esterification include tin, antimony, titanium, and zirconium compounds, including titanium alkoxides and derivatives thereof, such as tetra (2 -ethylhexyl) titanate, tetrastearyl titanate, diisopropoxy-bis (acetylacetonato) titanium, di-n-butoxy- bis (triethanolaminoato) titanium, tributyl monoacetyltitanate triisopropyl monoacetyltitanate and tetrabenzoic acid titanate; titanium complex salts such as alkali titanium oxalates and malonates, potassium hexafluorotitanate and titanium complexes with hydroxycarboxylic acids such as
  • Xylene/water can be added before the reaction starts to facilitate the removal of water formed during the reaction.
  • 1, 3-propanediol was substituted for neopentyl glycol in molar increments of 0, 15, 30, 50, and 100%.
  • a commercial scale reaction would probably rarely use xylene/water and could start with an ester, such as dimethylterephthalate (DMT) or dimethylisophthalate (DMI) . It is also possible to use acid chlorides.
  • Powder coatings may be prepared from the 1,3- propanediol derived polyesters formulated with an epoxy resin crosslinking agent, a flow control agent, and a crosslinking catalyst. Conventional pigmenting materials (pigments or dye) , such as titanium dioxide, may also be included in the formulation to impart a desirable colour to the coated substrate.
  • Epoxy resins suitable for the invention composition are generally any epoxy resins which are solid at room temperature.
  • the epoxy resin preferably has an average weight per epoxide (WPE) within the range of 400 to 1400 and a number average molecular weight within the range of 800 to 5000. More preferably, the epoxy resin has a WPE of 500 to 1000 and a number average molecular weight of 1000 to 2000. Higher WPE's and molecular weights may be used, provided that the resin is blended at the processing temperature and processable in a high shear mixer or a melt blender. Generally the epoxy resin will have a 1,2 -epoxy equivalency greater than one and preferably about two or more.
  • the epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic .
  • epoxy resins suitable for use in the present invention include polyglycidyl ethers of polyhydric compounds, brominated epoxies, epoxy novolacs or similar polyhydroxyphenol resins, polyglycidyl ethers of glycols or polyglycols, and polyglycidyl esters of polycarboxylic acids.
  • the epoxy resin is a polyglycidyl ether of a polyhydric phenol .
  • Polyglycidyl ethers of polyhydric phenols can be produced, for example, by reacting an epihalohydrin with a polyhydric phenol in the presence of an alkali.
  • suitable polyhydric phenols include: 2 , 2-bis (4-hydroxyphenyl) propane (bisphenol-A); 2 , 2-bis (4-hydroxy-tert-butylphenyl) propane; 1 , 1-bis (4-hydroxyphenyl) ethane; 1, 1-bis (4- hydroxyphenyl) isobutane; 2, 2-bis (4- hydroxytertiarybutylphenyl) propane; bis (2- hydroxynapthyl ) methane; 1, 5-dihydroxynaphthalene; and 1 , 1-bis (4-hydroxy-3-alkylphenyl) ethane.
  • the preferred polyhydric phenol is bisphenol-A.
  • a preferred epoxy resin is a diglycidyl ether of 2 , 2-bis (4-hydroxyphenyl) propane which has been reacted with bisphenol-A and has a weight per epoxy of 450 to 900.
  • suitable epoxy resins include advanced EPON (trade mark) Resin 828, a product of Shell Chemical Company, which is a diglycidyl ether of 2, 2-bis (4-hydroxyphenyl) propane having an average molecular weight of 380 and a weight per epoxy in the range of 180 to 195.
  • the preferred crosslinking agents are EPON Resins 1001F, 1002F, and 2002, which are advanced EPON 828 resins reacted with bisphenol-A which have a weight per epoxy of 450 to 900.
  • a flow control or levelling agent is desirably incorporated into the coating formulation to aid in levelling the applied and thermoset coatings.
  • Such flow control agents typically comprise acrylic polymers and are available from several suppliers, i.e., MODAFLOW from Monsanto Company, BYK 36OP from BYK Mallinkrodt and ACRONAL from BASF.
  • a suitable concentration range for incorporation of the flow control agent into the coating is 0.25 to 2.0% based on the weight of the resin solids, and preferably in the range of 0.60 to 1.5%.
  • the powder coatings can be cured or crosslinked without the use of a catalyst.
  • a catalyst to promote the crosslinking reaction of the epoxy resin with the polyesters.
  • the uncatalyzed rate of reaction has been found to be too slow to suit the baking schedules established in the industry.
  • Suitable catalysts include amine containing compounds, such as amides, imides, imidazoles, quaternary ammonium salts, phosphonium salts, metal salts of acidic and fatty acids, tin and zinc compounds. Specific samples of these catalysts are tetrabutylammonium and choline chloride. These catalysts may be used either alone or in combination.
  • a suitable concentration range for incorporation of the catalyst into the coating is 0.01 to 1% based on the weight of the resin solids, and preferably in the range of 0.05 to 0.5%.
  • TPA terephthalic acid
  • IPA isophthalic acid
  • NPG isophthalic acid
  • PDO trimellitic anhydride
  • TMA trimellitic anhydride
  • the total reaction time was approximately 10 to 15 hours.
  • Dibutyltin oxide (0.4%) as used as a catalyst and xylene/water were added to facilitate the removal of water formed during the reaction.
  • Polyester compositions with molar substitutions of PDO for NPG from 0 to 100% are listed in Table 1.
  • Polyester/epoxy hybrid powder coatings were prepared from the PDO derived polyesters formulated with epoxy resin via equal equivalents of carboxyl/epoxy groups.
  • EPON 1001F Resin from Shell Chemical Company, having an equivalent weight of 525-550, was used as a crosslinking agent for the polyesters.
  • EPON 1001F Resin has very low equivalent weight among the commercial available epoxy resins. 0.2% Choline chloride, Actiron CC-6 from Synthron, Inc., was used as a catalyst.
  • a flow control agent Modaflow Powder III, Monsanto
  • a degassing agent benzoin (Uraflow-B, GCA Chemical Corporation) were also incorporated into the coatings.
  • Pigmented powder coatings were prepared by using R-960 TiO- (DuPont) at a pigment/binder ratio of 0.7/1 by weight.
  • the final powder coating compositions are listed in Table 2. All the ingredients were initially premixed in a high speed mixer for 2 minutes to assure homogeneous mixing and the solids were then fragmented into small particles. The resulting intimate mixture was then continuously processed through a twin screw extruder to produce a uniform viscous melt. The extrusion temperature was maintained at 75 °C in zone 1 and 80 °C in zone 2 at 50 rpm. The molten extrudates were passed through a pair of water cooled squeeze rolls to yield a friable product. The products were then pulverized using a hammer mill with liquid nitrogen fed slowly into the grinding chamber.
  • the final powders were electrostatic-spray applied to grounded cold-rolled steel panels (Q Panel QD-36 and S- 36) and the coating properties were evaluated after curing at 190 °C for 15 minutes. The curing was carried out by placing panels in a hot air oven. Table 2 Powder Coatings formulations
  • Tg glass transition temperatures
  • Figure 1 glass transition temperatures
  • the carboxyl functional polyesters were 6 to 8 degrees higher than the corresponding hydroxyl functional polyesters. This characteristic of the carboxyl polyesters is expected to improve the storage stability of the corresponding powder coatings.
  • T g s for the polyesters were reported for the second heating cycle via Differential Scanning Calorimetry (DSC) at a scanning rate of 10°C/minute. The second heating cycle involved heating the samples to a melt and then cooling the resin prior to measuring the
  • polyester resins for powder coatings should be high enough to achieve good storage stability.
  • Commercially available polyesters for polyester/epoxy hybrid powder coatings typically have Tg values around 50 to 60 °C.
  • the powder coatings formulated with up to 50 percent PDO derived carboxyl polyesters had very good storage stability, since they had Tg values over 55 °C.
  • the inclined plate flow was measured according to the PCI standard method. It is a useful indicator of the degree of flow occurring during the curing of powder coated parts.
  • the inclined plate flow is related to the zero shear melt viscosity of the base resin and is influenced by the reactivity of crosslinking agent with the polyester resins. It was very clear that the plate flow increased with increasing PDO concentrations in the PDO/NPG mixtures at both 175°C and 190°C (Table 5) .
  • the inclined plate flow was 50, 68, and 79 mm for pure NPG, 30 percent, and 50 percent PDO levels, respectively. Therefore, incorporation of PDO improved the flow properties of the powder coatings.
  • the powders also had higher plate flows at 175°C than at 190 °C, because of higher reaction rates at higher temperatures. Gel Time Reactivity.
  • Gel time reactivity is the time required for a powder to advance to a gelled state through a liquid phase at a defined temperature. The test was performed via rubbing the powder coating with the tip of a wooden applicator stick over a hot plate until a solid gel was produced. Gel times for polyester powder coatings were determined at 180 °C according to the PCI standard method. As seen in Table 5, all the coatings provided similar gel times, which is in accord with DSC studies.
  • the reactivity of the carboxyl functional polyester polymers with epoxy resin crosslinking agents was studied via Differential Scanning Calorimetry (DSC) at a scanning rate of 10°C/minute.
  • DSC Differential Scanning Calorimetry
  • Table 6 The DSC curves shown in Figure 3, and the testing results shown in Table 6 indicate the onset of cure--exothermal peak and enthalpy are very close the powder coatings.
  • polyesters based on NPG and PDO/NPG mixtures have similar reactivity with the crosslinking agent.
  • Conical mandrel bend tests were performed via bending the coating panels on a conical mandrel tester (Gardner Laboratory, Inc. 3.2 mm (1/8") diameter) over a period of 3 seconds. The testing results are listed in Table 10. All clear coating panels passed the test, i.e. no cracking. However, the pigmented coating formulated with pure NPG polyester showed about 6 mm cracking upon mandrel bending, while coating incorporation of 30 percent PDO derived polyester passed the test.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
EP01919392A 2000-03-24 2001-03-23 Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol Withdrawn EP1268693A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US19211100P 2000-03-24 2000-03-24
US192111P 2000-03-24
PCT/EP2001/003441 WO2001070893A2 (en) 2000-03-24 2001-03-23 Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol

Publications (1)

Publication Number Publication Date
EP1268693A2 true EP1268693A2 (en) 2003-01-02

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EP01919392A Withdrawn EP1268693A2 (en) 2000-03-24 2001-03-23 Carboxyl-functional polyester epoxy resin powder coatings based on 1,3-propanediol

Country Status (8)

Country Link
EP (1) EP1268693A2 (zh)
JP (1) JP2003528200A (zh)
KR (1) KR20020084241A (zh)
CN (1) CN1179007C (zh)
AU (1) AU2001246509A1 (zh)
CA (1) CA2403812A1 (zh)
MX (1) MXPA02009280A (zh)
WO (1) WO2001070893A2 (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020061963A1 (en) * 2000-09-25 2002-05-23 Thames Shelby Freland Polyester triglycidyl isocyanurate resin powder coatings based on 1,3-propanediol
EP1798267A1 (en) * 2005-12-15 2007-06-20 Dupont Powder Coatings France S.A.S. Powder coating composition suitable for coil coating
EP2085441A1 (en) * 2008-01-31 2009-08-05 Cytec Surface Specialties, S.A. Powder Composition
CN108570277B (zh) 2011-08-04 2021-11-02 阿克佐诺贝尔国际涂料股份有限公司 耐久热固性粉末涂料组合物
CN103497316B (zh) * 2013-08-08 2015-12-02 山东汇盈新材料科技有限公司 低端羧基含量的生物降解聚酯的制备方法
CN103554451B (zh) * 2013-10-25 2016-04-27 滁州市全丰物资有限公司 一种抗晒耐水性聚酯树脂及其生产工艺
CN103588967B (zh) * 2013-10-25 2016-01-20 滁州市全丰物资有限公司 一种混合型聚酯树脂的生产工艺
CN103554454A (zh) * 2013-10-25 2014-02-05 滁州市全丰物资有限公司 一种户外型聚酯树脂及其生产工艺
CN104530927A (zh) * 2014-12-29 2015-04-22 浙江明泉工业涂装有限公司 一种高光型、高效抑泡型粉末涂料及其制备方法
CN105294995B (zh) * 2015-12-02 2018-06-22 河北麦格尼菲复合材料股份有限公司 生物基环氧树脂固化剂及其制备方法

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DE2536641A1 (de) * 1974-11-04 1976-05-06 Schenectady Chemical Niedermolekulare polyester und ihre verwendung zum haerten von epoxyharzen und herkoemmlichen polyesterharzen

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Also Published As

Publication number Publication date
AU2001246509A1 (en) 2001-10-03
WO2001070893A3 (en) 2001-12-27
WO2001070893A2 (en) 2001-09-27
KR20020084241A (ko) 2002-11-04
JP2003528200A (ja) 2003-09-24
CN1179007C (zh) 2004-12-08
CA2403812A1 (en) 2001-09-27
CN1425048A (zh) 2003-06-18
MXPA02009280A (es) 2003-05-23

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