EP0594691A1 - Aqueous coating composition - Google Patents

Aqueous coating composition

Info

Publication number
EP0594691A1
EP0594691A1 EP92914881A EP92914881A EP0594691A1 EP 0594691 A1 EP0594691 A1 EP 0594691A1 EP 92914881 A EP92914881 A EP 92914881A EP 92914881 A EP92914881 A EP 92914881A EP 0594691 A1 EP0594691 A1 EP 0594691A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
range
polyolefin
grams
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Withdrawn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
EP92914881A
Other languages
German (de)
French (fr)
Inventor
Paul Jackson Greene
Stephen Louis Poteat
James Arnold Stykes
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.)
Eastman Chemical Co
Original Assignee
Eastman Kodak Co
Eastman Chemical Co
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 Eastman Kodak Co, Eastman Chemical Co filed Critical Eastman Kodak Co
Publication of EP0594691A1 publication Critical patent/EP0594691A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/06Ethers; Acetals; Ketals; Ortho-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D123/00Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • This invention relates to aqueous compositions useful as primers useful for enhancing the adhesion of coatings to polyolefin substrates.
  • adhesion promoting compositions This problem has previously been overcome by use of two different approaches which employ adhesion promoting compositions.
  • One approach is to use an adhesion promoting composition as a separate primer coating between the polyolefin substrate and the paint.
  • the primer coating adheres adequately to both the polyolefin and the paint and thereby creates a unitary three component structure with the paint as the outer portion of the structure.
  • Another approach to coating is to use of two different approaches which employ adhesion promoting compositions.
  • polyolefins has been to use an adhestion promoting composition as an additive along with the paint. This technique is sometimes known in the art as use of a "stir in" adhesion promoter.
  • Chlorinated polyolefins have been found to be very satisfactory as the polymeric component for primer compositions due to their cost and performance.
  • U.S. 3,579,485, U.S. 4,070,421, U.S. 4,966,947, U.S. 4,962,149 and U.S. 4,954,573 disclose chlorinated polyolefins which are entirely satisfactory for the polymeric component of adhesion promoting compositions useful for coating polyolefin substrates.
  • chlorinated polyolefins have been used to prepare adhesion promoting compositions which are entirely satisfactory, the chlorinated polyolefins had to be formulated with an organic solvent, such as xylene or toluene.
  • an organic solvent is undesirable because unless elaborate solvent recovery methods are employed application of the primer coating composition results in release of the organic solvent into the atmosphere which can result in both pollution problems and health problems for workers applying the primer coating composition.
  • polyolefin containing primer coating composition which is substantially free of organic solvents is disclosed in WO90/12656.
  • This composition is a five component composition containing a chlorinated polyolefin, a surfactant, an amine, a polyol and water.
  • polyol in the composition disclosed in WO/12656 can create a significant toxicity problem, particularly if the polyol is ethylene glycol.
  • polyol toxacology In addition to the concers about polyol toxacology,
  • volatilization of the polyols during heat curing of the coating can cause polution problems similar to those encountered when organic solvents are used.
  • composition of this invention can be thought of as a four component composition containing A) a chlorinated polyolefin having a particular range of molecular weight, softening point and amount of chlorine,
  • chlorinated polyolefin having a molecular weight in the range of 9,000 to 45,000, a softening point in the range of 75 to 105°C and an amount of chlorine in the range of 15 to 35 weight percent, based on the weight of the polyolefin.
  • These polymers are known in the art and are disclosed in U.S. 3,579,485.
  • the chlorinated polyolefin having a molecular weight in the range of 9,000 to 45,000, a softening point in the range of 75 to 105°C and an amount of chlorine in the range of 15 to 35 weight percent, based on the weight of the polyolefin.
  • chlorinated polyolefin has a molecular weight in the range of 9,000 to 16,000, a softening point in the range of 80 to 95oC and an amount of chlorine in the range of 18 to 22 percent, based on the weight of the polyolefin.
  • the molecular weight of the chlorinated polyolefin is average number molecular weight.
  • the total amount of polyolefin in the composition is not significant as long as the relative amounts of components (B) and (C) are within the ranges for these materials.
  • non-ionic surfactant we mean a surfactant which contains no positively or negatively charged functional groups.
  • the surfactants can have a molecular weight of up to 500 or even higher and can include polymeric materials.
  • the surfactants include materials which contain groups of varying polarity whereby one part of the molecule is hydrophilic and the other part of the molecule is hydrophobic. Examples of such materials include polyethyleneoxy polyols and ethoxylated alkly phenols. Particularly preferred classes of surfactants include alkyl phenoxy
  • the surfactant is a primary ethoxylated alcohol having 12 to 15 carbon atoms or a secondary ethoxylated alcohol having 11 to 15 carbon atoms.
  • the amount of surfactant is broadly in the range of 18 to 50 weight % and is preferably in the range of 20 to 25 weight %, based on the weight of the chlorinated polyolefin.
  • composition of this invention can be a primary
  • amine can be aromatic or aliphatic, aliphatic amines are preferred. In a preferred embodiment the aliphatic amine has an amine functionality of between 1 and 3, and optionally contains other oxygen containing functional groups.
  • the amines useful in this invention generally have a
  • a highly preferred group of amines are primary, secondary and tertiary aliphatic amines having a
  • R 1 R 7 are independently selected from H or straight or branched chain alkyl, hydroxyalkyl, or alkoxylalkyl groups of 1 to 20 carbon atoms; R 1 - R 7 can additionally include a substituted alkyl group, i.e., where one or more of the carbons in the radical is replaced with or has substituted thereon another
  • an amine, ether, hydroxy or - mercapto moiety e.g., tris-(3-aminopropyl) amine.
  • Another group of highly preferred amines within the above classes are those primary, secondary or tertiary aliphatic amines of the above Formulae in which R 1 - R 7 is specifically substituted with or contains one or more hydroxyl (-OH) functionalities.
  • Another group of preferred amines can be
  • n 1 or 2 and R 8 , R 9 , R 10 and R 11 are
  • amines preferred in the practice of the present invention are primary, secondary and tertiary aliphatic amines with an amine functionality of 1-3 which also contain one or more ether or alkoxy linkages. Such materials are sometimes referred to as poly(oxyalkylene)diamines. Ethoxylated or propoxylated materials are particularly preferred.
  • Exemplary amines preferred for use in the present invention include:
  • Preferred amines are morpholine, triethanolamine, ethanolamine, 2-dimethylaminoethanol, triethylamine and ammonium hydroxide. Particularly preferred amines are morpholine and ammonium hydroxide.
  • the amount of amine can be in the range of 2 to 10 weight % and preferably is in the range of 4 to 6 weight %, based on the weight of the chlorinated polyolefin.
  • compositions of this invention further contain water.
  • the amount of water can vary widely depending on numerous factors, such as the needs of the manufacturer, transportation efficiencies and the needs of the
  • compositions of this invention are selected from these compounds having the same
  • compositions can be manufactured using less water than would typically be required to apply the compositions as a coating and water can be subsequently added by the customer at a later time to prepare a coating
  • composition This can be done by simply pouring
  • concentration is also often desired if the adhesion promoter composition is to be used as an additive to the paint in order to prevent excessive dilution of the paint.
  • the amount of water can vary widely and there is no upper limit on the amount of water there is a lower limit on the amount of water because there must at least be sufficient water in the composition to result in the formation of an admixture of the four components.
  • the precise amount of water necessary to form the required admixture can vary, generally there must be at least 40 weight % water in the composition, based on the weight of the total composition, in order to form an admixture with pourable viscosity characteristics.
  • compositions of this invention are:
  • compositions of this invention can contain other materials in major amounts.
  • compositions of this invention can contain materials typically used in the paint industry to prepare paint formulations, such as thickeners, wetting agents and flow aids, pigments, resins and solvents.
  • compositions can contain organic solvents but preferably the compositions are substantially free of organic solvents.
  • the compositions of this invention preferably contain less that 10%, more preferably less than 5% and most preferably less than 1% organic
  • the preferably small quantity of organic solvent can be present as an impurity or can be present as in intended component of the composition.
  • compositions of this invention do not contain
  • polyols that are not present in significant quantities in the compositions of this invention include the polyols disclosed in WO/12656.
  • compositions of this invention can be used as aa adhesion promoting composition according to two different approaches. Selection of the preferred approach depends on numerous factors, such as the specific characteristics of the paint, the particular substrate to be painted, the nature and extent of the other materials to be used in the paint formulation and other factors.
  • the coating compositions of this invention can be used as a separate primer coat by preferably diluting the
  • compositions of this invention can be used as a so-called "stir-in" paint additive.
  • the composition is added admixed with the paint and the resulting admixture is applied to the polyolefin substrate to form a single coating which adheres to the polyolefin substrate.
  • the compositions of this invention can be prepared according to techniques well known in the art for preparing polyolefin wax emulsions. For example, the compositions can be prepared by introducing the four components into an agitated pressure vessel and
  • the agitating the components at a suitable temperature and pressure for a suitable time typically the temperature will be in the range of 100°C to 150°C, the pressure in the range of 14 psi to 70 psi, and the time will be in the range of 10 minutes to 45 minutes.
  • the temperature will be in the range of 100°C to 150°C
  • the pressure in the range of 14 psi to 70 psi
  • the time will be in the range of 10 minutes to 45 minutes.
  • compositions can be prepared using a temperature of 120°C, a pressure of 30 psi and a time of 20 minutes.
  • compositions of this invention are admixtures which have a particle size suitably small to make the admixtures useful in coating enbodiments. Therefore, the compositions of this invention include not only what some authorizes call “emulsions” and “dispersions” but include as well as all other physical forms in which the various components can be become admixed. For example, some authorities characterize water containing
  • compositions of this invention are particularly useful as adhesion promoters to enhance the adhesion of paints to polyolefin substrates it is within the scope of the invention for the compositions to be used by themselves as a paint to form a final protective coating which not only protects the substrate but also is decorative as a result of the addition of pigments.
  • compositions of the invention were prepared from a chlorinated polyolefin, a nonionic surfactant, an amine and sufficient water to produce emulsions having 24 percent, based on the weight of the total composition, of the chlorinated polyolefin.
  • the compositions were prepared by introducing the four components into a sealed vessel equipped with a means for agitation. Agitation was started and the contents of the vessel heated to 120°C and the resulting pressure was 30 psi. This temperature and pressure was
  • This example illustrates preparation of a
  • composition of the invention using a particular
  • chlorinated polyolefin one type of nonionic surfactant and a secondary amine.
  • the resultant composition was diluted with sufficient additional water to result in a primer coating
  • composition composed of 8 percent chlorinated
  • polyolefin based on the weight of total composition. This composition was applied to polypropylene. The composition was also applied to a polyolefin which has been modified with an elastomeric polymer. These materials are generally designated in the trade as “thermoplastic olefins” and are abbreviated "TPO”. The composition was applied by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance witASTM D2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • chlorinated polyolefin based on the weight of total composition. This composition was applied to
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • chlorinated polyolefin based on the weight of the total composition. This composition was applied to
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection. Results of this test were no change after 5 cycles.
  • Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows: Paint adhesion on polypropylene: 50%
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
  • composition composed of 8 percent chlorinated
  • composition This composition was applied to
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • chlorinated polyolefin based on the weight of the total composition. This composition was applied to
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
  • chlorinated polyolefin based on the weight of the total composition. This composition was applied to
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
  • composition composed of 8 percent chlorinated polyolefin, based on the weight of the total
  • composition This composition was applied to
  • polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
  • Stability at 75°F for 8 weeks Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, a different nonionic surfactant and a secondary anine.
  • This example illustrates preparation of a
  • composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic

Abstract

Composition renfermant: (A) une polyoléfine chlorée, (B) un tensioactif non ionique, (C) un amine primaire, secondaire ou tertiaire, et (D) de l'eau.Composition containing: (A) a chlorinated polyolefin, (B) a nonionic surfactant, (C) a primary, secondary or tertiary amine, and (D) water.

Description

Aqueous Coating Composition
This invention relates to aqueous compositions useful as primers useful for enhancing the adhesion of coatings to polyolefin substrates.
The application of paints and other coatings to substrates of polyolefin, such as polypropylene, thermoplastic olefin and polyethylene, is typically difficult because polyolefins are substantially
chemically inert.
This problem has previously been overcome by use of two different approaches which employ adhesion promoting compositions. One approach is to use an adhesion promoting composition as a separate primer coating between the polyolefin substrate and the paint. The primer coating adheres adequately to both the polyolefin and the paint and thereby creates a unitary three component structure with the paint as the outer portion of the structure. Another approach to coating
polyolefins has been to use an adhestion promoting composition as an additive along with the paint. This technique is sometimes known in the art as use of a "stir in" adhesion promoter.
Numerous polymeric materials have been investigated as possible components for such ashesion promoters.
Chlorinated polyolefins have been found to be very satisfactory as the polymeric component for primer compositions due to their cost and performance. For example, U.S. 3,579,485, U.S. 4,070,421, U.S. 4,966,947, U.S. 4,962,149 and U.S. 4,954,573 disclose chlorinated polyolefins which are entirely satisfactory for the polymeric component of adhesion promoting compositions useful for coating polyolefin substrates. Even though chlorinated polyolefins have been used to prepare adhesion promoting compositions which are entirely satisfactory, the chlorinated polyolefins had to be formulated with an organic solvent, such as xylene or toluene. Use of an organic solvent is undesirable because unless elaborate solvent recovery methods are employed application of the primer coating composition results in release of the organic solvent into the atmosphere which can result in both pollution problems and health problems for workers applying the primer coating composition.
One approach to overcoming the problems associated with the use of organic solvents in primer coating compositions has been to replace the vast majority of the organic solvent. For example, a chlorinated
polyolefin containing primer coating composition which is substantially free of organic solvents is disclosed in WO90/12656. This composition is a five component composition containing a chlorinated polyolefin, a surfactant, an amine, a polyol and water.
The use of the polyol in the composition disclosed in WO/12656 can create a significant toxicity problem, particularly if the polyol is ethylene glycol. In addition to the concers about polyol toxacology,
volatilization of the polyols during heat curing of the coating can cause polution problems similar to those encountered when organic solvents are used.
We have now discovered an entirely satisfactory water based chlorinated polyolefin composition which does not contain a polyol. Thus, the elimination of the polyol results in a composition which exhibits
significantly improved toxicity properties and is more environmentally friendly that the polyol containing composition. Broadly, the composition of this invention can be thought of as a four component composition containing A) a chlorinated polyolefin having a particular range of molecular weight, softening point and amount of chlorine,
(B) a nonionic surfactant,
(C) a primary, secondary or tertiary amine, and
(D) water.
The chlorinated polyolefins useful in this
invention are can be broadly described as a chlorinated polyolefin having a molecular weight in the range of 9,000 to 45,000, a softening point in the range of 75 to 105°C and an amount of chlorine in the range of 15 to 35 weight percent, based on the weight of the polyolefin. These polymers are known in the art and are disclosed in U.S. 3,579,485. In a preferred embodiment, the
chlorinated polyolefin has a molecular weight in the range of 9,000 to 16,000, a softening point in the range of 80 to 95ºC and an amount of chlorine in the range of 18 to 22 percent, based on the weight of the polyolefin.
In this invention the molecular weight of the chlorinated polyolefin is average number molecular weight.
The total amount of polyolefin in the composition is not significant as long as the relative amounts of components (B) and (C) are within the ranges for these materials.
The surfactant useful in this invention can be broadly described as a non-ionic surfactant. By the term "non-ionic surfactant" we mean a surfactant which contains no positively or negatively charged functional groups.
In this invention the surfactants can have a molecular weight of up to 500 or even higher and can include polymeric materials. The surfactants include materials which contain groups of varying polarity whereby one part of the molecule is hydrophilic and the other part of the molecule is hydrophobic. Examples of such materials include polyethyleneoxy polyols and ethoxylated alkly phenols. Particularly preferred classes of surfactants include alkyl phenoxy
poly(ethyleneoxy) alcohols, primary ethoxylated alcohols and secondary ethoxylated alcohols. Preferably the surfactant is a primary ethoxylated alcohol having 12 to 15 carbon atoms or a secondary ethoxylated alcohol having 11 to 15 carbon atoms.
The amount of surfactant is broadly in the range of 18 to 50 weight % and is preferably in the range of 20 to 25 weight %, based on the weight of the chlorinated polyolefin.
The amine component which is used in the
composition of this invention can be a primary,
secondary or tertiary amine. Although the amine can be aromatic or aliphatic, aliphatic amines are preferred. In a preferred embodiment the aliphatic amine has an amine functionality of between 1 and 3, and optionally contains other oxygen containing functional groups. The amines useful in this invention generally have a
molecular weight of less than 100.
A highly preferred group of amines are primary, secondary and tertiary aliphatic amines having a
functionality of 1 to 3 and can be generally represented by the general formulae:
or
; or
wherein R1 = R7 are independently selected from H or straight or branched chain alkyl, hydroxyalkyl, or alkoxylalkyl groups of 1 to 20 carbon atoms; R1 - R7 can additionally include a substituted alkyl group, i.e., where one or more of the carbons in the radical is replaced with or has substituted thereon another
functionality, e.g., an amine, ether, hydroxy or - mercapto moiety, e.g., tris-(3-aminopropyl) amine.
Another group of highly preferred amines within the above classes are those primary, secondary or tertiary aliphatic amines of the above Formulae in which R1 - R7 is specifically substituted with or contains one or more hydroxyl (-OH) functionalities.
Another group of preferred amines can be
represented by the formulae: or or
wherein n is 1 or 2 and R8, R9, R10 and R11 are
independently selected from straight or branched chain alkyl, hydroxyalkyl or alkoxyalkyl groups of 1 to 20 carbon atoms. These chains may also be substituted with another functionality as described above.
Yet another group which comprise amines preferred in the practice of the present invention are primary, secondary and tertiary aliphatic amines with an amine functionality of 1-3 which also contain one or more ether or alkoxy linkages. Such materials are sometimes referred to as poly(oxyalkylene)diamines. Ethoxylated or propoxylated materials are particularly preferred. Exemplary amines preferred for use in the present invention include:
2-amino-1-butanol;
4-amino-1-butanol;
2-aminoethanethiol;
2-aminoheptane;
2-amino-1-hexanol;
6-amino-1-hexanol;
allylamine;
2-amino-3-methyl-1-butanol;
2-amino-2-methyl-1,3-propanediol;
2-amino-2-methyl-1-propanol;
2-amino-1-pentanol;
5-amino-1-pentanol;
3-amino-1-propanol;
ammonium hydroxide
amylamine;
butylamine;
N,N'-bis(2-aminoethyl)-1,3-propanediamine;
N,N'-bis(3-aminopropyl)-1,3-propanediamine;
1,3-bis(dimethylamino)-2-propanol;
1-[N,N-bis(2-hydroxyethyl)amino]-2-propanol;
N,N'-bis(2-hydroxyethyl)ethylenediamine;
decylamine;
1,4-diaminobutane;
1,10-diaminodecane;
1,12-diaminododecane;
1,7-diaminoheptane;
1,3-diamino-2-hydroxypropane;
3,3'-diamino-N-methyldipropylamine;
1,2-diamino-2-methylpropane;
1,9-diaminononane;
1,8-diaminooctane;
1,5-diaminopentane;
1,2-diaminopropane; 1,3-diaminopropane;
dibutylamine;
3-(dibutylamino)propylamine;
diethanolamine;
diethylamine;
5-diethylamino-2-pentanol;
3-(diethylamino)-1,2-propanediol;
1-diethylamino-2-propanol;
3-diethylamino-1-propanol;
3-diethylaminopropylamine;
diethylenetriamine;
N,N-diethylethanolamine;
N,N-diethylethylenediamine;
N,N-diethylmethylamine;
N,N*-diethyl-1,3-propanediamine;
diisobutylamine;
diisopropanolamine;
diisopropylamine;
2-(diisopropylamino)ethanol;
3-diisopropylamino-1,2-propanediol;
N,N-diisopropylethylamine;
1-dimethylamino-2-propanol;
2-dimethylaminoethanol
3-dimethylamino-1-propanol;
3-dimethylaminopropylamine;
1,3-dimethylbutylamine;
3,3-dimethylbutylamine;
N,N-dimethylethanolamine;
N,N-dimethylethylamine;
N,N-dimethylethylenediamine;
N,N-dimethyl-N'-ethylethylenediamine;
N,N'-dimethyl-1-,6-hexanediamine;
2,5-dimethyl-2,5-hexanediamine;
1,5-dimethylhexylamine;
2,2-dimethyl-1,3-propanediamine; (±)-1,2-dimethylpropylamine;
dipropylamine;
dodecylamine;
ethanolamine;
3-ethoxypropylamine;
ethylamine;
2-(ethylamino) ethanol;
N-ethylbutylamine;
2-ethylbutylamine;
N-ethyldiethanolamine;
ethylenediamine;
hexamethylenediamine;
1,6-hexanediamine;
hexylamine;
isoamylamine;
isopropylamine;
N-isopropylethylenediamine;
N'-isopropyl-2-methyl-1,2-propanediamine;
N,N,N',N'-tetramethyl-1,4-butanediamine; N,N,N',N'-tetramethyldiaminomethane;
N,N,N',N'-tetramethylethylenediamine;
N,N,N',N'-tetramethyl-1,6-hexanediamine;
N,N,N',N'-tetramethyl-1,3-propane-diamine;
N,N,2,2-tetramethyl-1,3-propanediamine; tributylamine;
tridecyamine;
triethanolamine;
triethylamine;
triisooctylamine;
triisopropyanolamine;
trimethylamine;
methylamine;
2-(methylamino)ethanol;
N-Methylbutylamine;
1-methylbutylamine; 2-methylbutylamine;
N-methyldiethanolamine;
N-methylethylenediamine;
N-methyl-1,3-propanediamine;
morpholine
nonylamine;
octylamine;
teri-octylamine;
propylamine;
2-(propylamino)ethanol;
1-tetradecylamine; and
tris(3-aminopropyl)amine. Mixtures of such materials may also be employed.
Preferred amines are morpholine, triethanolamine, ethanolamine, 2-dimethylaminoethanol, triethylamine and ammonium hydroxide. Particularly preferred amines are morpholine and ammonium hydroxide.
The amount of amine can be in the range of 2 to 10 weight % and preferably is in the range of 4 to 6 weight %, based on the weight of the chlorinated polyolefin.
The compositions of this invention further contain water. The amount of water can vary widely depending on numerous factors, such as the needs of the manufacturer, transportation efficiencies and the needs of the
particular customer. An important property of the compositions of this invention is that these
compositions can be manufactured using less water than would typically be required to apply the compositions as a coating and water can be subsequently added by the customer at a later time to prepare a coating
composition. This can be done by simply pouring
additional water into the composition prepared by the manufacturer without having to consider in detail any particular temperature, pressure or time used to prepare the diluted composition. Thus the manufacturer can prepare a "concentrated" product which is low in water and ship the concentrated product to the customer without the necessity of incurring the additional cost of also shipping additional amount to customer. A
"concentrated" product is also often desired if the adhesion promoter composition is to be used as an additive to the paint in order to prevent excessive dilution of the paint.
Even though the amount of water can vary widely and there is no upper limit on the amount of water there is a lower limit on the amount of water because there must at least be sufficient water in the composition to result in the formation of an admixture of the four components. Although the precise amount of water necessary to form the required admixture can vary, generally there must be at least 40 weight % water in the composition, based on the weight of the total composition, in order to form an admixture with pourable viscosity characteristics.
The compositions of this invention are
characterized as "containing" of the four components. By the term "containing" we mean that the compositions can contain other materials in major amounts. For example, the compositions of this invention can contain materials typically used in the paint industry to prepare paint formulations, such as thickeners, wetting agents and flow aids, pigments, resins and solvents.
The term "containing" also means that the
compositions can contain organic solvents but preferably the compositions are substantially free of organic solvents. Thus, the compositions of this invention preferably contain less that 10%, more preferably less than 5% and most preferably less than 1% organic
solvent. The preferably small quantity of organic solvent can be present as an impurity or can be present as in intended component of the composition.
The term "containing" also means that the
compositions of this invention do not contain
significant quantities of polyol. Examples of polyols that are not present in significant quantities in the compositions of this invention include the polyols disclosed in WO/12656.
The compositions of this invention can be used as aa adhesion promoting composition according to two different approaches. Selection of the preferred approach depends on numerous factors, such as the specific characteristics of the paint, the particular substrate to be painted, the nature and extent of the other materials to be used in the paint formulation and other factors. In accordance with one approach, the coating compositions of this invention can be used as a separate primer coat by preferably diluting the
manufactured composition with water, adding any desired additives and then applying the diluted composition to a polyolefin substrate to form a coating using
conventional means, such as spraying, brushing or dipping. After the composition has been applied as a coating and the coating has dried a paint is applied over the primer coating. The primer coating adheres to both the polyolefin and the paint and thereby creates a unitary three component structure with the paint as the outer portion of the structure. In accordance with the other approach, the compositions of this invention can be used as a so-called "stir-in" paint additive. In this approach the composition is added admixed with the paint and the resulting admixture is applied to the polyolefin substrate to form a single coating which adheres to the polyolefin substrate. The compositions of this invention can be prepared according to techniques well known in the art for preparing polyolefin wax emulsions. For example, the compositions can be prepared by introducing the four components into an agitated pressure vessel and
agitating the components at a suitable temperature and pressure for a suitable time. Although the particular conditions must be selected based on the particular equipment available, the particular components of the composition and other factors, typically the temperature will be in the range of 100°C to 150°C, the pressure in the range of 14 psi to 70 psi, and the time will be in the range of 10 minutes to 45 minutes. Other
temperatures, pressures and times can be used and are within the understanding of those skilled in the art. In a preferred embodiment the compositions can be prepared using a temperature of 120°C, a pressure of 30 psi and a time of 20 minutes.
The compositions of this invention are admixtures which have a particle size suitably small to make the admixtures useful in coating enbodiments. Therefore, the compositions of this invention include not only what some authorizes call "emulsions" and "dispersions" but include as well as all other physical forms in which the various components can be become admixed. For example, some authorities characterize water containing
admixtures wherein the particle size in the range of 0.1 to 10 microns as an "emulsions". Other authorities regard water containing admixtures wherein the particle size is greater than 10 microns as a "dispersion".
While both of these types of admixtures are within the scope of this invention, the invention is not limited to these or any other kind of particular admixture and includes all possible types of admixtures regardless of physical form as long as the particle size is small enough for the admixtures to have utility in coating applications.
While the compositions of this invention are particularly useful as adhesion promoters to enhance the adhesion of paints to polyolefin substrates it is within the scope of the invention for the compositions to be used by themselves as a paint to form a final protective coating which not only protects the substrate but also is decorative as a result of the addition of pigments.
In the following examples compositions of the invention were prepared from a chlorinated polyolefin, a nonionic surfactant, an amine and sufficient water to produce emulsions having 24 percent, based on the weight of the total composition, of the chlorinated polyolefin. The compositions were prepared by introducing the four components into a sealed vessel equipped with a means for agitation. Agitation was started and the contents of the vessel heated to 120°C and the resulting pressure was 30 psi. This temperature and pressure was
maintained and the vessel was agitated for 20 minutes.
Example 1
This example illustrates preparation of a
composition of the invention using a particular
chlorinated polyolefin, one type of nonionic surfactant and a secondary amine.
40 grams of a chlorinated polyolefin which has a molecular weight in the range of 9,000 to 16,000, a softening point in the range of 80 to 95°C and an amount of chlorine in the range of 18 to 22 percent, based on the weight of the polyolefin, 10 grams of a nonyl phenoxy poly(ethyleneoxy) alcohol, 2 grams of
morpholine, and 114 grams of water were charged to the vessel and the above described procedure undertaken.
The resultant composition was diluted with sufficient additional water to result in a primer coating
composition composed of 8 percent chlorinated
polyolefin, based on the weight of total composition. This composition was applied to polypropylene. The composition was also applied to a polyolefin which has been modified with an elastomeric polymer. These materials are generally designated in the trade as "thermoplastic olefins" and are abbreviated "TPO". The composition was applied by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 30%
Paint adhesion on TPO: 100% Example 2
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 grams of 2-dimethyl-aminoethanol, and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chlorinated polyolefin, based on the weight of the total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance witASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 45%
Paint adhesion on TPO: 100%
Example 3
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 grams of triethanol amine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F. Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling
Freeze/thaw stability tests were conducted in accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 95%
Paint adhesion on TPO: 100% Example 4
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 grams of triethyl amine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of the total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 45%
Paint adhesion on TPO: 100% Example 5
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
surfactant and a secondary amine.
40 grams of polyolefin, 10 grams of a nonyl phenoxy poly(ethyleneoxy) alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chlorinated polyolefin, based on the weight of the total composition. This composition was applied to polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection. Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows: Paint adhesion on polypropylene: 50%
Paint adhesion on TPO: 100%
Example 6
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
surfactant and a primary amine.
40 grams of polyolefin, 10 grams of a C11-C15 secondary ethoxylated alcohol, 2 grams of ethanolamine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating
composition composed of 8 percent chlorinated
polyolefin, based on the weight of the total
composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 35%
Paint adhesion on TPO: 100% Example 7
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 6 and a secondary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 grams of morpholine and 114 grams of water are
introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chlorinated polyolefin, based on the weight ofthe total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling
Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 50%
Paint adhesion on TPO: 100% Example 8
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 7 and ammonium hydroxide. 40 grams of polyolefin, 10 grams of surfactant, 2 grams of ammonium hydroxide and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of the total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 95%
Paint adhesion on TPO: 100%
The use of CP 343-1, a nonionic surfactant and a primary amine in this Example represents a more
preferred embodiment of the invention.
Example 9
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonionic
surfactant used in Example 8 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 grams of triethanolamine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of the total composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 80%
Paint adhesion on TPO: 100%
Example 10
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
surfactant and a secondary amine.
40 grams of polyolefin, 10 grams of a C11-C15 secondary ethyloxylated alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating
composition composed of 8 percent chlorinated polyolefin, based on the weight of the total
composition. This composition was applied to
polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 45%
Paint adhesion on TPO: 100%
Example 11
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, a different nonionic surfactant and a secondary anine.
40 grams of polyolefin, 10 grams of a C12-C15 primary ethlyoxylated alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chlorinated polyolefin, based on the weight of the total composition. This composition was applied to polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F. Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling
Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 40%
Paint adhesion on TPO: 100%
The use of CP 343-1, a nonionic surfactant and a secondary amine in this Example represents a more preferred embodiment of the invention.
Example 12
This example illustrates preparation of a
composition of the invention using the same chlorinated polyolefin used in Example 1, another nonionic
surfactant and a secondary amine.
40 grams of polyolefin, 10 grams of a C12-C15 primary ethyloxylated alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel and the above described procedure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chlorinated polyolefin, based on the weight of the total composition. This composition was applied to polypropylene and TPO by spraying and then dried by baking for 10 minutes at 160°F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows: Stability at 75°F for 8 weeks: Slight settling Stability at 125°F for 4 weeks: Slight settling Freeze/thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection. Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance with ASTM D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 50%
Paint adhesion on TPO: 100%

Claims

1. A composition containing
(A) a chlorinated polyolefin having a molecular weight in the range of 9,000 to 45,000, a softening point in the range of 75 to 105°C and an amount of chlorine in the range of 15 to 35 weight percent, based on the weight of the polyolefin,
(B) from 18 to 50 weight percent, based on the weight of component (A), of a nonionic
surfactant,
(C) from 2 to 10 weight percent, based on the
weight of component (A), of a primary, secondary or tertiary amine, and
(D) water.
2. The composition of claim 1 wherein component (A) is a chlorinated polyolefin having a molecular weight in the range of 9,000 to 16,000, a softening point in the range of 80 to 95°C and an amount of
chlorine in the range of 18 to 22 weight percent.
3. The composition of claim 1 wherein component (B) is selected from the group consisting of alkyl phenoxy poly(ethyleneoxy) alcohols, primary ethoxylated alcohols and secondary ethoxylated alcohols.
4. The composition of claim 3 wherein component (B) is selected from the group consisting of primary ethoxylated alcohols having 12 to 15 carbon atoms and secondary ethoxylated alcohols having 11 to 15 carbon atoms.
5. The composition of claim 1 wherein component (C) is selected from the group consisting of morpholine, triethanolamine, ethanolamine,
2-dimethylaminoethanol, triethylamine and ammonium hydroxide.
6. The composition of claim 4 wherein component (C) is selected from the group consisting of ammonium hydroxide and morpholine.
7. The composition of claim 1 wherein component (B) is in the range of 20 to 25.
8. The composition of claim 1 wherein component (C) is in the range of 4 to 6.
9. A composition containing
(A) a chlorinated polyolefin having a molecular weight in the range of 9,000 to 16,000, a softening point in the range of 80 to 95°C and an amount of chlorine in the range of 18 to 22 percent, based on the weight of the
polyolefin,
(B) from 20 to 25 weight percent, based on the
weight of component (A), of a surfactant selected from the group consisting of primary ethoxylated alcohols having 12 to 15 carbon atoms and secondary ethoxylated alcohols having 11 to 15 carbon atoms,
(C) from 4 to 6 weight percent, based on the
weight of component (A), of an amine selected from the group consisting of ammonium hydroxide and morpholine, and
(D) water.
10. A polyolefin article coated with the composition of claim 1.
11. A composition comprised of a paint and the
composition of claim 1.
EP92914881A 1991-07-01 1992-06-25 Aqueous coating composition Withdrawn EP0594691A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US72426691A 1991-07-01 1991-07-01
US724266 1991-07-01
PCT/US1992/005393 WO1993001244A1 (en) 1991-07-01 1992-06-25 Aqueous coating composition

Publications (1)

Publication Number Publication Date
EP0594691A1 true EP0594691A1 (en) 1994-05-04

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EP (1) EP0594691A1 (en)
JP (1) JPH06509130A (en)
KR (1) KR940701432A (en)
CA (1) CA2112230A1 (en)
WO (1) WO1993001244A1 (en)

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US5756566A (en) * 1989-04-20 1998-05-26 A-Line Products Corp. Aqueous coating composition
US5288780A (en) * 1991-03-13 1994-02-22 Tioga International, Inc. Water based adhesion promoting compositions
EP0721968A1 (en) * 1995-01-10 1996-07-17 Betz Europe, Inc. Method for improving paint adhesion
TW364002B (en) 1995-11-15 1999-07-11 Bee Chemical Co A one-coat, waterborne coating system for untreated polypropylene-based substrates
ES2159402T3 (en) * 1996-09-03 2001-10-01 Du Pont MULTIPLE LAYER LAYERING PROCEDURE FOR MOTOR VEHICLES.
WO2010126962A1 (en) * 2009-04-29 2010-11-04 Dow Global Technologies Inc. Polyhydroxy-diamines as multi-functional additives for paints, coatings and expoxies
US8466218B2 (en) 2009-09-04 2013-06-18 Basf Coatings Gmbh Adhesion promoter and coating composition for adhesion to olefinic substrates
WO2014085010A1 (en) * 2012-11-30 2014-06-05 Dow Global Technologies Llc Aminoalcohol compounds as low voc free-thaw stabilizers for paints and coatings

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US4966947A (en) * 1988-05-20 1990-10-30 Eastman Kodak Company Modified chlorinated polyolefins
DE3910901A1 (en) * 1989-04-04 1990-10-11 Ppg Ind Deutschland Gmbh METHOD FOR PRODUCING AN AQUEOUS PARTICULAR DISPERSION OF A CHLORINE POLYOLEFIN AND USE THEREOF IN AQUEOUS COATING COMPOSITIONS
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WO1993001244A1 (en) 1993-01-21

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