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WO1995015361A1 - Pigment metallique dispersible dans l'eau - Google Patents

Pigment metallique dispersible dans l'eau Download PDF

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Publication number
WO1995015361A1
WO1995015361A1 PCT/IE1994/000058 IE9400058W WO9515361A1 WO 1995015361 A1 WO1995015361 A1 WO 1995015361A1 IE 9400058 W IE9400058 W IE 9400058W WO 9515361 A1 WO9515361 A1 WO 9515361A1
Authority
WO
WIPO (PCT)
Prior art keywords
metallic pigment
surfactant
composition
pigment composition
water
Prior art date
Application number
PCT/IE1994/000058
Other languages
English (en)
Inventor
Philip Thornton
David Byrne
Sheila Donegan
Original Assignee
Dahlia Ireland Limited
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 Dahlia Ireland Limited filed Critical Dahlia Ireland Limited
Priority to AU11184/95A priority Critical patent/AU1118495A/en
Priority to EP95902257A priority patent/EP0731825A1/fr
Publication of WO1995015361A1 publication Critical patent/WO1995015361A1/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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/644—Aluminium treated with organic compounds, e.g. polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/66—Copper alloys, e.g. bronze
    • 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
    • C09D11/00—Inks
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/006—Metal
    • 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
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the invention relates to water dispersible compositions of metallic pigments.
  • Aluminium pigments are widely used in coatings, particularly in paints and inks.
  • Aluminium pigments are one of the main metallic pigments and are generally bright flake-like particles. In the presence of water however the pigmentation properties of the aluminium particles are destroyed by reaction between water and aluminium producing aluminium hydroxide and hydrogen gas in accordance with the following equation:
  • the hydrated oxide form of aluminium is not suitable for use as a metallic pigment.
  • the hydrogen gas generated by the reaction is a fire and explosion hazard.
  • a water dispersible metallic pigment composition having dispersion and gassing stability comprising a metallic pigment incorporated in an associated surfactant structure formed from surfactant concentrations above the critical micelle concentration.
  • the surfactant structure is a micelle.
  • the surfactant system is a binary system comprising surfactant and water.
  • the surfactant system is a ternary system comprising water, a surfactant and a co-surfactant.
  • the surfactant system has a relatively large micellar region in the water corner of the phase diagram for the surfactant system.
  • the surfactant structure is formed prior to the addition of the metallic pigment.
  • the weight ratio of the metallic pigment to the surfactant structure composition is at least 1:1, most preferably at least 3:1.
  • the metallic pigment includes an organic entity.
  • the organic entity may be a milling aid such as mineral spirits.
  • the organic entity includes a lubricant such as a fatty acid, typically stearic acid or isostearic acid.
  • the metallic pigment is in the form of a filter cake.
  • the metallic pigment is in the form of a paste.
  • the metallic pigment is in the form of flake.
  • the metallic pigment is a leafing metallic pigment.
  • the metallic pigment is a non-leafing metallic pigment.
  • the metallic pigment may be an aluminium pigment or may, for example be a zinc pigment or a gold-bronze pigment.
  • gold-bronze refers to copper or copper alloys, especially copper/zinc, with small amounts of other metals to inhibit oxidation.
  • the surfactant whether in a binary or ternary system may be an ionic surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, a zwitteronic surfactant, or an amphoteric surfactant.
  • co-surfactant may be any suitable hydrocarbon or mixture of hydrocarbons, typically pentanol or an alcohol higher than pentanol.
  • the invention also provides a coating composition comprising a metallic pigment of the invention and an appropriate vehicle.
  • the coating composition may be in the form of an ink, a paint, a water-based acrylic glaze, a water-based alkyd resin, a water-based acrylic melamine, an acrylic latex or the like.
  • the invention further provides a method for preparing a metallic pigment composition of the invention comprising the steps of :
  • This invention is based on the discovery that metallic pigments may be located in a surfactant structure such as the centre of the micelle, thereby preventing interaction with water and the evolution of hydrogen gas.
  • the invention provides a metallic pigment composition which is easily dispersed, and has improved dispersion and gassing stability. Unlike other passivating treatments, if the metallic particle is damaged during processing of the pigment or composition the surfactant structure will form around the newly exposed surface giving continuing protection of the metal particle.
  • a surfactant is a chemical species containing a hydrophillic (water loving) and hydrophobic (water hating) moiety.
  • the hydrophobic portion is normally a long chain hydrocarbon in which length, degree of branching and chemical structure differ from one species to another.
  • the hydrophillic region comprises the headgroup of the surfactant and may be ionic or nonionic depending on the surfactant involved.
  • CMC critical micelle concentration
  • the interior of the micelle is composed of hydrocarbon chains, it resembles a hydrocarbon liquid.
  • material in the interior of the micelle dispersed in the hydrocarbon liquid and protected from the aqueous phase.
  • an associated surfactant structure such as a micelle is used to provide protection to metallic pigments such as aluminium.
  • a surfactant structure such as a micelle is prepared.
  • the metallic pigment is then added to the micellar solution and, preferably, thoroughly mixed to ensure that the pigment particles are wetted out. It is believed that the micelles wet out on the newly introduced surface of the metallic pigment to give an electrostatic and/or steric barrier.
  • these pigments may be in the form of a filter cake.
  • the filter cake is manufactured by milling chopped aluminium foil. The milling is usually carried out in a rotating ball mill using steel balls. Mineral spirits are added to the ball mill as a milling aid. A milling lubricant in the form of stearic acid is also added to the ball mill. After milling, the aluminium slurry is filtered on a filter press to produce filter cake.
  • the filter cake generally comprises 72% to 77% by weight of aluminium, 20% to 25% mineral spirits and 1 to 3% stearic acid.
  • the filter cake may be modified by the addition of further components to form an aluminium paste.
  • Such components may include fatty acid(s) and/or hydrocarbon liquid(s).
  • the fatty acid may be stearic acid and/or the hydrocarbon liquid may be mineral spirits.
  • the filter cake may also be dried to substantially remove the mineral spirits to form an aluminium flake.
  • a micelle is prepared.
  • the micelle in this case is prepared from an anionic surfactant - AOT (Sodium Dioctyl Sulphosuccinate) supplied by Aldrich Chemicals.
  • AOT Sodium Dioctyl Sulphosuccinate
  • the micelle has a micellar composition by weight of 1% AOT and 99% distilled water.
  • micellar composition 20 g of the micellar composition thus formed is placed in a storage jar and 60 g of aluminium filter cake is added to the micellar composition.
  • the micellar composition and aluminium filter cake are mixed together on a high speed vortex mixer for about 5 minutes to form the micelle shielded -aluminium paste (MSAP) .
  • MSAP micelle shielded -aluminium paste
  • Example A was repeated by first preparing a micelle having a micellar composition by weight of 20% SDS and 80% distilled water.
  • Sodium dodecyl sulphate (SDS) is an anionic surfactant which in this case was from Aldrich Chemicals and had a purity of not less than 99%.
  • a micelle shielded aluminivun paste (MSAP) was then prepared as outlined in Example A using the micellar composition described above.
  • Example A was repeated by first preparing a micelle having a micellar composition by weight of 25% TRITON X100 and 75% distilled water.
  • TRITON X100 is a non-ionic surfactant available from Union Carbide.
  • EXAMPLE D - Ink/Paints
  • Example A 50 g of the MSAP prepared in accordance with Example A is placed in a clean beaker and to it is added 10 g of distilled water. This is mixed into a slurry. 40 g of a vehicle is added to the beaker and the slurry is again mixed by hand until a smooth mixture is obtained. A final
  • the viscosity of the ink/paint system is measured and if required the ink/paint viscosity is adjusted to 30 - 50 seconds using a Zahn 2 cup using a 50/50 w/w IPA
  • a test apparatus 1 used for room temperature stability tests comprises a storage jar 2, typically of 120 mis capacity, closed by a lid 3 having a central hole 4.
  • the lid 3 is in this case of 40 mm diameter and the hole 4 is of 10 mm diameter.
  • a sample of ink is made up using the MSAP of Example A and vehicle for room temperature storage only. 10 g MSAP is placed into the storage jar 2 and to it added 2 g of distilled water which is then mixed into a slurry. 8 g of vehicle is added and mixed in with a spatula to form a smooth mixture. A final 20 g of vehicle is added and stirred in thoroughly by hand to form the ink.
  • the impermeable plastic film 5 is placed over the top of the storage jar 2 and pulled taut.
  • the lid 3 with the hole 4 in it is then placed over the plastic film 5 and screwed on securely. This sample is then weighed and placed on a shelf in the laboratory to be checked weekly for gas production. If gas is produced then a bubble forms in the plastic film 5. The sample is reweighed at the end of each test period to check for weight loss.
  • a test apparatus 10 for carrying out a gassing stability test comprises a gas washing bottle 11 which is typically filled to a level L with a base coat.
  • An extension 12 is fitted to the bottle 11.
  • the extension 12 includes a lower floor 13 and an upper floor 14.
  • a first pipe 15A communicates between the bottle 11 and the head space above the lower floor 13.
  • a second pipe 15B communicates between a lower chamber CL above the floor 13 and an upper chamber CU above the upper floor 14.
  • a stopper 16 is used to close the extension 12.
  • a side leg 17 projecting from the extension 12 is closed by a screw cap 18.
  • Each stability test is allowed to produce ⁇ 25 mis of water in the upper chamber CU during the 30 day test period. At the end of the test period the vessel is reweighed to check for weight loss.
  • Aerosol OT (AOT) micelle was prepared by weighing 1 g AOT and adding 99 g distilled water in a suitable container. This was stirred until a completely clear solution was obtained and knowing that the surfactant concentration is above the CMC this clarity confirms the presence of a micelle structure.
  • micellar solution 20 g was placed into a container and to it 60 g of aluminium filter cake was added. This was mixed together on a high speed vortex mixer for approximately 5 minutes. 50 g of the above paste was placed into a clean beaker and to it 10 g of distilled water was added and this was mixed by hand into a slurry. 40 g of Carboset GA 1594 (B F Goodrich) was added to the beaker and the slurry further mixed by hand until a smooth mixture was obtained. A final 100 g of Carboset GA 1594 was added and the mixture was then stirred on an electric stirrer for 0.5 hours at ⁇ 200 rpm.
  • Carboset GA 1594 B F Goodrich
  • the viscosity of the system was measured using a Zahn 2 cup and found to be between the required 30 - 50 seconds. If the viscosity is outside the 30 - 50 seconds range it must be adjusted using a 50/50 w/w IPA/water solution.
  • Example No. 1 from Table. 1.
  • the ink/paint systems described below were all prepared in a similar manner.
  • Aluminium ink/paint systems based on micelle A 1% AOT / 99% H z O
  • Example A which demonstrated gassing stability over a three month period at room temperature.
  • Al ink with an MSAP containing 1:10 micelle A aluminium pigment and pH adjusted water.
  • the main variant in this table is the type of resin used in the systems. All the above MSAPs are based on aluminium pigment 210NA - refer to Table 11. Explanatory Notes
  • Carboset GA 1594 is a commercial vehicle supplied by BF Goodrich.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • Zinchem 146 is a commercial vehicle supplied by E.H. Worlee & Co. (UK) Ltd.
  • Zinpol 146 is a commercial vehicle supplied by E.H. Worlee & Co. (UK) Ltd.
  • Worleecryl 8410 is a commercial vehicle supplied by E.H. Worlee & Co (UK) Ltd.
  • Neocryl BT-20 is a commercial vehicle supplied by Zeneca Resins.
  • Neocryl BT-44 is a commercial vehicle supplied by Zeneca Resins.
  • Morcryl 1503 is a commercial vehicle supplied by Morton International Ltd.
  • Zinpol 132 is a commercial vehicle supplied by E.H. Worle ⁇ & Co. (UK) Ltd.
  • Silres MP42E is a commercial vehicle supplied by Wacker Chemicals. TABLE 2
  • Aluminium ink/paint systems based on micelle A (1% AOT / 99% H-,0) - Example A & different aluminium pigments, which demonstrated gassing stability over a three month period at room temperature.
  • the main variant in this table is the type of aluminium pigment used in the systems. Details of the various aluminium pigments are given in Table 11. Explanatory Notes :
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • pH adjusted water is adjusted to a pH of ⁇ 8.00.
  • the main variant in the above table is the type of resin used in the systems. All the above MSAPs are based on aluminium pigment 210NA - see Table 11.
  • Silres MP42E is a commercial vehicle supplied by Wacker Chemicals.
  • Carboset GA 1594 is a commercial vehicle supplied by BF Goodrich.
  • Zinchem 146 is a commercial vehicle supplied by E.H. Worlee & Co. (UK) Ltd.
  • Morcryl 1503 is a commercial vehicle by Morton International Ltd.
  • the main variant is the type of aluminium pigment used in the systems. Details of the various aluminium pigments are given in Table 11.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • pH adjusted water is adjusted to a pH of ⁇ 8.00.
  • Aluminium ink/paint systems based on micelle C (25% TX-100 / 75% H 2 0) - Example C above which demonstrated gassing stability over a 3 month period at room temperature.
  • the main variant in the above table is the type of resin used in the systems. All the above MSAPs are based on aluminium pigment 210NA - Table 11.
  • Silres MP42E is a commercial vehicle supplied by Wacker Chemicals.
  • Zinchem 146 is a commercial vehicle supplied by E.H. Worlee & Co. (UK) Limited.
  • Morcryl 1503 is a commercial vehicle supplied by Morton International Limited.
  • Neocryl W-1200 is a commercial vehicle supplied by Zeneca Resins.
  • Neocryl BT-20 is a commercial vehicle supplied by Zeneca Resins.
  • Zinpol 146 is a commercial vehicle supplied by E. H. Worlee & Co. (UK) Limited.
  • the main variant in the above table is the filter cake used in the systems. Details of the various aluminium pigments are given in Table 11. Explanatory notes.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • pH adjusted water is adjusted to a pH of ⁇ 8.00. Aluminium ink/paint systems with different micelles which demonstrated gassing stability over a 6 month period at room temperature.
  • Aluminium ink with an MSAP containing 1:2 micelle B aluminium pigment & pH adjusted water 1 .
  • the main variant in the above 3 tables is the type of resin used in the systems. All the above MSAPs are based on filter cake 210NA.
  • Zinchem 146 is a commercial vehicle supplied by E.H. Worle ⁇ & Co. (UK) Ltd.
  • Zinpol 146 is a commercial surfactant supplied by E.H. Worlee & Co. (UK) Ltd.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • Carboset GA 1594 is a commercial vehicle supplied by BF Goodrich.
  • Aluminium ink with an MSAP containing 20% Phospholan PNP9 and 1 Joncryl 1536 2 .
  • Aluminium ink with an MSAP containing 1% Sellogen HR 9 and pH adjusted water 3 100. Aluminium ink with an MSAP containing 1% Sellogen HR 9 and pH adjusted water 3 .
  • micellar composition used in the systems. All the above MSAPs are based on aluminium pigment 210NA. Explanatory notes.
  • Sellogen DFL is an anionic surfactant supplied by Henkel Performance Chemicals.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • pH adjusted water is adjusted to a pH of ⁇ 8.00.
  • Lucidene 202 is a commercial vehicle supplied by Morton International Ltd.
  • SDS (at least 99% pure) is an anionic surfactant supplied by Aldrich Chemical Co.
  • CTAB is a cationic surfactant supplied by Aldrich Chemical Co.
  • Tego Betain HS is a zwitterionic surfactant supplied by T.H. Goldscbmidt A.G..
  • Phospholan PNP9 is an anionic surfactant supplied by Harcross Chemicals (UK) Ltd.
  • Sellogen HR is an anionic surfactant supplied by Henkel Performance Chemicals.
  • Tego Betain F is a zwitterionic surfactant supplied by T.H. Goldschmidt AG.
  • composition of the various aluminium pigments filter cakes; pastes; and flakes
  • Aluminium Paste Non-Leafing in Isopropyl Alcohol manufactured by U.S. Aluminum Inc.
  • This system is on test at room temperature for almost three months and is passing the test.
  • Atlox 5320 is a commercial surfactant mix supplied by I.C.I. Surfactants.
  • Example 109 See also Tahlg 1 Example 7 for room t-f»mpf» ⁇ ature result
  • the solids content is 40% in water. It has excellent wetting properties, dries fast, excellent gloss, a low minimum film forming temperature (MFFT) and is thus highly flexible. It has excellent adhesion on various substrates. It has FDA approval, which makes it highly appropriate for use. It is claimed to be stable for a minimum of 30 days at 50°C and is designed for use in aqueous flexographic and gravure inks and overlay or overprint varnishes. It is also claimed to have been designed for use with metallic systems. For use, it must be reduced to 20-25% solids with water and must also be neutralised with ammonia to obtain a clear solution of medium viscosity with a pH of 7.5-8.0.
  • Example 110 (see also Tab1p> 1 f F.xample 10 for room temperature result)
  • Average number of mis of hydrogen produced over the 30 day test period 5.6 mis.
  • Neocryl W-1200 Zaeneca Resins
  • the main properties of this resin are as follows :
  • Neocryl W1200 has been developed for flexo printing inks on paper and cartons. It may also be used in temporary coatings and screen printing inks.
  • Example 112 (see also Table 1 Example 12 for room temperature result)
  • Zinpol 132 (Worlee Chemicals) This resin is a styrene acrylic emulsion, supplied at 40% solids in water. It is designed specifically for use with aluminiu and bronze powders. Due to this, it gives excellent metallic ink brilliance, with excellent ink stability on storage and shipping. It can be used for both flexo and gravure printing. It is reportedly stable at 40°C for 30 days. It has FDA approval from the following chapters : 175.105, 175.300, 175.320, 176,1700 and 176.180.
  • Average number of mis of hydrogen produced over the 30 day test period 12.5 mis.
  • a heat resistant water dilutable aluminium coating according to the following formulation was produced.
  • the paint was prepared using the following Micelle Shielded Aluminium Pastes (MSAP) :
  • the aluminium paste was stirred slowly with the HDK N20 into the emulsion MP42E.
  • the Silicon resin MP 42E was a shear stable, non ionically stabilised, storage stable aqueous emulsion of a medium-hard methylphenyl silicone resin, which dries tack free at room temperature. It has a low solvent content (7% xylene) which gives environmentally friendly coatings. Depending on pigmentation, temperature resistant and temperature shock- resistant coatings up to 650°C can be produced. It can be used in a wide variety of applications including the automotive industry for exhaust coatings and in industrial and chemical plants .
  • the paint prepared using the above formulation was subjected to the 40°C stability test as described in Test 2.
  • Paint based on (a) Average number of mis of hydrogen produced over the 30 day test period : 10 mis. Paint based on (b) : Average number of mis of hydrogen produced over the 30 day test period : 21.6 mis.
  • Both paints based on (a) and (b) are stable at room temperature for more than 6 months.
  • phase diagrams are included for illustrative purposes.
  • Fig. 3 is the phase diagram for the surfactant system sodium dodecyl sulphate (SDS)/water/pentanol (after Prof. S.E. Freiberg, Clarkson University, Potsdam, New York, U.S.A.)
  • SDS sodium dodecyl sulphate
  • Fig. 4 is the phase diagram for the surfactant system TRITON XlOO/water/pentanol.
  • Example A a micelle was prepared as described in Example A except that a co-surfactant was also added.
  • a micelle shielded aluminium paste was prepared as described in Example B and an Ink/Paint was prepared as described in Example D.
  • micellar systems were subjected to the 40°C stability test described in Test 2 above and remained stable after 30 days - see Table 12.
  • Table 13 • Ternary micellar systems which remained stable after 3 months at room temperature.
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Jonson Polymer.
  • Brij 96 is a non-ionic commercial surfactant supplied by ICI Surfactants.
  • CTAB Cetyltrimethylammomumbromide, a cationic surfactant supplied by Aldrich Chemical Co.
  • the alkyd resin chosen was Uradil XP 516 AZ (DSM Resins). It is composed of a long oil alkyd emulsion with an oil length of 63%. It is 60% solids in water and is amine free. It has a pH of 4.0, which was adjusted to pH 8 before use. Its main properties are good air drying, good gloss and excellent penetration/adhesion.
  • the exact amount of associated surfactant structure required to impart gassing stability to the aluminium pigment is difficult to calculate for the following reasons.
  • the packing and packing density of each surfactant is particular to that surfactant.
  • the packing efficiency of the surfactant will depend upon a number of factors including the size of the headgroup, the presence of multiple tail groups, aromatic structures in the tail group, the presence of unsaturation in the tail group, electrostatic interaction between the headgroups, the nature of the metallic surface to be covered and the formation of duplex layers.
  • micellar solution aluminium pigment content of 2:1 w/w using an SDS/Pentanol/Water (17%/13%/70%) micelle in both Joncryl 1536 and pH water have passed the three month room temperature stability test.
  • SDS/Pentanol/Water (17%/13%/70%) micelle in both Joncryl 1536 and pH water have passed the three month room temperature stability test.
  • other surfactants may give stable systems at even lower aluminium pigment concentration.
  • Example 2 Using the method of Example 1 above, two zinc paints were prepared using Micelle A - 1% AOT, 99% H 2 0 and Micelle B - 20% SDS 80% H z 0.
  • a micellar system in which zinc pigment was vortexed with the micelle to give a zinc paste.
  • a zinc pigment was used, namely : Larvik Zinc dust. Brand STD 7, sample no. 203.
  • a blank zinc paint was also prepared in which there was no micelle present. The samples were thickened by the addition of 1.5% Hydroxy ethyl cellulose (w/w based on the final formulation) .
  • Test 2 Using Test 2 above the following results were obtained. - 31 -
  • the presence of the micelle protects the zinc pigment from attack by water as seen by the reduction of hydrogen evolution in the presence of the micelle.
  • the protection offered by the micelle is sufficient to indicate a positive result, based on the limit of hydrogen evolution of 25 mis at 40°C for 30 days.
  • Gold bronze pigments are typically copper or copper alloys, usually copper/zinc, with small amounts of other metals to inhibit oxidation. They are produced by the attrition of finely divided, usually atomised, metal particles by mechanical means, usually ball milling, into platelet type structures. A lubricant, usually a saturated fatty acid, is added to assist the attrition, prevent cold welding of the particles and provide leafing.
  • micellar solutions were prepared :-
  • micellar solution 17.5 g micellar solution
  • a sample of ink is made up of using the above micelle shielded paste and vehicle for room temperature storage only.
  • 5g micelle shielded paste is placed into a storage jar and to it is added lg of distilled water which is then mixed into a slurry.
  • 4g of vehicle is added and mixed in with a spatula to form a smooth mixture.
  • a final lOg of vehicle is added and stirred in thoroughly by hand to form the ink.
  • a piece of impermeable film is placed over the top of the storage jar and pulled taut.
  • a lid is then placed over the film and screwed on securely.
  • This sample is then weighed and placed on a shelf in the laboratory to be checked weekly for discoloration, this usually appears as a blue/green discoloration. If there is no discoloration the sample is kept on test for a further period. The sample is reweighed at the end of each test period to check for weight loss.
  • SDS (at least 99% pure) is sodium dodecyl sulphate supplied by Aldrich Chemical.
  • AOT is sodium dioctyl sulphosuccinate supplied by Aldrich Chemical Co.
  • Joncryl 1536 is a commercial vehicle supplied by S.C.
  • Gold bronze ink systems based on pastes made using micelle (a) and (b) above which exhibited no discoloration over a 3 month period at room temperature. - 34 -
  • Joncryl 1536 is a commercial vehicle supplied by S.C. Johnson Polymer.
  • Zinchem 146 is a commercial vehicle supplied by E.H. Worlee & Co. (UK) Ltd.
  • Lucidene 202 is a commercial vehicle supplied by Morton International Limited.
  • pH adjusted water is adjusted to a pH of ⁇ 8.00.
  • the surfactant structure may be a lyotropic liquid crystal structure.
  • Such a structure is formed by the addition of solvent to concentrated surfactant systems.
  • Fig. 5 is a phase diagram illustrating where different phases are normally found. The examples described above are within the L ! and D phases which are single phase associated surfactant systems.
  • Liquid crystals or mesophases are states of matter in between liquids and crystalline solids. In these systems there is long range order but not short range order.
  • the lamellar liquid crystal has a semi liquid and mucous consistency. They are optically anisotropic, when viewed between cross polars, they shine. Microscopic examination shows both planar and mosaic (Maltese crosses) pattern.
  • Hexagonal structures are the second most common type of liquid crystals. There are two types - normal and reverse. Low angle X-ray diffraction patterns have shown these structures to be composed of long cylindrical micelles packed in a hexagonal array, where the polar groups occupy the cylinder surfaces. The cylinders are separated by a continuous water environment. In the reverse hexagonal phase, the hydrocarbon tails occupy the spaces between the hexagonally packed water molecules.
  • This liquid crystal is very stiff. It is fairly transparent and is anisotropic. Microscopy studies between polaroid plates have shown a very angular structure.
  • the first group l or I 2 consists of close packed spherical micelles. Both body centred and face centred - 37 -
  • the second group of cubic phases (Vj and V 2 ) consists of interdispersed 3-D networks of water and surfactants. They are bicontinuous, in that both water and surfactant form separate continuous regions.
  • cubic phase is very stiff gel, which is transparent and shows no birefringence.
  • the surface tension of the surfactant solutions was measured by the du Nouy tensiometer ring method using a torsion balance from Whites Electrical Co.
  • the force needed to detach a ring from an interface is measured by suspending the ring using a torsion wire arrangement.
  • the detachment force is related to the surface tension by the following equation :
  • dynes/cm PF where P is the scale reading in dynes per cm when the film breaks, and F is the correction factor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)

Abstract

Composition à pigment métallique dispersible dans l'eau, comportant un pigment métallique tel qu'un pigment d'aluminium incorporé à une structure tensioactive associée telle qu'une micelle. La micelle est formée à partir de concentrations de tensioactif supérieures à la concentration critique en micelles. Le système tensioactif peut être un système à deux constituants comportant un tensioactif et de l'eau, ou un système à trois constituants comprenant également un cotensioactif. La structure tensioactive est formée avant l'adjonction du pigment métallique. Le pigment métallique peut comprendre un agent facilitant le broyage, par exemple du white-spirit et/ou un lubrifiant tel que l'acide stéarique. Cette composition à pigment métallique est facilement dispersible et présente une stabilité améliorée à la dispersion et au dégagement de gaz. On a également prévu différentes compositions de revêtement renfermant cette composition à pigment métallique
PCT/IE1994/000058 1993-12-01 1994-11-30 Pigment metallique dispersible dans l'eau WO1995015361A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU11184/95A AU1118495A (en) 1993-12-01 1994-11-30 Water dispersible metallic pigment
EP95902257A EP0731825A1 (fr) 1993-12-01 1994-11-30 Pigment metallique dispersible dans l'eau

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IE930929 1993-12-01
IE930929 1993-12-01

Publications (1)

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WO1995015361A1 true WO1995015361A1 (fr) 1995-06-08

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0974628A3 (fr) * 1998-05-29 2001-08-22 SESTRIERE VERNICI S.r.l. Pâtes universelles pigmentées, dispersibles dans l'eau, sans substance organique volatile
WO2002053658A3 (fr) * 2001-01-04 2002-09-12 Basf Coatings Ag Materiau de revetement a effet, aqueux, son procede de production et son utilisation
US6599353B2 (en) 2000-04-20 2003-07-29 Berol Corporation Shear-thinning writing compositions, writing instruments, and methods
US6986809B2 (en) 2000-07-03 2006-01-17 Berol Corporation Erasable inks, writing instruments, and methods
JP2020105338A (ja) * 2018-12-27 2020-07-09 堺化学工業株式会社 鱗片状亜鉛末の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1191205A (en) * 1967-05-09 1970-05-13 Showa Aluminium Powder Co Ltd Metallic Composition
JPS51119724A (en) * 1975-04-14 1976-10-20 Toyo Alum Kk Water-dispersible, metal pigment composition
FR2354300A1 (fr) * 1976-06-08 1978-01-06 Asahi Chemical Ind Composition aqueuse a base d'aluminium formant pate
JPS5516036A (en) * 1978-07-22 1980-02-04 Nippon Oil & Fats Co Ltd Water-dispersible metal composition
JPS57167361A (en) * 1981-04-09 1982-10-15 Dainippon Toryo Co Ltd Preparation of scaly aluminum paste pigment for water paint
DD258954A1 (de) * 1985-09-18 1988-08-10 Allami Penzveroe Verfahren zur herstellung von plaettchenfoermigen silberpigmenten mit aktiver oberflaeche zur elektronischen anwendung
US4884754A (en) * 1989-01-03 1989-12-05 Gte Products Corporation Process for producing fine copper flakes
US4976777A (en) * 1988-09-09 1990-12-11 Showa Alumi Powder Kabushiki Kaisha Metal powder having controlled particle size distribution for metallic pigments and process for producing the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1191205A (en) * 1967-05-09 1970-05-13 Showa Aluminium Powder Co Ltd Metallic Composition
JPS51119724A (en) * 1975-04-14 1976-10-20 Toyo Alum Kk Water-dispersible, metal pigment composition
FR2354300A1 (fr) * 1976-06-08 1978-01-06 Asahi Chemical Ind Composition aqueuse a base d'aluminium formant pate
JPS5516036A (en) * 1978-07-22 1980-02-04 Nippon Oil & Fats Co Ltd Water-dispersible metal composition
JPS57167361A (en) * 1981-04-09 1982-10-15 Dainippon Toryo Co Ltd Preparation of scaly aluminum paste pigment for water paint
DD258954A1 (de) * 1985-09-18 1988-08-10 Allami Penzveroe Verfahren zur herstellung von plaettchenfoermigen silberpigmenten mit aktiver oberflaeche zur elektronischen anwendung
US4976777A (en) * 1988-09-09 1990-12-11 Showa Alumi Powder Kabushiki Kaisha Metal powder having controlled particle size distribution for metallic pigments and process for producing the same
US4884754A (en) * 1989-01-03 1989-12-05 Gte Products Corporation Process for producing fine copper flakes

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 1180, Derwent World Patents Index; AN 80-19430C *
DATABASE WPI Week 4377, Derwent World Patents Index; AN 77-76987Y *
DATABASE WPI Week 4782, Derwent World Patents Index; AN 82-00911J *
DATABASE WPI Week 4976, Derwent World Patents Index; AN 76-91393X *
DATABASE WPI Week 4988, Derwent World Patents Index; AN 88-346653 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0974628A3 (fr) * 1998-05-29 2001-08-22 SESTRIERE VERNICI S.r.l. Pâtes universelles pigmentées, dispersibles dans l'eau, sans substance organique volatile
US6599353B2 (en) 2000-04-20 2003-07-29 Berol Corporation Shear-thinning writing compositions, writing instruments, and methods
US6986809B2 (en) 2000-07-03 2006-01-17 Berol Corporation Erasable inks, writing instruments, and methods
WO2002053658A3 (fr) * 2001-01-04 2002-09-12 Basf Coatings Ag Materiau de revetement a effet, aqueux, son procede de production et son utilisation
JP2020105338A (ja) * 2018-12-27 2020-07-09 堺化学工業株式会社 鱗片状亜鉛末の製造方法

Also Published As

Publication number Publication date
AU1118495A (en) 1995-06-19
EP0731825A1 (fr) 1996-09-18

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