CA2112230A1 - Aqueous coating composition - Google Patents
Aqueous coating compositionInfo
- Publication number
- CA2112230A1 CA2112230A1 CA002112230A CA2112230A CA2112230A1 CA 2112230 A1 CA2112230 A1 CA 2112230A1 CA 002112230 A CA002112230 A CA 002112230A CA 2112230 A CA2112230 A CA 2112230A CA 2112230 A1 CA2112230 A1 CA 2112230A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- polyolefin
- range
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions 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
- C08L23/28—Compositions 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
-
- 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
- C09D123/00—Coating 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
- C09D123/26—Coating 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
- C09D123/28—Coating 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Disclosed is a composition containing: (A) a chlorinated polyolefin, (B) a nonionic surfactant, (C) a primary, secondary or tertiary amine, and (D) water.
Description
2~ PCT/USg2/05393 21122~1) Aqueous coatina 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. 3,5~9,485, 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.
.
,, , , ., . ,, ,, ,, , ~ .. .. ...... , , ., . .. .. , .. .. , ,., Wo~3/012~ PCT/US92/05393 . . ~
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 W090~12656. This composition is a five component -~
composition containing a chlorina~ed 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 ethylens glycol~ In addition to the concers about polyol toxacology, volatilization of the polyols during heat curinq 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 environDentally friendly that the polyol containing composition.
WO93/012~ 2 1 1 2 2 3 ~ PCT/US92/05393 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 molecuIar 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 s,ooo to 45,000, a softening point in the range of 75 to 105C 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.5. 3,579,485. In a preferred embodiment, the chlorinated polyolefin has a molecular weig~t in the range of 9,000 to 16,000, a softening point in the range of 80 to 95C and an amount of chlorine in the ran~e of -~
l8 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 charqe~ 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 W093/012~ PCT/US92/053g3 . .
~ 4 _ 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 ranqe of 20 to 25 weight %, based on the weight of t~e 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.
2S 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:
... :
Rl - ~ R3 ; or Rl ~ R3 5 ; or W093/012~ 2 1 1 2 2 ~ o PCT~US92~0s393 R2 R~ R6 Rl ~ R3 _ ~ R5 ~ - R
wherein Rl = R7 are independently selected from H or straight or branched chain alkyl, hydroxyalkyl, or alkoxylalkyl groups of 1 to 20 carbon atoms; Rl - 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 Rl - R
is specifically substituted with or contains one or more hydroxyl (-OH) functionalities.
Another group of preferred amines can be represented by the formulae:
2S Rg Rg R8 - (NH2)n or Rg - (~H)n or R8 - (Rlo ~ Rll) wherein n is 1 or 2 and R8, Rg, Rlo and Rll are independently selected from straight or branched chain , 3S 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. Et~oxylated or propoxylated materials are particularly preferred.
W093/012~ PCT/US92/05393 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;
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. 3,5~9,485, 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.
.
,, , , ., . ,, ,, ,, , ~ .. .. ...... , , ., . .. .. , .. .. , ,., Wo~3/012~ PCT/US92/05393 . . ~
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 W090~12656. This composition is a five component -~
composition containing a chlorina~ed 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 ethylens glycol~ In addition to the concers about polyol toxacology, volatilization of the polyols during heat curinq 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 environDentally friendly that the polyol containing composition.
WO93/012~ 2 1 1 2 2 3 ~ PCT/US92/05393 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 molecuIar 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 s,ooo to 45,000, a softening point in the range of 75 to 105C 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.5. 3,579,485. In a preferred embodiment, the chlorinated polyolefin has a molecular weig~t in the range of 9,000 to 16,000, a softening point in the range of 80 to 95C and an amount of chlorine in the ran~e of -~
l8 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 charqe~ 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 W093/012~ PCT/US92/053g3 . .
~ 4 _ 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 ranqe of 20 to 25 weight %, based on the weight of t~e 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.
2S 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:
... :
Rl - ~ R3 ; or Rl ~ R3 5 ; or W093/012~ 2 1 1 2 2 ~ o PCT~US92~0s393 R2 R~ R6 Rl ~ R3 _ ~ R5 ~ - R
wherein Rl = R7 are independently selected from H or straight or branched chain alkyl, hydroxyalkyl, or alkoxylalkyl groups of 1 to 20 carbon atoms; Rl - 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 Rl - R
is specifically substituted with or contains one or more hydroxyl (-OH) functionalities.
Another group of preferred amines can be represented by the formulae:
2S Rg Rg R8 - (NH2)n or Rg - (~H)n or R8 - (Rlo ~ Rll) wherein n is 1 or 2 and R8, Rg, Rlo and Rll are independently selected from straight or branched chain , 3S 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. Et~oxylated or propoxylated materials are particularly preferred.
W093/012~ PCT/US92/05393 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)aminol-2-propanol;
N,N'-bis(2-hydroxyethyl)ethylenediamine;
decylamine;
1,4-diaminobutane;
l,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;
WOg3/012~ PCT/US92/05393 21~22~
1,3-diaminopropane;
dibutylamine;
3-(dibutylamino)propylamine;
diethanolamine;
S diethylamine;
5-diethylamino-2-pentanol;
3-(diethylamino)-1,2-propanediol;
l-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;
l-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;
WO93/012~ PCT/US92/05393 (+)-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;
l-methylbutylamine;
WO93/012~ PCT/US92/0539~
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 a}so 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 reguired 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 W093/0l2~ PCT/US92/053g3 q~ 10~
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 Ieast 40 weight % water in the composition, based on the weight of the total composition, in order to form an admixture with p~urable 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 formu}ations, 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 WO93/012~ PCT/US92/05393 `i 2112231) ``
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 S 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 adaitives and then applying the diluted composition to a polyolefin substrate to form a coating using conventional means, such as spraying, brushing or dipping. ~fter 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 resultinq admixture is applied to the polyolefin substrate to form a single coatinq which adheres to the polyolefin substrate. , WO93/012~ PCT/US92/05393 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 100C to 150C, 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 120C, 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, æome authorities characterize water containing admixtures wherein the particle size in the range of 0.1 to lO microns as an "emulsionsn. 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 WO93/012~ PCT/US92/05393 i 21~22311 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 foll~wing 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 120C and the resulting pressure wàs 30 psi. This temperature and pressure was i~
maintained and the vessel was agitated for 20 minutes. ~
: "
' ExamDle 1 ;~:
This example illustrates preparation~of a composition of the invention using a particular chlorinated poIyolefin, one type of nonionic surfactant and a ~econdary 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 95C 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 ch~rged to the ~;
vessel and the above described procedure undertaken.
The resultant composition was diluted with ~ufficient WO93/012~ PCT/US92/05393 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 polyol~fin 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 160DF.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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: lOQ%
~xam~le 2 This e~ample 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 WO93/012~ 2 1 1 2 2 3 0 PCT/USg2/05393 chlorinated polyolefin, based on the weight of the total composition. This composition was applied to polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 100% ~;
.
Exa D le 3 This example illustrates preparation of a composition of the invention using the same chlorinated polyolefin use* in Example l, the same nonionic 1'.' ~
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 -;
2S grams of triethanol amine and 114 grams of water are - introduced into the vesæel 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
WO93/012~ PCT/US92/05393 Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 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 amîne and 114 grams of water are ~
introduced into the vessel and the above described ~`
procèdure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chIorinated polyolefin, based on the weight of the total ~-~
composition. This composition was applied to polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F. `~
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling `~
Stability at 125F for 4 weeks: Slight settling WO93/012~ PCT/US92/05393 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 TP0: 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 TP0 by spraying and then dried by ba~ing for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests -are as follows:
Stability at 75~ for 8 weeks: Slight settling &tability at 125F 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 fol~ows:
W~93/012~ PCT/US92/05393 G
Paint adhesion on polypropylene: 50%
Paint adhesion on TP0: 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows: -~
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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~STN D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 35%
Paint adhesion on TP0: 100%
W093/0l2~ PCT/US92/053g3 21~22~0 Exam~le 7 This example illustrates preparation of a composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonion~c 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 `i primer coating composition composed of 8 percent `
chlorinated polyolefin, based on the weight ofthe total `~
composition. This composition was applied to `~
polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F. ~;
Storaqe stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows~
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 100%
.
ExamDle 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.
-WO93/012~ PCT/US92/05393 s~
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 TP0 by spraying and then dried by baking for 10 minutes at 160F. ;
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settlinq Stability at 125F for 4 weeks: Slight settling Freeze~thaw stability tests were conducted in ~-~
accordance with ASTM D 2243 with visual inspection.
Result~ 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 TP0: 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, lO grams of surfactant, 2 grams of triethanolamine and 114 grams of water are introduced into the vessel and the above described W093/012~ PCT/US92/05393 2112~0 ~
' "
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 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 ~ 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 Cll-C15 ; 30 secondary ethyloxylated alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel --and the above deQcribed procedure undertaken. The `
resultant composition was diluted with sufficient additional water to result in a primer coating composition co~posed of 8 percent chlorinated WO93/012~ P~T/US92/05393 polyolefin, based on the weight of the total composition. This composition was applied to p~lypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F for 4 weeks: Slight settling Freeze~thaw stability tests were conducted in accordance with ASTM D 2243 with ~isual 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 TP0: 100%
Example 11 This example illustrates preparation of a composition of the inv,ention 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
W O 93/01244 PC~r/US92/05393 21122~0 Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling ~`
Stability at 125F for 4 weekc: 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 TP0: 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
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)aminol-2-propanol;
N,N'-bis(2-hydroxyethyl)ethylenediamine;
decylamine;
1,4-diaminobutane;
l,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;
WOg3/012~ PCT/US92/05393 21~22~
1,3-diaminopropane;
dibutylamine;
3-(dibutylamino)propylamine;
diethanolamine;
S diethylamine;
5-diethylamino-2-pentanol;
3-(diethylamino)-1,2-propanediol;
l-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;
l-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;
WO93/012~ PCT/US92/05393 (+)-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;
l-methylbutylamine;
WO93/012~ PCT/US92/0539~
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 a}so 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 reguired 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 W093/0l2~ PCT/US92/053g3 q~ 10~
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 Ieast 40 weight % water in the composition, based on the weight of the total composition, in order to form an admixture with p~urable 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 formu}ations, 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 WO93/012~ PCT/US92/05393 `i 2112231) ``
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 S 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 adaitives and then applying the diluted composition to a polyolefin substrate to form a coating using conventional means, such as spraying, brushing or dipping. ~fter 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 resultinq admixture is applied to the polyolefin substrate to form a single coatinq which adheres to the polyolefin substrate. , WO93/012~ PCT/US92/05393 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 100C to 150C, 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 120C, 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, æome authorities characterize water containing admixtures wherein the particle size in the range of 0.1 to lO microns as an "emulsionsn. 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 WO93/012~ PCT/US92/05393 i 21~22311 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 foll~wing 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 120C and the resulting pressure wàs 30 psi. This temperature and pressure was i~
maintained and the vessel was agitated for 20 minutes. ~
: "
' ExamDle 1 ;~:
This example illustrates preparation~of a composition of the invention using a particular chlorinated poIyolefin, one type of nonionic surfactant and a ~econdary 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 95C 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 ch~rged to the ~;
vessel and the above described procedure undertaken.
The resultant composition was diluted with ~ufficient WO93/012~ PCT/US92/05393 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 polyol~fin 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 160DF.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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: lOQ%
~xam~le 2 This e~ample 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 WO93/012~ 2 1 1 2 2 3 0 PCT/USg2/05393 chlorinated polyolefin, based on the weight of the total composition. This composition was applied to polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 100% ~;
.
Exa D le 3 This example illustrates preparation of a composition of the invention using the same chlorinated polyolefin use* in Example l, the same nonionic 1'.' ~
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 -;
2S grams of triethanol amine and 114 grams of water are - introduced into the vesæel 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
WO93/012~ PCT/US92/05393 Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 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 amîne and 114 grams of water are ~
introduced into the vessel and the above described ~`
procèdure undertaken. The resultant composition was diluted with sufficient additional water to result in a primer coating composition composed of 8 percent chIorinated polyolefin, based on the weight of the total ~-~
composition. This composition was applied to polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F. `~
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling `~
Stability at 125F for 4 weeks: Slight settling WO93/012~ PCT/US92/05393 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 TP0: 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 TP0 by spraying and then dried by ba~ing for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests -are as follows:
Stability at 75~ for 8 weeks: Slight settling &tability at 125F 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 fol~ows:
W~93/012~ PCT/US92/05393 G
Paint adhesion on polypropylene: 50%
Paint adhesion on TP0: 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows: -~
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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~STN D 3359-83, Method A. Results of this test were as follows:
Paint adhesion on polypropylene: 35%
Paint adhesion on TP0: 100%
W093/0l2~ PCT/US92/053g3 21~22~0 Exam~le 7 This example illustrates preparation of a composition of the invention using the same chlorinated polyolefin used in Example 1, the same nonion~c 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 `i primer coating composition composed of 8 percent `
chlorinated polyolefin, based on the weight ofthe total `~
composition. This composition was applied to `~
polypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F. ~;
Storaqe stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows~
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 TP0: 100%
.
ExamDle 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.
-WO93/012~ PCT/US92/05393 s~
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 TP0 by spraying and then dried by baking for 10 minutes at 160F. ;
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settlinq Stability at 125F for 4 weeks: Slight settling Freeze~thaw stability tests were conducted in ~-~
accordance with ASTM D 2243 with visual inspection.
Result~ 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 TP0: 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, lO grams of surfactant, 2 grams of triethanolamine and 114 grams of water are introduced into the vessel and the above described W093/012~ PCT/US92/05393 2112~0 ~
' "
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 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F 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 ~ 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 Cll-C15 ; 30 secondary ethyloxylated alcohol, 2 grams of morpholine and 114 grams of water are introduced into the vessel --and the above deQcribed procedure undertaken. The `
resultant composition was diluted with sufficient additional water to result in a primer coating composition co~posed of 8 percent chlorinated WO93/012~ P~T/US92/05393 polyolefin, based on the weight of the total composition. This composition was applied to p~lypropylene and TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F for 4 weeks: Slight settling Freeze~thaw stability tests were conducted in accordance with ASTM D 2243 with ~isual 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 TP0: 100%
Example 11 This example illustrates preparation of a composition of the inv,ention 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
W O 93/01244 PC~r/US92/05393 21122~0 Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling ~`
Stability at 125F for 4 weekc: 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 TP0: 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 TP0 by spraying and then dried by baking for 10 minutes at 160F.
Storage stability tests were conducted by visual inspection in glass jars. The results of these tests are as follows:
Stability at 75F for 8 weeks: Slight settling Stability at 125F for 4 weeks: Slight settling Freeze~thaw stability tests were conducted in accordance with ASTM D 2243 with visual inspection.
Re~sults 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 TP0: 100%
Re~sults 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 TP0: 100%
Claims (11)
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.
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72426691A | 1991-07-01 | 1991-07-01 | |
| US07/724,266 | 1991-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2112230A1 true CA2112230A1 (en) | 1993-01-21 |
Family
ID=24909731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002112230A Abandoned CA2112230A1 (en) | 1991-07-01 | 1992-06-25 | Aqueous coating composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0594691A1 (en) |
| JP (1) | JPH06509130A (en) |
| KR (1) | KR940701432A (en) |
| CA (1) | CA2112230A1 (en) |
| WO (1) | WO1993001244A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP0925121B1 (en) * | 1996-09-03 | 2001-06-20 | E.I. Du Pont De Nemours And Company | Motor vehicle multilayered enamelling process |
| 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 |
| CA2892825C (en) * | 2012-11-30 | 2021-08-10 | Angus Chemical Company | Aminoalcohol compounds as low voc free-thaw stabilizers for paints and coatings |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP3144560B2 (en) * | 1989-04-20 | 2001-03-12 | エイ ― ライン プロダクツ コーポレイション | Aqueous paint composition |
-
1992
- 1992-06-25 CA CA002112230A patent/CA2112230A1/en not_active Abandoned
- 1992-06-25 EP EP92914881A patent/EP0594691A1/en not_active Withdrawn
- 1992-06-25 WO PCT/US1992/005393 patent/WO1993001244A1/en not_active Application Discontinuation
- 1992-06-25 JP JP5502255A patent/JPH06509130A/en active Pending
- 1992-06-25 KR KR1019930704085A patent/KR940701432A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06509130A (en) | 1994-10-13 |
| WO1993001244A1 (en) | 1993-01-21 |
| EP0594691A1 (en) | 1994-05-04 |
| KR940701432A (en) | 1994-05-28 |
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