EP0563183A4 - - Google Patents

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Publication number
EP0563183A4
EP0563183A4 EP19920901759 EP92901759A EP0563183A4 EP 0563183 A4 EP0563183 A4 EP 0563183A4 EP 19920901759 EP19920901759 EP 19920901759 EP 92901759 A EP92901759 A EP 92901759A EP 0563183 A4 EP0563183 A4 EP 0563183A4
Authority
EP
European Patent Office
Prior art keywords
water
minutes
weight
paint
petroleum
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Withdrawn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
EP19920901759
Other languages
French (fr)
Other versions
EP0563183A1 (en
Inventor
Bassam Shomali
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.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0563183A1 publication Critical patent/EP0563183A1/en
Publication of EP0563183A4 publication Critical patent/EP0563183A4/en
Withdrawn legal-status Critical Current

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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
    • C09D15/00—Woodstains
    • 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

Definitions

  • This invention relates to paint and stain formulations, in particular to paint formulations including petroleum-derived oils especially re-refined petroleum-derived oils.
  • Paints are liquids that solidify when exposed to air and are used to cover surfaces for decorative and protective purposes.
  • paints are formed by mixing a pigment and a liquid vehicle that solidifies when exposed to air and a solvent.
  • paint formulations consist of different categories of chemical compounds.
  • the vehicle ultimately forms the adherent, flexible, skin-like coating.
  • the pigment is dispersed throughout the vehicle and gives the final film its colour and hiding power.
  • the vehicle generally may be an unsaturated, or drying, oil, which is an ester formed from the reaction of a long-chain carboxylic acid, for example, linoleic acid, with a polyfunctional alcohol, such as glycerine; or it can be a synthetic polymer.
  • a long-chain carboxylic acid for example, linoleic acid
  • a polyfunctional alcohol such as glycerine
  • Linseed oil is a typical drying vehicle used in paints. On exposure to the oxygen in the ambient atmosphere, the unsaturated bonds of the hydrocarbon chain of the ester molecules making up linseed oil are attacked and an oxide, or ether, is formed thereby cross-linking one molecule to another. This results in a tough, insoluble macro molecule which becomes a polymer after being applied to an exposed surface.
  • the vehicle may also be a synthetic polymer, dissolved or dispersed in a suitable solvent, so that as the solvent evaporates the individual macro molecules come into contact and become enmeshed with one another.
  • the solidification may be improved by the presence in the solvent of a polymerisation catalyst, called a drier.
  • a polymerisation catalyst called a drier.
  • the types of synthetic polymers most widely employed as paint vehicles are alkyd resins, nitro ⁇ cellulose (in which cellulose is de-polymerised and the small molecules are nitrated, and the substance is then re- polymerised), phenolic resins, acrylic resins, epoxy resins, polyvinyl acetate resins, and polyurethanes.
  • Paint pigments are generally fine powders that either strongly scatter light, to yield a white effect or absorb certain wavelengths of light, producing a coloured effect.
  • Typical white pigments are inorganic oxides such as titanium dioxide, antimony oxide, and zinc oxide. Other white, insoluble, inorganic compounds may also be used. Coloured inorganic oxides may be used as coloured pigments as may a variety of organic solids.
  • the solvent or thinner for the drying oil paints is generally turpentine, which is a mixture of cyclic hydrocarbons containing ten carbon atoms, or the thinner may be mixture of suitably volatile hydrocarbons derived from petroleum distillates.
  • the solvent for most synthetic vehicles is generally a mixture of hydrocarbons, alcohols, ketones, or esters.
  • the non ⁇ volatile and non-drying solvent be absorbed by the substrate within a time short enough to resist wash-off by rain, say within 3 to 4 hours of the product being applied; the residual part of the paint product must stay in place and dry in the same or similar manner as a normal oil or alkyd paint and must have reasonable durability; a single applied coat should be sufficiently opaque to hide surface defects such as gum veins, iron stains, knots etc. as well as colour variations due to different stages of weathering; the product in the container must be readily reincorporated after storage and transport and retain a reasonable uniformity during use; advantageously, the cost of raw materials should be as low as possible to enable the product to compete in the existing market now dominated by water-borne fence finishes.
  • an alkyd resin-containing paint or stain formulation which comprises from 1 to 52.5% by weight of petroleum-derived oil, from 5 to 30% weight (solids) of alkyd resin vehicle, from 1 to 20% by weight of pigment(s), from 15 to 40% by weight of conventional paint solvent(s), if desired, from 10-20% by weight of gloss control agent, and optionally additives as normally used in paint or stain formulations.
  • the present invention provides a water-based alkyd resin-containing paint or stain formulation which comprises:- from 1 to 30% by weight of petroleum-derived oil, from 5 to 30% by weight (solids) of alkyd resin vehicle, from 0 to 20% by weight of pigments, from 0.5 to 10% by weight of emulsifier, balance water, and optionally additives as normally used in water-based paint or stain formulations.
  • the present invention provides a water- based petroleum-derived oil emulsion which comprises:- from 1 to 30% by weight of petroleum-derived oil, from 5 to 30% by weight (solids) of alkyd resin vehicle, from 0.5 to 10% by weight of emulsifier, balance water, and if desired, drying additives.
  • the present invention provides several methods of making a water-based alkyd resin-containing petroleum-derived oil emulsion.
  • Formulations according to the present invention include fence stains, surface paints for bare timber surfaces, or timber preservatives, with the natures and amounts of components being varied to meet requirements. Stain formulations will normally use a lower percentage of pigments than paint formulations.
  • formulations according to the present invention may have flash points significantly higher than known oil-based paints and stains.
  • the non-water based formulations according to the invention contain in excess of 30% by volume of petroleum- derived oil or recycled oil ("RBO").
  • petroleum-derived oil is meant an oil derived from petroleum which is generally useful for producing lubricants. This definition and the limitations on quantities present does not exclude the presence of other petroleum-derived products used for purposes such as thinning.
  • RBO used petroleum-derived oil which has been re- refined by:-
  • a typical RBO has the characteristics:-
  • the type of alkyd used according to the invention is preferably a long oil alkyd based on soybean oil.
  • the oil length is preferably from 50 to 90%.
  • References in the Examples to quantity of alkyd used refer: in the case of oil-based formulations to alkyd by itself; and in the case of water-based formulations to about one part alkyd resin solids to two parts latex resin solids, such latex resins being those conventionally used in the paint industry.
  • the emulsifiers used according to the invention are preferably ethylene oxide propylene oxide block copolymers or nonyl phenol ethylene oxide surfactants.
  • the R.B.O. emulsion is stabilised further using water soluble thickener.
  • Non-limiting examples of oil-based formulations according to the present invention include fence stains as follows:-
  • the alkyd resin used was a long-chain alkyd resin being 63% semi- drying oil penta alkyd with a 70% solids content in a high boiling hydrocarbon solvent, having a flash point above 61°C. Other alkyd resins may be used in substitution thereof.
  • the drier mixture used in the formulation was prepared from three driers as follows:
  • the metal content of the preceding four formulations, based on the alkyd oil was calculated to be: lead - 0.8%; cobalt - 0.1%; manganese - 0.1%;. These levels are typical for dark colour stains.
  • Exkin No. 2 methyl ethyl ketoxime is an anti-skinning agent used to promote stability of the formulations during storage and transport. Other similar anti-skinning agents may be substituted.
  • the method of preparation was essentially the same as for the MISSION BROWN Stain.
  • Water-based products according to the invention may be made in three steps:-
  • the vehicle is mixed with petroleum-derived or recycled petroleum-derived oil in the presence of an emulsifier
  • step 1 is emulsified with water
  • the emulsion is mixed with further water and filler and, if desired, pigments.
  • Bevaloid 643 .080g Bevaloid
  • Examples 13 to 17 illustrate a two-step process for making water- based products according to the invention:
  • This recipe is designed to check the effect of R.B.O. emulsion on colour, drying, hardness and enamel recoatability of gloss 100% acrylic.
  • the R.B.O. Emulsion was made by mixing:
  • Latex 50% non-volatile 280.0

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

An oil or water based alkyl resin-containing paint or stain formulation which comprises: from 1-52.5 % by weight of petroleum-derived oil; from 5-30 % by weight (solids) of alkyl resin vehicle; from 0-20 % by weight of pigment(s); other conventional additives.

Description

TITLE; Paint and Stain Formulations
FIELD OF THE INVENTION: This invention relates to paint and stain formulations, in particular to paint formulations including petroleum-derived oils especially re-refined petroleum-derived oils.
BACKGROUND OF THE INVENTION: Paints are liquids that solidify when exposed to air and are used to cover surfaces for decorative and protective purposes. In general, paints are formed by mixing a pigment and a liquid vehicle that solidifies when exposed to air and a solvent. In general modern paint formulations consist of different categories of chemical compounds. The vehicle ultimately forms the adherent, flexible, skin-like coating. The pigment is dispersed throughout the vehicle and gives the final film its colour and hiding power. The solvent, or thinner, evaporates shortly after the coating has been applied. The vehicle generally may be an unsaturated, or drying, oil, which is an ester formed from the reaction of a long-chain carboxylic acid, for example, linoleic acid, with a polyfunctional alcohol, such as glycerine; or it can be a synthetic polymer.
Linseed oil is a typical drying vehicle used in paints. On exposure to the oxygen in the ambient atmosphere, the unsaturated bonds of the hydrocarbon chain of the ester molecules making up linseed oil are attacked and an oxide, or ether, is formed thereby cross-linking one molecule to another. This results in a tough, insoluble macro molecule which becomes a polymer after being applied to an exposed surface.
The vehicle may also be a synthetic polymer, dissolved or dispersed in a suitable solvent, so that as the solvent evaporates the individual macro molecules come into contact and become enmeshed with one another. The solidification may be improved by the presence in the solvent of a polymerisation catalyst, called a drier. The types of synthetic polymers most widely employed as paint vehicles are alkyd resins, nitro¬ cellulose (in which cellulose is de-polymerised and the small molecules are nitrated, and the substance is then re- polymerised), phenolic resins, acrylic resins, epoxy resins, polyvinyl acetate resins, and polyurethanes.
Paint pigments are generally fine powders that either strongly scatter light, to yield a white effect or absorb certain wavelengths of light, producing a coloured effect.
Typical white pigments are inorganic oxides such as titanium dioxide, antimony oxide, and zinc oxide. Other white, insoluble, inorganic compounds may also be used. Coloured inorganic oxides may be used as coloured pigments as may a variety of organic solids.
The solvent or thinner for the drying oil paints is generally turpentine, which is a mixture of cyclic hydrocarbons containing ten carbon atoms, or the thinner may be mixture of suitably volatile hydrocarbons derived from petroleum distillates. The solvent for most synthetic vehicles is generally a mixture of hydrocarbons, alcohols, ketones, or esters.
Conventionally, it has been not considered possible to use petroleum-derived oils as solvent replacers or substitutes in paints because those oils are not drying oils. Further, problems of separation of phases have also arisen.
In painting surfaces or substrates it is desirable that the non¬ volatile and non-drying solvent be absorbed by the substrate within a time short enough to resist wash-off by rain, say within 3 to 4 hours of the product being applied; the residual part of the paint product must stay in place and dry in the same or similar manner as a normal oil or alkyd paint and must have reasonable durability; a single applied coat should be sufficiently opaque to hide surface defects such as gum veins, iron stains, knots etc. as well as colour variations due to different stages of weathering; the product in the container must be readily reincorporated after storage and transport and retain a reasonable uniformity during use; advantageously, the cost of raw materials should be as low as possible to enable the product to compete in the existing market now dominated by water-borne fence finishes.
It would also be desirable to produce a formulation which not only incorporates mineral or petroleum oils but is water-based. BRIEF SUMMARY OF THE INVENTION:
Surprisingly, it has been found possible to prepare satisfactory paint or stain formulations incorporating up to 52.5% by weight (or 60% by volume) of petroleum-derived oil.
Thus according to one aspect of the present invention there is provided an alkyd resin-containing paint or stain formulation which comprises from 1 to 52.5% by weight of petroleum-derived oil, from 5 to 30% weight (solids) of alkyd resin vehicle, from 1 to 20% by weight of pigment(s), from 15 to 40% by weight of conventional paint solvent(s), if desired, from 10-20% by weight of gloss control agent, and optionally additives as normally used in paint or stain formulations.
In another aspect the present invention provides a water-based alkyd resin-containing paint or stain formulation which comprises:- from 1 to 30% by weight of petroleum-derived oil, from 5 to 30% by weight (solids) of alkyd resin vehicle, from 0 to 20% by weight of pigments, from 0.5 to 10% by weight of emulsifier, balance water, and optionally additives as normally used in water-based paint or stain formulations.
In yet another aspect the present invention provides a water- based petroleum-derived oil emulsion which comprises:- from 1 to 30% by weight of petroleum-derived oil, from 5 to 30% by weight (solids) of alkyd resin vehicle, from 0.5 to 10% by weight of emulsifier, balance water, and if desired, drying additives.
Finally, the present invention provides several methods of making a water-based alkyd resin-containing petroleum-derived oil emulsion.
DETAILED DESCRIPTION OF THE INVENTION:
Formulations according to the present invention include fence stains, surface paints for bare timber surfaces, or timber preservatives, with the natures and amounts of components being varied to meet requirements. Stain formulations will normally use a lower percentage of pigments than paint formulations.
It has been found that if the petroleum-derived oil is contaminated by residual anti-oxidants the maximum percentage of oil has to be reduced to 30% by volume or less. Materials such as anti-oxidants, anti-rust additives, and zinc salt anti-wear compounds act adversely on the normal "drying" (oxidative) process undergone by alkyd resins. Also, resistance to rain is reduced during the early part of the drying process, and resistance to rub-off is reduced. It is also believed that formulations according to the present invention may have flash points significantly higher than known oil-based paints and stains. Preferably the non-water based formulations according to the invention contain in excess of 30% by volume of petroleum- derived oil or recycled oil ("RBO").
By "petroleum-derived oil" is meant an oil derived from petroleum which is generally useful for producing lubricants. This definition and the limitations on quantities present does not exclude the presence of other petroleum-derived products used for purposes such as thinning.
By "RBO" is meant used petroleum-derived oil which has been re- refined by:-
1. the acid/clay process, in which waste lubricant is first dewatered, then treated with concentrated sulphuric acid and a clay treatment carried out on the acid-treated, dehydrated oil; or
2. the use of a thin-film evaporator.
A typical RBO has the characteristics:-
Density at 15°C 0.872
Viscosity at 40°C 35
Viscosity at 100°C 6.0 min
Viscosity Index 104
Total Acid No. (mg KOH/g) 0.1
The type of alkyd used according to the invention is preferably a long oil alkyd based on soybean oil. The oil length is preferably from 50 to 90%. References in the Examples to quantity of alkyd used refer: in the case of oil-based formulations to alkyd by itself; and in the case of water-based formulations to about one part alkyd resin solids to two parts latex resin solids, such latex resins being those conventionally used in the paint industry.
The emulsifiers used according to the invention are preferably ethylene oxide propylene oxide block copolymers or nonyl phenol ethylene oxide surfactants.
The R.B.O. emulsion is stabilised further using water soluble thickener.
Non-limiting examples of oil-based formulations according to the present invention include fence stains as follows:-
EXAMPLE 1
MISSION BROWN STAIN
Composition Volume Wei ht %
Alkyd resin FL63/70 cut in Shellsol 2046
Drier mixture
Bentone 38
Shellsol 2046
Diacetone alcohol
Bayer Brown Oxide 660
Talc TX
RBO
Exkin No. 2
Total Mass Total Volume
Method of Preparation
136.1 ml of alkyd resin and 3.9 ml of the drier mixture were mixed using a high speed stirrer or cavitation mixer for five minutes. A slurry of 4.4 ml of Bentone 38 and 39.6 ml of Shellsol 2046 was then added to the resin mix when blended, followed by 25 ml of the diacetone alcohol. Mixing was continued for five minutes. The Bayer Brown pigment and talc were added under high speed stirring and mixing was continued for ten minutes. 42.0 ml of RBO and 0.3 ml of Exkin No. 2 was added gradually under high speed stirring and the viscosity was adjusted with Shellsol. This process yielded a "Mission Brown" fence stain with a theoretical specific gravity of 1.056. The formulation had a viscosity of between 35 and 40 sec./British Flow Cup "B"/25°C.
The alkyd resin used was a long-chain alkyd resin being 63% semi- drying oil penta alkyd with a 70% solids content in a high boiling hydrocarbon solvent, having a flash point above 61°C. Other alkyd resins may be used in substitution thereof.
The drier mixture used in the formulation was prepared from three driers as follows:
Lead 24% lOOg
Cobalt 6% 50g
Manganese 6% 50g
With 4 grams of this drier mixture, the metal content of the preceding four formulations, based on the alkyd oil was calculated to be: lead - 0.8%; cobalt - 0.1%; manganese - 0.1%;. These levels are typical for dark colour stains.
Exkin No. 2 (methyl ethyl ketoxime) is an anti-skinning agent used to promote stability of the formulations during storage and transport. Other similar anti-skinning agents may be substituted. EXAMPLE 2
PINE OOD GREEN STAIN:
Composition Weight %
Alkyd resin F163/70 cut in Shellsol 2046 20.6
Drier Mixture 0.6
Bentone 38 1.2
Shellsol 2046 18.5
Diacetone alcohol 3.6
Yellow Oxide 920 7.8
Black Universal Tinter 1.6
Talc TX 12.5
RBO 33.7
Exkin No. 2 0.05
Total Mass 641.8g Theoretical Volume 610ml Theoretical Specific Gravity 1.062 Viscosity (fresh) 40-45 sec./British Flow Cup "B"/25°C
The method of preparation of this stain was essentially the same as that for the MISSION BROWN stain except that the addition of Black Universal Tinter was performed by a skilled colour tinter. Simply adding a specified quantity by weight or volume was too risky owing to the possible variations in strength of the yellow oxide base and with the precision required in measuring the black tinter. However, with very rigid process control, and repeat batch mixing, a level of accuracy of 90% or more on first addition may be obtained. Since Yellow Oxide 920 is a needle shaped pigment, the end product was rather more thixotropic than the other stains. However, the apparently "thicker" product gave a higher flow cup reading without detracting from ease of brushability.
EXAMPLE 3
WALNUT STAIN
Composition Weight %
Alkyd resin F163/70 cut in Shellsol 2046 20.9
Drier mixture 0.6
Bentone 38 1.2
Shellsol 2046 18.8
Diacetone alcohol 3.6
Bayer Light Brown Oxide 610 6.3
Bayer Brown Oxide 660 1.6
Talc TX 12.7
RBO 34.2
Exkin No. 2 0.05
Total Mass 631.8g Theoretical Volume 600ml Theoretical Specific Gravity 1.053 Viscosity (fresh) 35-40 sec./British Flow Cup "B"/25°C
The method of preparation was essentially the same as that for the MISSION BROWN stain, although a blending of the pigments was required. EXAMPLE 4
AMERICAN REDWOOD STAIN:
Composition Weight %
Alkyd resin F163/70 cut in Shellsol 2046 20.8
Drier Mixture 0.6
Bentone 38 1.2
Shellsol 2046 18.8
Diacetone alcohol 3.6
Bayer Yellow Oxide 960 6.3
Bayer Light Brown 610 1.9
Talc TX 12.6
RBO 34.1
Exkin No. 2 0.05
Total Mass 633.8g
Theoretical Volume 600ml
Theoretical Specific Gravity 1.056
Viscosity 35-40 sec./British Flow Cup "B"/250C
The method of preparation was essentially the same as for the MISSION BROWN Stain.
Water-based products according to the invention may be made in three steps:-
1. the vehicle is mixed with petroleum-derived or recycled petroleum-derived oil in the presence of an emulsifier;
2. the product of step 1 is emulsified with water; and
3. the emulsion is mixed with further water and filler and, if desired, pigments.
The following Examples serve to illustrate this aspect of the invention. EXAMPLE 5 (STEP 1)
ALKYD R.B.O. MIXTURE
PRODUCT
Alkyd resin F163/70
Manganese 6% (drier)
Cobalt 6%
Exkin No. 2 (anti-skinning agent)
R.B.O.
Teric ng (emulsifier)
This amounted to 1000 litres
Mixed well under high speed stirring ("H.S.S.") for 10 minutes.
(STEP 2)
ALKYD/R.B.O. EMULSION Water 43.5 Public Utility
Natrosol 250 HR (thickener) .330g Hatrick Bevaloid 643 (defoamer) .080g Bevaloid
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I,
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112 kg. (STEP 3) AMERICAN REDWOOD FENCE & TIMBER FINISH
Water 464 Public Utility
Natrosol 250 HR 8.8 Hatrick
Bevaloid 2.8 Bevaloid
Acticide PMODS AZ (fungicide) .550g Thor
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite (anti-rust) 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson (dispersant)
Mixed well under H.S.S .for 5 minutes Added
Bayer Yellow Oxide 56 Victor Leggo
Bayer Light Brown 610 17 Victor Leggo
Kaolin KG30 (filler) 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 (resin) 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol (coalescent) 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 1000 litres)
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water 43.5 Public Utility
Natrosol 250 HR .330g Hatrick
Bevaloid 643 .080g Bevaloid
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I.
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112 kg. (STEP 3 )
Water
Natrosol 250 HR
Bevaloid 643
Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Bayer Light Brown 610 56 Victor Leggo
Bayferrox 660 14 Victor Leggo
Kaolin *KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S.
Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 1000 litres)
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water
Natrosol 250 HR
Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% ,080 I.C.I.
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg (STEP 3) PINEWOOD GREEN FENCE & TIMBER FINISH
Water
Natrosol 250 HR
Bevaloid 643
Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Yellow Oxide 70 Victor Leggo
Black Universal Tinter 14 Victor Leggo
Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 1000 litres). EXAMPLE 8
(STEP 1)
ALKYD R.B.O. MIXTURE
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water Natrosol Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% ,080 I.C.I
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg. (STEP 3) MISSION BROWN FENCE & TIMBER FINISH
Water
Natrosol 250 HR
Bevaloid 643
Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Bayerferrox 660 76 Victor Leggo
Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63-847 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 1000 litres). EXAMPLE 9 (STEP 1)
ALKYD R.B.O. MIXTURE
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water
Natrosol 250 HR
Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I.
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg (STEP 3) WHITE FENCE & TIMBER FINISH
Water
Natrosol 250 HR Bevaloid 643 Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Titanium Oxide R.H.D.2 200 Victor Leggo Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S. Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 1030 litres approx). EXAMPLE 10
(STEP 1)
ALKYD R.B.O. MIXTURE
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water
Natrosol 250 HR
Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg. (STEP 3 )
EXAMPLES OF CLEAR FORMULAE FENCE & TIMBER FINISH
Water
Natrosol 250 HR
Bevaloid 643
Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 167 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 168 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 980 litres approx). EXAMPLE 11 (STEP 1)
ALKYD R.B.O. MIXTURE
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water
Natrosol 250 HR
Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I.
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.0. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg. (STEP 3) CLEAR FORMULA FENCE & TIMBER FINISH
Water
Natrosol 250 HR
Bevaloid 643
Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 195 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 140 (from STEP 2)
Added slowly under H.S.S. Texanol
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S.
Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 980 litres approx). EXAMPLE 12 (STEP 1)
ALKYD R.B.O. MIXTURE
This amounted to 1000 litres
Mixed well under H.S.S. for 10 minutes
(STEP 2)
ALKYD/R.B.O. EMULSION
Water
Natrosol 250 HR
Bevaloid 643
Mixed well under H.S.S. for 5 minutes Added
Ammonia 30% .080 I.C.I.
Mixed well under H.S.S. for 10 minutes
Added slowly while mixing for 10 to 15 minutes
Alkyd/R.B.O. Mixture 68 (from STEP 1)
Mixed well under H.S.S. for 15 minutes Total mixture amounted to 112kg. (STEP 3) CLEAR FORMULA FENCE & TIMBER FINISH
Water
Natrosol 250 HR Bevaloid 643 Acticide PMODS AZ
Mixed well under H.S.S. for 5 minutes Added
Ammonia .550g I.C.I.
Mixed well under H.S.S. for 10 minutes Added
Sodium Nitrite 3.3 I.C.I.
Tetrapotassium Pyrophosphate 3.3 Albright & Wilson
Mixed well under H.S.S. for 5 minutes Added
Kaolin KG30 55 Commercial Minerals
Dispersed well under H.S.S. for 20 to 30 minutes Added slowly under H.S.S.
Acropol 63 - 847 223 Hatrick
Added slowly under H.S.S. Alkyd/R.B.O. Emulsion 112 (from STEP 2)
Added slowly under H.S.S. Texanol 6 Swift or Eastman
Added slowly under H.S.S. Water 153 Public Utility
Added slowly under H.S.S. Ammonia 1.7 I.C.I.
Stirred Well
(STEP 3 amounted to 980 litres approx) . Examples 13 to 17 illustrate a two-step process for making water- based products according to the invention:
EXAMPLE 13 (STEP 1)
OIL EMULSION kg VOLUME, 1
2% Thickener Soln 20.0
Water 60.0
Teric P E 68 (emulsifier) 3.3
Propylene Glycol 14.0
Ammonia 880 2.3
Dissolved under H.S.S. in a 200 litre drum then R.B.O. added slowly, stirred for 10 minutes to emulsify
(STEP 2) MISSION BROWN FENCE & TIMBER FINISH
2% Thickener
Water
Teric N40 (nonyl phenol)
226/40
(pigment dispersing agent)
Defoamer 642
Tetrapotassium Pyrophosphate
Whiting
Bayferrox (Bayer)
Kaolin
Then let down with F E 30/55 alkyd resin from Frankston Manufacturing, stirred for 2 minutes, then R.B.O. emulsion added. Stirred for 2 minutes. Defoamer 642 1.4 1.54
Texanol (coalescent solvent) 6.0 6.22
Cosan (fungicide) 0.6 0.66
Sodium Nitrite 3.3 2.0
Viscosity adjusted by adding
Water 53.4 53.4
2% Thickener Soln 380.0 380.0
1263.9 1050.58
EXAMPLE 14 (STEP 1)
OIL EMULSION kg VOLUME, 1
2% Thickener Soln 20.0
Water 60.0
Teric P E 68 3.3
Propylene Glycol 14.0
Ammonia 880 2.3
Dissolved under H.S.S. in a 200 litre drum then R.B.O. added slowly, stirred for 10 minutes to emulsify
(STEP 2) PINEWOOD GREEN FENCE & TIMBER FINISH
2% Thickener Soln 60.0 60.0 Water 70.0 70.0 Teric N40 2.6 2.5 226/40 2.0 1.5 Defoamer 642 1.4 1.54
Tetrapotassium Pyrophosphate 0.3 0.2
Whiting 150.0 54.15
*Yellow Oxide 920 C 77.0
*Bayferrox 318m 16.0 16.8
Kaolin 50.0 19.23
The let down with F E 30/55. Stirred for 2 minutes then R.B.O. emulsion added. Stirred for 2 minutes. Defoamer 642
Texanol
Cosan
Sodium Nitrite
Viscosity adjusted by ad Water 2% Thickener Soln
EXAMPLE 15 (STEP 1)
OIL EMULSION kg VOLUME, 1
2% Thickener Soln 20.0
Water 60.0
Teric P E 68 3.3
Propylene Glycol 14.0
Ammonia 880 2.3
Dissolved under H.S.S. in a 200 litre drum then, R.B.O. added slowly, stirred for 10 minutes to emulsify.
(STEP 2) WALNUT FENCE & TIMBER FINISH
2% Thickener Soln 60.0 60.0 Water 70.0 70.0 Teric N40 2.6 2.5 226/40 2.0 1.5 Defoamer 642 1.4 1.54
Tetrapotassium Pyrophosphate 0.3 0.2
Whiting 150.0 54.15
Bayer Light Brown Oxide 610 62.0
Bayferrox 660 15.5 (16.8)
Kaolin 50.0 19.23
The let down with F E 30/55, stirred for 2 minutes then R.B.O. emulsion added. Stirred for 2 minutes. Defoamer 642
Texanol
Cosan
Sodium Nitrite
Viscosity adjusted by ad Water 2% Thickener Soln
EXAMPLE 16 (STEP 1)
OIL EMULSION kg VOLUME, 1
2% Thickener Soln 20.0
Water 60.0
Teric P E 68 3.3
Propylene Glycol 14.0
Ammonia 880 2.3
Dissolved under H.S.S. in a 200 litre drum then R.B.O. added slowly. Stirred for 10 minutes to emulsify
(STEP 2) AMERICAN REDWOOD FENCE & TIMBER FINISH
2% Thickener Soln 60.0 60.0
Water 70.0 70.0
Teric N40 2.6 2.5
226/40 2.0 1.5
Defoamer 642 1.4 1.54
Tetrapotassium Pyrophosphate 0.3 0.2
Whiting 150.0 54.15
Bayer Yellow Oxide 960 C 62.0
Brown Oxide Water Base Tinter 19.0 (16.8)
Kaolin 50.0 19.23
Then let down with F E 30/55. Stirred for 2 minutes, then R.B.O. emulsion added. Stirred for 2 minutes. Defoamer 642
Texanol
Cosan
Sodium Nitrite
Viscosity adjusted by ad Water 2% Thickener Soln
EXAMPLE 17 (STEP 1)
OIL EMULSION kg VOLUME, 1
2% Thickener Soln 20.0
Water 60.0
Teric P E 68 3.3
Propylene Glycol 14.0
Ammonia 880 2.3
Dissolved under H.S.S. in a 200 litre drum then R.B.O. added slowly. Stirred for 10 minutes to emulsify
(STEP 2) CHARCOAL FENCE & TIMBER FINISH
2% Thickener Soln 60.0 60.0 Water 70.0 70.0 Teric N40 2.6 2.5 226/40 2.0 1.5 Defoamer 642 1.4 1.54
Tetrapotassium Pyrophosphate 0.3 0.2
Whiting 150.0 54.15
Titanium Dioxide R H D 2 18.0
Bayferrox 318m 66.0 (16.8)
Kaolin 50.0 19.23
Then let down with F E 30/55. Stirred for 2 minutes then R.B.O. emulsion added. Stirred for 2 minutes Defoamer 642
Texanol
Cosan
Sodium Nitrite
Viscosity adjusted by ad Water 2% Thickener Soln
Now follow a number of examples having miscellaneous applications:
EXAMPLE 18
This recipe is designed to check the effect of R.B.O. emulsion on colour, drying, hardness and enamel recoatability of gloss 100% acrylic.
A Base R f 51* 133 ml = 256 g
Viscopol 5337 236 g
R.B.O. Emulsion 154 g
Propylene Glycol 20 g
Texanol 11 g
Cosan MSA 1.5 g
CB 643 (defoamer) 1.5 g
2% Thickener 24.0 g
Water 24.0 g
The R.B.O. Emulsion was made by mixing:
2% Thickener 20 g
Water 58 g
P E 68 3.3 g
Propylene Glycol 16.0 g
Ammonia 880 2.3 g
R.B.O. 66.4g
166.0 From Standard Formula 51 (Pale Tint Base)
Breox L85.80 (ethylene oxide propylene oxide block copolymer) 0.5
Tetrapotassium Pyrophosphate 0.5
Defoamer 642 1.0
SCM RCL 575(Titanium Dioxide) 160
Glascol 970 (acrylic acid associative thickener) 18.8
Ammonia 880 0.3
Water 23.6
Viscopol 5337 (100% acrylic
Latex 50% non-volatile) 280.0
R.B.O. Emulsion 134.0
2.0% Thickener 24.0
Propylene Glycol 20.0 Texanol 11.0 Cosan 1.5
Defoamer 642 1.5 2.0% Thickener 24.0
752.2
(The underlining indicates stirring for some time) EXAMPLE 20
Water 23.6
Viscopol 5337 224.0
R.B.O. Emulsion 108.0
2.0% Thickener 24.0
Propylene Glycol Texanol Cosan
Defoamer 642 2.0% Thickener
821.7
(The underlining indicates stirring for some time) EXAMPLE 21
Interior/Exterior Flat (Pale Tint Base) kg Water 80.0
Propylene 24.2
Bevaloid 226/40 2.0
Teric N40 2.7
Breox L85.80 0.5
Tetrapotassium Pyrophosphate 0.5 Defoamer 642 1.0
SCM RCL 575 160.0
Whiting 111.0
Silica 400 WQ 52.0
Mica DF 26.0
Glascol 970 12.0
Ammonia 880 0.3
Water 23.6
Viscopol 5337 180.0
R.B.O. Emulsion 86.0
2% Thickener 54.0
Propylene Glycol 20.0
Texanol 8.0
Cosan 1.5
Defoamer 642 1.5
2% Thickener 50.0
(The underlining indicates stirring from some time) EXAMPLE 22
Interior/Exterior Primer & Sealer kg Water 44.0
Propylene Glycol 24.2
Bevaloid 226/40 2.0
Breox L85.80 0.5
Teric N40 2.6
Tetrapotassium Pyrophosphate 0.5 Defoamer 642 1.0
SCM RCL 575 160.0
Whiting 111.0
800.7
(The underlining indicates stirring for some time) EXAMPLE 23 Undercoat Low Sheen without Propylene Glycol kg Water 68.2
Bevaloid 226/40 2.0
Teric N40 2.6
Breox L85.80 0.5
Tetrapotassium Pyrophosphate 0.5 Defoamer 642 1.0
SCM RCL 575 160.0
Whiting 111.0
Glascol 970 15.0
Ammonia 880 0.3
Water 23.6
Viscopol 5337 224.0
R.B.O. Emulsion 108.0
2% Thickener 24.0
Texanol 9.0
Cosan 1.5
Defoamer 642 1.5
2.0% Thickener 59.0
Water 10.0
(The underlining indicates stirring for some time) EXAMPLE 24 Low Cost Fence Paint kg
2% Thickener Soln 30.0
Water 35.0
Teric N40 1.3
Breox L85.80 0.3
Bevaloid 226/40 1.0
Defoamer 642 0.7
Tetrapotassium Pyrophosphate 0.1
Whiting 75.0
Bayferrox 42.0
Kaolin 25.0
FE 30/55 58.0
R.B.O. Emulsion 42.0
Defoamer 642 0.7
Texanol 1.5
Cosan 0.3
Sodium Nitrite 1.5
Water 177.0
2% Thickener 190.0
(The underlining indicates stirring for some time) EXAMPLE 25
Ranch Stain Semi-Transparent kg
2% Thickener Soln 30.0
Water 30.0
Teric N40 1.3
Breox L85.80 0.3
Bevaloid 226/40 0.9
Defoamer 642 0.7 Tetrapotassium Pyrophosphate 0.1
Whiting 75.0
**Bayferrox 20.0
Kaolin 25.0
FE 30/55 107.0
R.B.O. Emulsion 76.0
Defoamer 0.7
Texanol 3.0
Cosan 0.3
Sodium Nitrite 1.5
Water 69.0
2% Thickener 190.0
(The underlining indicates stirring for some time) It is to be understood that the foregoing examples are not limiting and merely illustrate several aspects of the invention.

Claims

The claims defining the invention are as follows:-
1. A paint or stain formulation incorporating up to 52.5% by weight (or 60% by volume) of petroleum-derived oil.
2. An alkyd resin-containing paint or stain formulation which comprises:- from 1 to 52.5% by weight of petroleum-derived oil; from 5 to 20% by weight (solids) of alkyd resin vehicle; from 1 to 20% by weight of pigment(s); from 15 to 40% by weight of conventional paint solvent(s); and, if desired, from 10 to 20% by weight of gloss control agent.
3. A paint or stain formulation as claimed in claim 2, wherein the petroleum-derived oil is a recycled oil.
4. A paint or stain formulation as claimed in claim 2 or claim 3, which comprises in addition other additives normally used in paint or stain formulations.
5. A water-based alkyd resin-containing paint or stain formulation which comprises:- from 1 to 30% by weight of petroleum-derived oil; from 5 to 30% by weight of (solids) of alkyd resin vehicle; from 0 to 20% by weight of pigment(s); from 0.5 to 10% by weight of emulsifier; and balance water.
6. A paint or stain formulation as claimed in claim 5, wherein the petroleum-derived oil is a recycled oil.
7. A paint or stain formulation as claimed in claim 5 or claim 6, which comprises in addition other additives normally used in paint or stain formulations.
8. A water-based petroleum-derived oil emulsion which comprises:- from 1 to 30% by weight of petroleum-based oil, from 5 to 30% by weight (solids) of alkyd resin vehicle, from 0.5% to 10% by weight of emulsifier, balance water, and, if desired, drying additives.
9. A method of making a water-based alkyd resin-containing paint or stain formulation as claimed in any one of claims 5, 6 or 7 which comprises:- mixing the alkyd resin vehicle with the petroleum- derived oil in the presence of an emulsifier; emulsifying the product of the first step with water; and mixing the emulsion with further water and filler and, if desired, pigments.
10. A method of making a water-based alkyd resin-containing paint or stain formulation which comprises:- mixing a petroleum-derived oil into a water solution containing an emulsifier; and mixing the emulsion into a water solution containing alkyd resin and, if desired, pigments.
EP92901759A 1990-12-21 1991-12-18 Paint and stain formulations Withdrawn EP0563183A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPK401190 1990-12-21
AU4011/90 1990-12-21
AU7179/91 1991-07-12
AUPK717991 1991-07-12

Publications (2)

Publication Number Publication Date
EP0563183A1 EP0563183A1 (en) 1993-10-06
EP0563183A4 true EP0563183A4 (en) 1994-03-02

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JP (1) JPH06509121A (en)
NZ (1) NZ241053A (en)
WO (1) WO1992011326A1 (en)

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Publication number Priority date Publication date Assignee Title
CA2142098A1 (en) * 1992-08-14 1994-03-03 David W. Erismann Water-in-oil-composition for wood stains
GB2408511A (en) * 2003-11-29 2005-06-01 David George Cobbett Preservative timber stain
CN102257082B (en) * 2008-12-18 2014-02-26 威士伯采购公司 Color composition
US11091664B2 (en) 2016-09-30 2021-08-17 The Sherwin-Williams Company Tung oil-based non-lapping water-compatible wood stain

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GB752155A (en) * 1953-06-18 1956-07-04 Bataafsche Petroleum Improvements in or relating to coating compositions containing air-drying synthetic resins
JPS5823862A (en) * 1981-08-04 1983-02-12 Kubokou Paint Kk Coating composition for wood preservation
JPH0639353A (en) * 1992-01-27 1994-02-15 Takasago Denki Sangyo Kk Recovering machine for waste can

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GB1242463A (en) * 1969-05-06 1971-08-11 Nippon Petrochemicals Co Ltd Improvements in or relating to alkyd resins
US3764537A (en) * 1970-03-05 1973-10-09 D Macleod Synthetic petrolatum compositions
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DE3811199A1 (en) * 1988-04-01 1989-10-19 Mueller Bauchemie Wood preservative
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Publication number Priority date Publication date Assignee Title
GB752155A (en) * 1953-06-18 1956-07-04 Bataafsche Petroleum Improvements in or relating to coating compositions containing air-drying synthetic resins
JPS5823862A (en) * 1981-08-04 1983-02-12 Kubokou Paint Kk Coating composition for wood preservation
JPH0639353A (en) * 1992-01-27 1994-02-15 Takasago Denki Sangyo Kk Recovering machine for waste can

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DATABASE WPI Week 7146, Derwent World Patents Index; AN 71-73727S *
DATABASE WPI Week 8426, Derwent World Patents Index; AN 83-28437K *
See also references of WO9211326A1 *

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NZ241053A (en) 1995-04-27
WO1992011326A1 (en) 1992-07-09
JPH06509121A (en) 1994-10-13

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