WO2002034843A1 - Composition de revetement comprenant un diluant reactif - Google Patents

Composition de revetement comprenant un diluant reactif Download PDF

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Publication number
WO2002034843A1
WO2002034843A1 PCT/EP2001/011929 EP0111929W WO0234843A1 WO 2002034843 A1 WO2002034843 A1 WO 2002034843A1 EP 0111929 W EP0111929 W EP 0111929W WO 0234843 A1 WO0234843 A1 WO 0234843A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
acid
citraconimide
formula
reactive
Prior art date
Application number
PCT/EP2001/011929
Other languages
English (en)
Inventor
Keimpe Van Den Berg
Heert Andringa
Frederik Rous
Robert Paul Klaasen
Huig Klinkenberg
Berend Hoving
Original Assignee
Akzo Nobel N.V.
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 Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to AU2002215024A priority Critical patent/AU2002215024A1/en
Publication of WO2002034843A1 publication Critical patent/WO2002034843A1/fr

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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
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • Reactive diluents for air drying coating compositions are known from WO 97/02229, WO 97/02230 and WO 97/02326. These diluents are rather difficult to synthesize and have plural reactive groups.
  • Another example of a reactive diluent used in air drying compositions is cyclo pentadiene-modified linseed oil.
  • a coating composition comprising a compound, preferably a binder, having functional groups which are reactive to olefinically unsaturated bonds, and one or more compounds according to the following formula 1 : formula 1
  • R1 - R3 are hydrogen or substitute groups.
  • R1 is hydrogen, or an alkyl, hydroxyalkyl, carboxy alkyl, alkoxy silyl alkyl, alkoxy, alkenyl, or aryl group.
  • R2 is a methyl group, but may alternatively be a larger group, such as an alkyl group, an alkoxy group or an aryl group.
  • R3 is generally a hydrogen, but may alternatively be any suitable group, e.g. an alkyl group, such as methyl, if so desired.
  • R1 , R2, and R3 of the compound of formula 1 or R1 - R5 of the compound of formula 2 may be chosen such as to obtain a desired molecular weight.
  • Low molecular weights generally result in low viscosity.
  • the molecular weight Mw is preferably between 80 - 800.
  • Optimum molecular weight ranges from 100 to 400.
  • a suitable way for preparing compounds according to formula 1 is to prepare a citraconic anhydrid by reacting citraconic acid with acetic anhydride in the presence of a tertiary amine, a hindered secondary amine or a phosphine, followed by reacting the citraconic anhydride with an amine salt of acetic acid or propionic acid.
  • a tertiary amine a hindered secondary amine or a phosphine
  • Such a method is disclosed in EP-A 0 495 544.
  • Suitable examples of reactive diluents according to the invention are N-benzyl citraconimide, N-octyl citraconimide, N-(2-hydroxyethyl) citraconimide, and N- (3-methoxy propyl) citraconimide.
  • the coating composition according to the present invention may be based on any suitable crosslinking chemistry.
  • the binder comprises functional groups for crosslinking which may for example be hydroxy groups, alkoxy silane, isocyanate carboxyl, and / or epoxy groups. Oxidatively drying compositions, such as alkyd based compositions, or radically curing systems are preferred.
  • Alkyd resins suitable for use in a coating composition according to the invention can be prepared from unsaturated and saturated fatty acids, polycarboxylic acids, and di- or polyvalent hydroxyl compounds.
  • the number of unsaturated fatty acids eligible for use in the preparation of the alkyd resins to be employed according to the invention is large. Preference is given to the use of mono- and polyunsaturated fatty acids, preferably those containing 12 to 26 carbon atoms.
  • mono-unsaturated fatty acids such as lauroleic acid, my stolenic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid; bi-unsatu rated fatty acids, such as linoleic acid; tri-unsaturated acids, such as linolenic acid, eleostearic acid, and licanic acid; quadri-unsaturated fatty acids, such as arachidonic acid and clupanodonic acid, and other unsaturated fatty acids obtained from animal or vegetable oils.
  • the number of saturated fatty acids is also large. Preference is given to the use of saturated fatty acids containing 12 to 26 carbon atoms.
  • mixtures of two or more of such monocarboxylic acids or triglycerides may be employed, optionally in the presence of one or more saturated, (cyclo)aliphatic or aromatic monocarboxylic acids, e.g., pivalic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, 4-tert.butyl-benzoic acid, cyclopentane carboxylic acid, naphthenic acid, cyclohexane carboxylic acid, 2,4-dimethyl benzoic acid, 2-methyl benzoic acid, and benzoic acid.
  • saturated, (cyclo)aliphatic or aromatic monocarboxylic acids e.g., pivalic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, 4-tert.butyl-benzoic acid, cyclopentane carboxylic acid, naphthenic acid, cyclohexane carboxy
  • the carboxylic acids in question may be used as anhydr
  • the alkyd resin comprises di- or polyvalent hydroxyl compounds.
  • suitable divalent hydroxyl compounds are ethylene glycol, 1 ,3- propane diol, 1 ,6-hexane diol, 1 , 12-dodecane diol, 3-methyl-1 ,5-pentane diol, 2,2,4-trimethyl-1 ,6-hexane diol, 2,2-dimethyi-1 ,3-propane diol, and 2-methyl-2- cyclohexyl-1 ,3-propane diol.
  • suitable triols are glycerol, trimethylol ethane, and trimethylol propane.
  • Suitable polyols having more than 3 hydroxyl groups are pentaerythritol, sorbitol, and etherification products of the compounds in question, such as ditrimethylol propane and di-, tri-, and tetrapentaerythritol.
  • etherification products of the compounds in question such as ditrimethylol propane and di-, tri-, and tetrapentaerythritol.
  • the alkyd resins can be obtained by direct esterification of the constituent components, with the option of a portion of these components having been converted already into ester diols or polyester diols.
  • the unsaturated fatty acids can be added in the form of a drying oil, such as sunflower oil, linseed oil, tuna fish oil, dehydrated castor oil, coconut oil, and dehydrated coconut oil.
  • Transesterification with the other added acids and diols will then give the final alkyd resin. This transesterification generally takes place at a temperature in the range of 115 to 250°C, optionally with solvents such as toluene and/or xylene also present.
  • transesterification catalysts suitable for use include acids such as p-toluene sulphonic acid, a basic compound such as an amine, or compounds such as calcium oxide, zinc oxide, tetraisopropyl orthotitanate, dibutyl tin oxide, and tnphenyl benzyl phosphonium chloride
  • the number average molecular weight of the alkyd resin thus prepared preferably is at least 1000 , preferably from 2000 to 5000
  • the coating composition may comprise a binder system which is curable by radical copolyme ⁇ zation, for instance initiated by irradiation of UV- light
  • a binder system which is curable by radical copolyme ⁇ zation, for instance initiated by irradiation of UV- light
  • Suitable examples of such a binder system are (meth)acryloyl-funct ⁇ onal binders, such as acryloyl functional polyurethanes
  • Such (meth)acryloyl groups- containing polyurethanes can be prepared using conventional methods of polyurethane synthesis by conversion of polyisocyanates with hydroxyalkyl (meth)acrylates and a chain extender if desired
  • Suitable chain extenders include diols, polyols, dithiols, polythiols, diamines, and polyamines
  • the coating composition according to the invention may furthermore contain various additives such as pigments, fillers, siccatives, anti-skinning agents, dispersants, surfactants, inhibitors, fillers, anti-static agents, flame-retardant agents, lubricants, anti-foammg agents, cosolvents, extenders, film formation aids, plasticizers, anti-oxidants, anti-freezing agents, waxes, preservatives, thickeners, thixotropic agents, etc.
  • additives such as pigments, fillers, siccatives, anti-skinning agents, dispersants, surfactants, inhibitors, fillers, anti-static agents, flame-retardant agents, lubricants, anti-foammg agents, cosolvents, extenders, film formation aids, plasticizers, anti-oxidants, anti-freezing agents, waxes, preservatives, thickeners, thixotropic agents, etc
  • composition according to the invention is suitable for various industrial applications, e g , automotive or car repair field, or in decorative applications, e g in the do-it-yourself market or in the professional market
  • Coating compositions according to the invention can be used for coating precoated or uncoated substrates of wood, metal, plastics, ceramics, concrete, etc
  • the coating composition may be water-borne, in order to further reduce the volatile organic content.
  • the reactive diluents are also suitable for use in solvent-borne coatings, preferably in so-called high-solids coatings having a solids content of at least 60 % by weight of the composition.
  • the coating composition according to the present invention can be applied by conventional methods, including brushing, roll coating, spray coating, or dipping.
  • Examples 1 and 2 and Comparative Example A viscosity was measured in a DIN flow cup number 4 in accordance with DIN 53221 -1987. The viscosity is given in seconds.
  • Examples 3 and 4 and Comparative Examples A and B viscosity was measured using a Brookfield Cap 2000 at a temperature of 23 °C and a shear of 10000 s "1 .
  • the VOC of the coating composition was calculated as the weight ratio of the non-reactive solvents content to the total solids content.
  • the total solids content includes the content of reactive diluents, but not water.
  • Phase 1 the line traced by the pin closes up again ("open time”).
  • Phase 2 the pin traces a scratchy line ("dust free”).
  • Desmodur ® W polyisocyanate available from Bayer
  • Dilulin ® reactive diluent available from Croda Resins
  • Kronos ® 2310 Ti0 2 (rutile) based pigment available from Kronos; Nuodex ® Combi APB a siccative comprising cobalt, zirconium and calcium, commercially available from Servo Delden
  • Shellsol ® D40 non-reactive aliphatic diluent available from Shell.
  • a 3 I 4-neck flask fitted with a variable speed stirrer, thermocouples in combination with a controller, a distillation column, a reflux condenser, a nitrogen sparge, and a heating mantle was charged with a mixture composed of 332 g of hexahydrophthalic anhydride and 1614 g of polyethylene glycol monomethyl ether of an average molecular weight of 750.
  • the mixture was heated to 170°C for 30 minutes, cooled to 140°C, and 269 g of di(trimethylol- propane) were added, followed by 132 g of xylene and 3.3 g of a 85% aqueous phosphoric acid solution.
  • a 3 I 4-neck flask fitted with a variable speed stirrer, thermocouples in combination with a controller, a condenser, a dry air sparge, and a heating mantle was charged with a mixture composed of 273.2 g of acryloyl-functional diol b), 146.7 g of polyester a), 12.26 g of trimethylol propane, 99.1 g of 4- hydroxybutyl acrylate, 260.8 g of Desmodur ® W, 1.50 g of 2,6-ditert. butyl-p- cresol, and 250 g of 2-butanone.
  • the mixture was heated to 45°C and stirred until homogeneous, while bubbling with dry air.
  • the obtained polyurethane was used to prepare a solvent borne coating composition without a reactive diluent (Comparative Example A) and a similar coating composition with octyl citraconimide as a reactive diluent (Example 1). Contents of the compositions are given in Table 1.
  • Comparative Example B a composition was made based on this alkyd and further comprising titanium dioxide, a siccative, and an anti-skinning agent. A non-reactive solvent was added to obtain a viscosity of 0,6 Pa.s. VOC was calculated as 270 g/l.
  • Comparative Example C 45 pbw of a prior art reactive diluent (Dilulin ® ) was used, to obtain a composition with the same viscosity as in Comparative Example B. To obtain a composition with the same viscosity, VOC, and solids content as in Comparative Example C, only 30 pbw of N-octyl citraconimide was needed in Example 3, while only 30 pbw of N-benzyl citraconimide was needed in Example 4. Table 3

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention se rapporte à une composition de revêtement comprenant un ou plusieurs composés contenant des groupes fonctionnels qui réagissent aux liaisons à insaturation oléfinique, et un composé fonctionnel citraconimide tel que benzyl-citraconimide, octyl-citraconimide ou méthoxypropyl-citraconimide, et/ou un composé fonctionnel itaconimide, tel qu'un diluant réactif. Ces diluants réactifs sont particulièrement appropriés pour sécher par voie oxydative des compositions de revêtement, telles que des revêtements à base d'alkyde, ou des compositions de revêtement qui sont durcissables par copolymérisation radicalaire.
PCT/EP2001/011929 2000-10-25 2001-10-15 Composition de revetement comprenant un diluant reactif WO2002034843A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002215024A AU2002215024A1 (en) 2000-10-25 2001-10-15 Coating composition comprising a reactive diluent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00203720.8 2000-10-25
EP00203720 2000-10-25

Publications (1)

Publication Number Publication Date
WO2002034843A1 true WO2002034843A1 (fr) 2002-05-02

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WO (1) WO2002034843A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1950237A1 (fr) * 2007-01-29 2008-07-30 Cognis IP Management GmbH Procédé pour la préparation des résines alkyd modifiées

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495545A1 (fr) * 1991-01-16 1992-07-22 Akzo Nobel N.V. (Co)polymères de citraconimide et réticulation avec un catalyseur anionique
US5223582A (en) * 1990-10-16 1993-06-29 Bayer Aktiengesellschaft Polymers capable of oxidative crosslinking
WO2000064959A1 (fr) * 1999-04-26 2000-11-02 Akzo Nobel N.V. Composition contenant des composes mercapto-fonctionnels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223582A (en) * 1990-10-16 1993-06-29 Bayer Aktiengesellschaft Polymers capable of oxidative crosslinking
EP0495545A1 (fr) * 1991-01-16 1992-07-22 Akzo Nobel N.V. (Co)polymères de citraconimide et réticulation avec un catalyseur anionique
WO2000064959A1 (fr) * 1999-04-26 2000-11-02 Akzo Nobel N.V. Composition contenant des composes mercapto-fonctionnels

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1950237A1 (fr) * 2007-01-29 2008-07-30 Cognis IP Management GmbH Procédé pour la préparation des résines alkyd modifiées

Also Published As

Publication number Publication date
AU2002215024A1 (en) 2002-05-06

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