EP0000087A1 - Dispersions aqueuses de résines alkydes séchant à l'air et leur utilisation - Google Patents

Dispersions aqueuses de résines alkydes séchant à l'air et leur utilisation Download PDF

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Publication number
EP0000087A1
EP0000087A1 EP78200039A EP78200039A EP0000087A1 EP 0000087 A1 EP0000087 A1 EP 0000087A1 EP 78200039 A EP78200039 A EP 78200039A EP 78200039 A EP78200039 A EP 78200039A EP 0000087 A1 EP0000087 A1 EP 0000087A1
Authority
EP
European Patent Office
Prior art keywords
water
alkyd
dispersion
weight
drying
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.)
Granted
Application number
EP78200039A
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German (de)
English (en)
Other versions
EP0000087B1 (fr
Inventor
Eimbert Gerrit Belder
John Charles Legg
Robert Van Der Linde
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0000087A1 publication Critical patent/EP0000087A1/fr
Application granted granted Critical
Publication of EP0000087B1 publication Critical patent/EP0000087B1/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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps

Definitions

  • This invention relates to alkyds, more in particular to water-dispersible, air-drying alkyd resins suitable for the preparation of'aqueous alkyd dispersions including water-based paints with a gloss finish.
  • Water-based paints having a gloss finish have been known for some time.
  • Water-dispersibility of the alkyds which constitute the resin of these paints has been conferred generally by including in the alkyd alkylene oxide groups from e.g. polyethylene glycol in an amount of at least 9% by weight of the alkyd resin.
  • This amount of alkylene oxide addition product whilst considered necessary to obtain water-dispersibility and a gloss finish, also caused the paint films obtained therefrom to be soft and to have a poor water-resistance.
  • Attempts have been made to improve the quality of the coating e.g. by the incorporation of a vinylic monomer such as styrene, but the results have not been entirely satisfactory, especially not. as regards water-resistance, gloss and hardness of the coatings obtained.
  • novel water-dispersible air-drying alkyds can be obtained by building into an alkyd 1.25-3.75% by_weight of polyalkylene oxide radicals. These novel alkyds can be dispersed in water so as to form stable dispersions useful in the preparation of water-based paints.
  • alkyd resin a polyester product composed by polyhydric alcohols, polybasic acids and monobasic fatty acid (of. Encyclopedia of Polymer Science and Technology, Vol. 1, page 663, Interscience New York). In the case of air-drying alkyd a substantial amount of the fatty acids are polyunsaturated.
  • alkyds are based on a drying oil or suitable unsaturated fatty acids, a polyol, an aromatic and/or aliphatic polycarboxylic acid and an alkylene oxide addition product in which
  • the esterification reaction leading to the alkyd resin is conveniently carried out at a temperature of 180-260 o c, whilst removing water or any other volatiles • of reaction.
  • the addition to the reaction mixture of an entrailment agent such as xylene for the removal of water by azeotropic distillation is preferred.
  • the reaction is optionally carried out in the presence of a catalyst.
  • Suitable catalysts are e.g. metal oxides, especially of the alkaline earth metals, in quantities of (1-10)x 10 -5 of the reaction mixture.
  • drying oil component any of the drying or semi-drying oils can be used; also fatty acids derived therefrom and other suitable unsaturated fatty acids, such as tall oil fatty acids, can be used.
  • Suitable oils are e.g. linseed oil, soyabean oil, perilla oil, safflower oil and dehydrated castor oil.
  • Modified (semi) drying oils such as e.g. styrenated oils can also be used.
  • Suitable styrenated alkyds can also be prepared by the addition of styrene to the alkyd at 140-160°C for a period of several hours until a suitable viscosity has been reached.
  • Analogously isocyanate-modified alkyds can be prepared.
  • any alcohol having 2-6 hydroxyl groups and 3-10 carbon atoms can be used. In general at least 50% of the polyol should contain at least 3 hydroxyl groups in the molecule.
  • Suitable alcohols are e.g. glycol, glycerol, trimethylol alkanes containing 1-3 carbon atoms'in the alkane group, pentaerythritol,etc. These alcohols may also contain a smaller amount of higher oligomeric forms, such as e.g. dipentaerythritol.
  • polycarboxylic acid any acid containing 2-4 carboxyl groups and 3-9 carbon atoms in the molecule can be used. These acids may be aliphatic, aromatic or cycloaliphatic.Dicarboxylic acids are generally preferred as the major acid constituent. Suitable acids are the phthalic acids, maleic acids, fumaric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid etc.
  • polyalkylene oxide compound any compound having the structure of a number of C 2 -C 4 alkylene oxide units
  • C 1 -C 6 mono- or poly-hydroxy compound can be used, including the addition.products of partial ethers of polyhydroxy compounds.
  • the average molecular weight of the alkylene oxide addition product which preferably is an ethylene oxide addition product, in particular polyethylene glycol, should range from 200 to 6000, preferably from 1000 to 3000.
  • Polyethylene glycol is a preferred compound.
  • Certain ethylene oxide addition products are sold under the trade-name of Carbowax (ex. Union Carbide Co.).
  • the novel alkyd resins obtained upon esterification of the above components are yellow-brown semi-solid resins usually having a Gardner colour of 4-8, and can be worked into a stable aqueous dispersion.
  • the alkyd resin is optionally diluted with a minor amount of an organic solvent of the alcohol type such as a C 2 -C 6 mono- or diol, e.g. butanol, ethylene glycol, propylene glycol or a half ether thereof in an amount of 0-10%, preferably 0-5% by weight.
  • the solvent if any, is added after cooling the alkyd to a temperature of 60-150°C, dependent on the nature of the solvent. Whether or not a solvent is used depends, inter alia, on the viscosity of the alkyd.
  • the alkyd is then dispersed in water, using alkyd and water in weight ratios of 30:70 to 70:30, preferably demineralised water at a temperature of 20-100, preferably 56-90°C in the presence of 0.25-5, preferably 1-3 weight percent of an emulsifying agent and 0.05-5 weight percent of a volatile water-soluble base, preferably an amine.
  • the exact amount of base added is such that the final pH of the dispersion ranges between 5 and 9.
  • the dispersion is prepared by means of a high speed dissolver, such as a Cowless disperser.
  • a high speed dissolver such as a Cowless disperser.
  • the emulsifying agent and the amine are previously dissolved in an aqueous phase.
  • the emulsifying agent is preferably of the nonionic or anionic type or a combination thereof. Certain combinations of a nonionic and an anionic yield excellent results.
  • an ethylene oxide addition product of a C 12 -C 20 hydroxy or carboxyl compound carrying 2-50, preferably 4-20 ethylene oxide groups in the molecule is preferably used; in case an anionic is used, an alkali metal C10-C22 soap, a sulfo-succinate or an inorganic C 10 -C 22 .alkyl ether ester such asapolyalkoxysulphate or -phosphate is preferred.
  • the volatile base, in particular water-soluble amino-compound used is preferably a C 1 -C 6 amine or alkanolamine and the amount of amine is so chosen that at least 30 equivalent percent, preferably at least 50 eq. % of the carboxyl groups of the alkyd (as evidenced by its acid value) is neutralised and the final pH of the dispersion ranges between 5 and 9.
  • a novel aqueous dispersion of alkyd in water is obtained containing 30-70 weight percent of alkyd and 70-30 weight percent of water, preferably 50-70 weight percent of alkyd, 50-30 weight percent of water, 0.25-5 weight percent of emulsifying agent and 0.05-5 weight percent of a volatile base.
  • the average particle size of the dispersed alkyd may range between 0.5 and 15 microns.
  • a water-based paint or like coating composition comprising a water-dispersible alkyd resin as described above, dispersed as a substantially stable emulsion in an aqueous medium with one or more finely divided pigment. (10-50, preferably 20-40% ww), fillers, extenders and drying agents and capable of yielding a glossy coating can thus be obtained.
  • the stable alkyd emulsion is thus a colourless varnish and a starting material in the preparation of water-based paints.
  • the pigment-fillers, extenders, drying agents and other adjuncts can be added directly to the aqueous dispersion of the alkyd but it is generally preferred first to prepare a pigment paste and to incorporate this paste into the aqueous dispersion of the alkyd.
  • a dispersant and/or wetting agent, water and optionally an at least partially water-soluble.solvent such as a glycol and a thickening agent/protective colloid are ground together until homogeneous.
  • the pigment content generally ranges between 33 and 66 parts by weight, the solvent content from 0-10 parts by weight and the wetting agent/ dispersant from 2-10 parts by weight. In cases where high amounts of pigments (more than 50%; based on the emulsion) are used it may be difficult to obtain a glossy finish.
  • the pigment paste thus obtained is then dispersed in the aqueous dispersion of the alkyd by means of a high speed disperser or a similar device.
  • the aqueous dispersion of the alkyd may be present in one part by weight to 0.5 to 2 parts by weight of pigment paste, small amounts (a few percents) of one.or more defoamers, a thickening agent and a few percent (calculated as free metal) of a drying agent, which is a mixture of metal salts such as cobalt, calcium and lead salts e.g. naphtenates in an organic solvent. Dispersing is continued until a fine dispersion has been obtained.
  • the water-based air-drying coating composition thus obtained is capable of drying to non-tack in 2-6 hours, yielding a gloss finish, dependent on the pigment content, which is water-resistant and hard.
  • a 3-litre, 4 necked reaction vessel equipped with a stirrer, a gas inlet tube, a thermometer and a Dean and Stark apparatus connected to a condensor was charged with drying oil and/or fatty acid, polyol and calcium hydroxide as indicated in Table I and subsequently heated to 250°C under a nitrogen blanket, until alcoholysis was complete (checked by complete solubility of a sample in ethanol).
  • the mixture was then cooled to about 200°C and the acid/anhydride, polyalkylene oxide addition compound (Carbowax 1540) and optionally a polyol and xylene were added.
  • the contents of the flask were heated to 240-245°C while distilling off the reaction water azeotropically and maintained at this temperature until a sample of the resin had the indicated acid value and viscosity. See Table I.
  • the resin obtained as described under A was cooled to 140°C and added over a period of 1.5 h. to an aqueous phase having a temperature in the range from 20°-100°C, which contained the emulsifiers and base as indicated in Table II. Stirring was effected by means of a Cowless-type disperser.
  • the pigment was dispersed in water together with dispersants and a protective colloid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP78200039A 1977-06-13 1978-06-12 Dispersions aqueuses de résines alkydes séchant à l'air et leur utilisation Expired EP0000087B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2456277 1977-06-13
GB2456277 1977-06-13
GB1137978 1978-03-22
GB1137978 1978-03-22

Publications (2)

Publication Number Publication Date
EP0000087A1 true EP0000087A1 (fr) 1978-12-20
EP0000087B1 EP0000087B1 (fr) 1981-09-09

Family

ID=26248235

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200039A Expired EP0000087B1 (fr) 1977-06-13 1978-06-12 Dispersions aqueuses de résines alkydes séchant à l'air et leur utilisation

Country Status (8)

Country Link
US (1) US4299742A (fr)
EP (1) EP0000087B1 (fr)
AT (1) AT381112B (fr)
DE (2) DE2861047D1 (fr)
DK (1) DK149614C (fr)
FR (1) FR2394565A1 (fr)
NL (1) NL7806349A (fr)
NO (1) NO146602C (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441527A3 (en) * 1990-02-07 1991-11-13 Ici Americas Inc. Stabilized polymer latex composition
WO1992009667A1 (fr) * 1990-11-23 1992-06-11 Berol Nobel Ab Composition aqueuse d'alkydes a sechage par auto-oxydation
WO2011098584A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Complexe de sels de manganèse servant d'agent de séchage pour des compositions de revêtement
WO2014014125A1 (fr) * 2012-07-20 2014-01-23 Fujifilm Corporation Procédé de gravure, procédé de production d'un substrat semi-conducteur et dispositif à semi-conducteur l'utilisant
WO2014087418A1 (fr) * 2012-12-05 2014-06-12 Asian Paints Ltd. Dispersions aqueuses d'alkyde acrylé

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6039283B2 (ja) * 1980-06-12 1985-09-05 日立化成工業株式会社 ポリブタジエン変性不飽和ポリエステルの製造法
US4600441A (en) * 1985-03-21 1986-07-15 Westinghouse Electric Corp. Oil and dirt repellent alkyd paint
US6333378B1 (en) 1997-08-12 2001-12-25 Eastman Chemical Company Acrylic modified waterborne alkyd or uralkyd dispersions
US6242528B1 (en) 1997-08-12 2001-06-05 Eastman Chemical Company Acrylic modified waterborne alkyd dispersions
GB0025213D0 (en) * 2000-10-14 2000-11-29 Avecia Bv Polyester polymer compositions
US6727314B2 (en) 2001-12-13 2004-04-27 Basf Ag Crosslinking systems for acrylic latex films
CN101142263B (zh) * 2005-03-17 2012-10-10 路博润高级材料公司 纳米颗粒/乙烯基聚合物复合材料
ATE529488T1 (de) * 2008-12-29 2011-11-15 Rohm & Haas Hochglänzende emulsionsfarben mit erweitertem alkalyd
US8987346B2 (en) 2013-05-31 2015-03-24 Lion Copolymer Geismar, Llc High solids cross-linked ethylene propylene diene terpolymer latex
US8859638B1 (en) 2013-05-31 2014-10-14 Lion Copolymer Geismar, Llc Method for making a high solids cross-linked ethylene propylene diene terpolymer latex

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1155644A (fr) * 1955-07-15 1958-05-06 Lewis Berger & Sons Ltd Procédé de fabrication d'une résine alkyde pouvant être mise en dispersion dans l'eau
FR1386701A (fr) * 1963-02-12 1965-01-22 Allied Chem Résines alkydes, leur procédé de préparation et peintures émaillées les contenant
FR2253057A1 (en) * 1973-11-30 1975-06-27 Vianova Kunstharz Ag Aq. dispersions of air drying alkyd resins - made using a polyethylene glycol modified alkyd resin as emulsifying agent
DE2622646A1 (de) * 1975-07-30 1977-02-17 Vianova Kunstharz Ag Verfahren zur herstellung von wasseremulgierbaren luft- und ofentrocknenden alkydharzen

Family Cites Families (15)

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Publication number Priority date Publication date Assignee Title
US2634245A (en) * 1950-04-27 1953-04-07 Pittsburgh Plate Glass Co Water dispersible alkyd type resins
US3379548A (en) * 1960-06-02 1968-04-23 Chevron Res Water-dispersible alkyds and alkyd resins
US3297605A (en) * 1961-01-10 1967-01-10 Textron Inc Water dispersible condensation products of a drying oil glyceride ester and a polyethylene glycol
US3438795A (en) 1961-08-10 1969-04-15 Textron Inc Water dispersible composition containing a reaction product of a modified drying oil component and an alkoxy polyalkylene glycol
BE632501A (fr) * 1962-05-18
DE1495031A1 (de) 1962-05-18 1969-01-02 Ashland Oil Inc Verfahren zur Herstellung in Wasser selbst dispergierender oder loeslicher,nicht oxydierender Alkydharze
GB1013933A (en) 1962-06-27 1965-12-22 Berger Jenson & Nicholson Ltd Improvements in or relating to the manufacture of alkyd resins
US3280057A (en) * 1963-02-12 1966-10-18 Allied Chem Water thinned industrial baking enamels comprising an adduct of an alkylene oxide and a polyhydroxy compound containing at least three hydroxyl groups
US3281222A (en) 1963-06-12 1966-10-25 Bell Telephone Labor Inc Activated rosin fluxes and cored solders made therefrom
GB1090593A (en) 1964-03-17 1967-11-08 Ici Ltd New polyesters
US3442835A (en) * 1965-08-19 1969-05-06 Ashland Oil Inc Water-dispersible polyalkylene glycol modified drying oil alkyd
GB1225059A (en) 1967-09-14 1971-03-17 Alba Pinturas Film-forming polyesters
JPS5212217B1 (fr) 1971-04-22 1977-04-05
IT981904B (it) 1973-04-09 1974-10-10 Duco Spa Resine alchidiche all acqua modi ficate con acido acrilico o meta crilico
US4051089A (en) * 1975-04-21 1977-09-27 Mobil Oil Corporation Water reducible short oil alkyd resins and process of making same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1155644A (fr) * 1955-07-15 1958-05-06 Lewis Berger & Sons Ltd Procédé de fabrication d'une résine alkyde pouvant être mise en dispersion dans l'eau
FR1386701A (fr) * 1963-02-12 1965-01-22 Allied Chem Résines alkydes, leur procédé de préparation et peintures émaillées les contenant
FR2253057A1 (en) * 1973-11-30 1975-06-27 Vianova Kunstharz Ag Aq. dispersions of air drying alkyd resins - made using a polyethylene glycol modified alkyd resin as emulsifying agent
DE2622646A1 (de) * 1975-07-30 1977-02-17 Vianova Kunstharz Ag Verfahren zur herstellung von wasseremulgierbaren luft- und ofentrocknenden alkydharzen

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441527A3 (en) * 1990-02-07 1991-11-13 Ici Americas Inc. Stabilized polymer latex composition
WO1992009667A1 (fr) * 1990-11-23 1992-06-11 Berol Nobel Ab Composition aqueuse d'alkydes a sechage par auto-oxydation
US5391649A (en) * 1990-11-23 1995-02-21 Berol Nobel Ab Aqueous, autoxidatively-drying alkyd composition containing polyunsaturated alkanolamide emulsifier
WO2011098584A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Complexe de sels de manganèse servant d'agent de séchage pour des compositions de revêtement
WO2011098587A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Complexe de manganèse servant d'agent de séchage pour des compositions de revêtement
WO2011098583A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Siccatif à base d'un complexe de manganèse pour compositions de revêtement
WO2014014125A1 (fr) * 2012-07-20 2014-01-23 Fujifilm Corporation Procédé de gravure, procédé de production d'un substrat semi-conducteur et dispositif à semi-conducteur l'utilisant
WO2014087418A1 (fr) * 2012-12-05 2014-06-12 Asian Paints Ltd. Dispersions aqueuses d'alkyde acrylé

Also Published As

Publication number Publication date
DK149614B (da) 1986-08-11
DK149614C (da) 1987-01-26
NO782045L (no) 1978-12-14
NL7806349A (nl) 1978-12-15
DE2861047D1 (en) 1981-11-26
ATA430178A (de) 1986-01-15
NO146602B (no) 1982-07-26
FR2394565A1 (fr) 1979-01-12
DE2825894A1 (de) 1978-12-21
NO146602C (no) 1984-04-17
AT381112B (de) 1986-08-25
US4299742A (en) 1981-11-10
EP0000087B1 (fr) 1981-09-09
DK262878A (da) 1978-12-14

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