CA2028677A1 - Aqueous polymer dispersions and a process for their production - Google Patents
Aqueous polymer dispersions and a process for their productionInfo
- Publication number
- CA2028677A1 CA2028677A1 CA 2028677 CA2028677A CA2028677A1 CA 2028677 A1 CA2028677 A1 CA 2028677A1 CA 2028677 CA2028677 CA 2028677 CA 2028677 A CA2028677 A CA 2028677A CA 2028677 A1 CA2028677 A1 CA 2028677A1
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- Prior art keywords
- weight
- chlorinated
- polymer
- dispersion
- water
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C08L57/08—Homopolymers or copolymers containing elements other than carbon and hydrogen containing halogen atoms
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- 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
- C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
- C09D195/005—Aqueous compositions, e.g. emulsions
Abstract
AQUEOUS POLYMER DISPERSIONS AND
A PROCESS FOR THEIR PRODUCTION
ABSTRACT OF THE DISCLOSURE
The present invention relates to an aqueous polymer dispersion containing at most 22% by weight of organic solvents and 30 to 60% by weight of dispersed polymers, characterized in that the dispersed polymers contain A) 20 to 80% by weight of chlorinated, natural or synthetic polymers having a chlorine content of 60 to 70% by weight and B) 20 to 80% by weight of non-chlorinated polymers.
The present invention also relates to a process for the production of an aqueous polymer dispersion characterized in that an at least 50% by weight solution in an inert solvent of a chlorinated, natural or synthetic polymer A) having a chlorine content of 60 to 70% by weight is mixed with water in the presence of external emulsifiers to form a water-in-oil emulsion and subsequently the water-in-oil emulsion is combined with an aqueous dispersion of at least one non-chlorinated polymer to form an oil-in-water dispersion, wherein the type of and quantitative ratios between the individual components are selected such that the resulting dispersion has a solvent content of at most 22% by weight, a dispersed polymer content of 30 to 60% by weight and a weight ratio of chlorine-containing polymers A) to non-chlorinated polymers B) of 80:20 to 20:80.
A PROCESS FOR THEIR PRODUCTION
ABSTRACT OF THE DISCLOSURE
The present invention relates to an aqueous polymer dispersion containing at most 22% by weight of organic solvents and 30 to 60% by weight of dispersed polymers, characterized in that the dispersed polymers contain A) 20 to 80% by weight of chlorinated, natural or synthetic polymers having a chlorine content of 60 to 70% by weight and B) 20 to 80% by weight of non-chlorinated polymers.
The present invention also relates to a process for the production of an aqueous polymer dispersion characterized in that an at least 50% by weight solution in an inert solvent of a chlorinated, natural or synthetic polymer A) having a chlorine content of 60 to 70% by weight is mixed with water in the presence of external emulsifiers to form a water-in-oil emulsion and subsequently the water-in-oil emulsion is combined with an aqueous dispersion of at least one non-chlorinated polymer to form an oil-in-water dispersion, wherein the type of and quantitative ratios between the individual components are selected such that the resulting dispersion has a solvent content of at most 22% by weight, a dispersed polymer content of 30 to 60% by weight and a weight ratio of chlorine-containing polymers A) to non-chlorinated polymers B) of 80:20 to 20:80.
Description
` 2~2~77 Mo3485 LeA 21,298 AQUEOUS POLYMER DISPERSIONS AND
A PROCESS FOR THEIR PRODUC~ION ~ -BACKGROUND OF THE INVENTION ;~i ~
. .:
Field of the Invention This invention relates to a new aqueous polymer dispersion wherein the disperse phase is basecl on a mixture of certain chlorine-containing polymers and certain chlorine-free copolymers of olefin1cally unsaturated monomers and to a process for their production.
10Description of the Prior Art Chlorinated, natural or synthetic polymers, such as chlorinated natural rubber, chlorinated polyethylene and chlorinated rubber obtained by chlorination of synthetic rubber (homopolymers and copolymers of butadiene and/or isoprene), are known. These chlorine-containing polymers are used for various ; àpplications, including the production of coating compositions for various substrates, the production of adhesives and the production of printing inks. The raw materials in question are ` generally processed from~organic solutions wherein the viscosity can unfortunately increase considerably with ~; increasing molecular weight of the chlorinated polymers, so ~ that in many cases the raw materials can only be processed from ;~ highly dilute solutions, i.e., those having a solvent content above 50% by weight.
Reducing the organic solvent content to make the end products, particularly paints, more environmentally friendly is not possible in practice. In addition, there are very narrow limits to the use of relatively low-viscosity chlorinated , rubbers because~the savingiof solvent in the final preparation iS minimal and, in addition, the chlorinated rubbers of different viscosity stages are distinguished by differences, in some cases, considerable differences, in their property spectrum. ~ -~`: :
:~ 35376TWR0969 202~77 Chlorine-containing polymers dissolved in organic solvents, especially chlorinated rubbers dissolved in organic solvents, can be emulsified in water. However, the solids content of the solution to be emulsified is limited because, with increasing concentration, manipulatability becomes increasingly limited due to the increase in viscosity. For example, if the viscosity of the chlorinated rubber solut;on in organic solvents exceeds a value of about 8000 mPa.s, further processing at room temperature is seriously complicated or even impossible~
Viscosities of this order are achieved, for example in the case of solutions in solvent naphtha, with a chlorinated rubber having an average molecular weight of approximately 60,000 (all ~ molecular weight data for the chlorinated polymers are based on :: 15 the weight average molecular weight, Mw, determined on a 0.1%
; solution at 20QC by the interference Archibald method using an ultracentrifuge) and a solids concentration of 60% by weight at approximately 23DC. A chlorinated rubber having an average molecular weight of 85,000 reaches this viscosity range when ` 20 adjusted to a solids concentration of approximately 50% by weight at approximately 23C~ while a product having an average molecular weight of 135,000 and a solids concentration of 50%
by weight has to be heated to 60 to 70C in order to reduce the viscosity to this range, which is necessary for further : 25 processing.
If a 50% by weight solution of a chlorinated rubber having an average molecular weight of 85,000 in solvent naphtha 100 is mixed with water containing an emulsifier by using shear forces (for example in a dissolver), an emulsion is initially formed ` i ` 30 which is organophilic in the outer phase, but hydrophilic in the inner phase. This means that dilutability with water in the absence of shear forces and cleaning of the units used for ~; application with~water is not possible. If more emulsifier-containing water is added to the water-in-oil emulsion (w/o 35: emulsion) in the presence of shear forces, the emulsion Mo3485 2~2g~
A PROCESS FOR THEIR PRODUC~ION ~ -BACKGROUND OF THE INVENTION ;~i ~
. .:
Field of the Invention This invention relates to a new aqueous polymer dispersion wherein the disperse phase is basecl on a mixture of certain chlorine-containing polymers and certain chlorine-free copolymers of olefin1cally unsaturated monomers and to a process for their production.
10Description of the Prior Art Chlorinated, natural or synthetic polymers, such as chlorinated natural rubber, chlorinated polyethylene and chlorinated rubber obtained by chlorination of synthetic rubber (homopolymers and copolymers of butadiene and/or isoprene), are known. These chlorine-containing polymers are used for various ; àpplications, including the production of coating compositions for various substrates, the production of adhesives and the production of printing inks. The raw materials in question are ` generally processed from~organic solutions wherein the viscosity can unfortunately increase considerably with ~; increasing molecular weight of the chlorinated polymers, so ~ that in many cases the raw materials can only be processed from ;~ highly dilute solutions, i.e., those having a solvent content above 50% by weight.
Reducing the organic solvent content to make the end products, particularly paints, more environmentally friendly is not possible in practice. In addition, there are very narrow limits to the use of relatively low-viscosity chlorinated , rubbers because~the savingiof solvent in the final preparation iS minimal and, in addition, the chlorinated rubbers of different viscosity stages are distinguished by differences, in some cases, considerable differences, in their property spectrum. ~ -~`: :
:~ 35376TWR0969 202~77 Chlorine-containing polymers dissolved in organic solvents, especially chlorinated rubbers dissolved in organic solvents, can be emulsified in water. However, the solids content of the solution to be emulsified is limited because, with increasing concentration, manipulatability becomes increasingly limited due to the increase in viscosity. For example, if the viscosity of the chlorinated rubber solut;on in organic solvents exceeds a value of about 8000 mPa.s, further processing at room temperature is seriously complicated or even impossible~
Viscosities of this order are achieved, for example in the case of solutions in solvent naphtha, with a chlorinated rubber having an average molecular weight of approximately 60,000 (all ~ molecular weight data for the chlorinated polymers are based on :: 15 the weight average molecular weight, Mw, determined on a 0.1%
; solution at 20QC by the interference Archibald method using an ultracentrifuge) and a solids concentration of 60% by weight at approximately 23DC. A chlorinated rubber having an average molecular weight of 85,000 reaches this viscosity range when ` 20 adjusted to a solids concentration of approximately 50% by weight at approximately 23C~ while a product having an average molecular weight of 135,000 and a solids concentration of 50%
by weight has to be heated to 60 to 70C in order to reduce the viscosity to this range, which is necessary for further : 25 processing.
If a 50% by weight solution of a chlorinated rubber having an average molecular weight of 85,000 in solvent naphtha 100 is mixed with water containing an emulsifier by using shear forces (for example in a dissolver), an emulsion is initially formed ` i ` 30 which is organophilic in the outer phase, but hydrophilic in the inner phase. This means that dilutability with water in the absence of shear forces and cleaning of the units used for ~; application with~water is not possible. If more emulsifier-containing water is added to the water-in-oil emulsion (w/o 35: emulsion) in the presence of shear forces, the emulsion Mo3485 2~2g~
ultimately undergoes phase reversal, so that an oil-in-water emulsion (o/w emulsion) is formed. Depending upon the type of chlorinated rubber, the type and quantity of solvent and the application of shear forces, the solids concentration at the phase reversal stage is about 20 to 30~0 by weight. This means that aqueous o/w emulsions of chlorinated rubber in water can have a maximum s017ds content of about 30% by weight which, of course, seriously impairs the economy of such aqueous emulsions because at least 70% of the transport and storage costs are o attributable to the organic solvent and water.
Accordingly, an object of the present invention was to develop an aqueous binder containing chlorinated polymers which can be diluted with water, contains at most 22% by weight of organic solvents and has a solids content of at least 30% by weight.
This object was solved by the process according to the invention, which is described in detail hereinafter and the aqueous polymer dispersions resulting therefrom.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous polymer dispersion containing at most 22% by weight of organic solvents and 30 to 60% by weight of dispersed polymers, characterized in that the dispersed polymers contain A) 20 to 80% by weight of chlorinated, natural or synthetic polymers having a chlorine content of 60 to 70% by weight and B) 20 to 80% by weight of non-chlorinated polymers.
The present invention also relates to a process for the production of an aqueous polymer dispersion characterized in that an at least 50% by weight solution in an inert solvent of a chlorinated, natural or synthetic polymer A) having a chlorine content of 60 to 70% by weight is mixed with water in the presence of external emulsifiers to form a water-in-oil emulsion and subsequently the water-in-oil emulsion is combined with an aqueous dispersion of at least one non-chlorinated Mo3485 polymer to form an oil-in-water dispersion, wherein the type of and quantitative ratios between the individual components are selected such that the resulting dispersion has a solvent content of at most 22% by weight, a dispersed polymer content of 30 to 60% by weight and a weight ratio of chlorine-containing polymers A) to non-chlorinated polymerç B) of 80:20 to 20:80.
DETAILED DESCRIPTION OF THE INVENTION
Starting materials for the process according to the o invention are A) chlorinated polymers and B) chlorine-free polymers.
The chlorinated polymers are either chlorinated olefins, particularly chlorinated polyethylene, having a chlorine content of 60 to 70% by weight or chlorinated rubbers having a chlorine content of 60 to 70% by weight, preferably 64 to 68%
by weight, and an average molecular weight of up to 185,000, preferably 60,000 to 185,000 and more preferably 60,000 to 135,000. In the context of the invention, the expression "chlorinated rubber" is intended to encompass both chlorinated 20 . natural rubber and also chlorinated homopolymers and copolymers of butadiene and isoprene.
` The chlorine-free polymers B) include, ;n particular, "polyacrylates," i.e., copolymers prepared from at least one alkyl ester of acrylic or methacrylic acid with other i 25 olefinically unsaturated monomers such as styrene, metha-crylonitrile, acrylonitrile, methacrylamide, acrylamide, methacrylic acid, acrylic acid and/or monomers containing groups capable of crosslinking reactions such as N-methoxy-methyl methacrylamide or N-methoxymethyl acrylamide.
30 i Copolymers of a) 20 to 50% by weight styrene, ~ b) 30 to 70% by weight of at least one C1 6 alkyl ester of ; acrylic or~methacrylic acid, c) O to 10% by weight acrylic acid and/or methacrylic acid and Mo3485 ff`. r~
202~7~
Accordingly, an object of the present invention was to develop an aqueous binder containing chlorinated polymers which can be diluted with water, contains at most 22% by weight of organic solvents and has a solids content of at least 30% by weight.
This object was solved by the process according to the invention, which is described in detail hereinafter and the aqueous polymer dispersions resulting therefrom.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous polymer dispersion containing at most 22% by weight of organic solvents and 30 to 60% by weight of dispersed polymers, characterized in that the dispersed polymers contain A) 20 to 80% by weight of chlorinated, natural or synthetic polymers having a chlorine content of 60 to 70% by weight and B) 20 to 80% by weight of non-chlorinated polymers.
The present invention also relates to a process for the production of an aqueous polymer dispersion characterized in that an at least 50% by weight solution in an inert solvent of a chlorinated, natural or synthetic polymer A) having a chlorine content of 60 to 70% by weight is mixed with water in the presence of external emulsifiers to form a water-in-oil emulsion and subsequently the water-in-oil emulsion is combined with an aqueous dispersion of at least one non-chlorinated Mo3485 polymer to form an oil-in-water dispersion, wherein the type of and quantitative ratios between the individual components are selected such that the resulting dispersion has a solvent content of at most 22% by weight, a dispersed polymer content of 30 to 60% by weight and a weight ratio of chlorine-containing polymers A) to non-chlorinated polymerç B) of 80:20 to 20:80.
DETAILED DESCRIPTION OF THE INVENTION
Starting materials for the process according to the o invention are A) chlorinated polymers and B) chlorine-free polymers.
The chlorinated polymers are either chlorinated olefins, particularly chlorinated polyethylene, having a chlorine content of 60 to 70% by weight or chlorinated rubbers having a chlorine content of 60 to 70% by weight, preferably 64 to 68%
by weight, and an average molecular weight of up to 185,000, preferably 60,000 to 185,000 and more preferably 60,000 to 135,000. In the context of the invention, the expression "chlorinated rubber" is intended to encompass both chlorinated 20 . natural rubber and also chlorinated homopolymers and copolymers of butadiene and isoprene.
` The chlorine-free polymers B) include, ;n particular, "polyacrylates," i.e., copolymers prepared from at least one alkyl ester of acrylic or methacrylic acid with other i 25 olefinically unsaturated monomers such as styrene, metha-crylonitrile, acrylonitrile, methacrylamide, acrylamide, methacrylic acid, acrylic acid and/or monomers containing groups capable of crosslinking reactions such as N-methoxy-methyl methacrylamide or N-methoxymethyl acrylamide.
30 i Copolymers of a) 20 to 50% by weight styrene, ~ b) 30 to 70% by weight of at least one C1 6 alkyl ester of ; acrylic or~methacrylic acid, c) O to 10% by weight acrylic acid and/or methacrylic acid and Mo3485 ff`. r~
202~7~
d) 0 to 20% by weight of other olefinically unsaturated monomers, wherein the percentages add up to 100, are particularly preferred.
The chlorine-free polymers are generally copolymers produced by radical polymerization which are used in the form of aqueous dispersions having solids contents of 30 to 60% by weight in the process according to the invention. The carboxyl groups of the copolymers are generally present in the dispersions in amine-neutralized or, more particularly, ammonia-neutralized form. In addition, the dispersions generally contain external emulsifiers in quantities of about 0.2 to 2.0% by weight. Polymers which are particularly suitable as component B) include the aqueous polymer dispersions marketed by Bayer AG, Leverkusen, under the names Ercusol 160 and Ercusol AS 250.
In addition, suitable auxiliaries for carrying out the process according to the invention include:
- Inert solvents, preferably those which do not have to be 20......... identified by law as hazardous materials. Suitable solvents include aromatic hydrocarbon solvents which are commercially available as "solvent naphtha," esters (such as ethyl or butyl acetate)5 ketones (such as methyl ethyl ketone or methyl isobutyl ketone) or mixtures of such sol vents.
- Plasticizers for the chlorine-containing polymers A) such i as adipic acid dibutyl ester, phthalic acid dibutyl ester, phosphoric acid tributyl ester or trihexyl ester, chlorinated paraffins or C10 14 alkane sulfonic acid 30 i phenyl esters present and commercially available as homolog mixtures (e.g., the plasticizer marketed by Bayer AG, Leverkusen, under the name Mesamoll).
- Emulsifiers for the production of a w/o emulsion of the chlorinated polymers such as ethoxylation products of substituted phenols, for example isononyl phenol Dr Mo3485 s ~:
20~6~7 bis(phenylethyl)-phenol, in which 10 to 50, preferably 10 to 20 ethylene oxide units, in the form of polyether chains are present per molecule.
- Foam inhibitors such as "Entschaumer PA 49," a product of Bayer AG, or Fsamex I488, a product of Th. Goldschmidt AG.
The first step of the process according to the invention, i.e., preparation of the aqueous w/o emulsion of the chlorinated polymer, may be carried out in two ways.
In a first variant, a highly concentrated solution of a chlorinated polymer in which the solvent content corresponds to a maximum viscosity at 23C of 10,000, preferably at most 6000 mPa.s, is initially introduced and plasticizers, emulsifiers or other additives are optionally added thereto. Water9 preferably demineralized water, is then introduced into the dispersion with intensive stirring, an emulsifier optionally being added to the water in a quantity sufficient to emulsify the chlorinated~polymer unless such a quantity of emulsifier was incorporated in the organic solution beforehand. A w/o emulsion is formed through the uniform introduction of the :`: 20 water in the presence of shear forces. The introduction of water is stopped when the solids content of the w/o emulsion has fallen to 30 to 60% by weight, preferably 40 to 50% by weight.
In a second variant of the first step of the process according to the invention, a solution of a chlorinated polymer in~an inert solvent having a solids content of more than 50% by weight, preferably at least 60% by weight, is heated to approximately 60 to 80C and emulsified in water at that temperature. The emulsifier required for emulsifiability is ~` i 30 incorporated beforehand iniat least one of the two components.
In this variant, an o/w emulsion is initially formed. The phase reversil to w/o~only takes place during the continuing introduction of the solution of the chlorinated polymer and at the latest when the entire quantity of solution has been ~` 35 emulsified. The amount of solution corresponds to a solids Mo3485 20~677 content of the resulting w/o emulsion of at least 30% by weight, preferably at least 40% by weight.
Regardless of the method used to prepare the w/o emulsion formed as an intermediate stage, it is subsequently mixed with polymer dispersion B). The water content or polymer dispersion B) causes a phase reversal from w/o to o/w without the sollds content of the resulting dispersion being significantly reduced.
In accordance with the process of the present invention, the type of components and the ratios in which they are blended are selected such that the resulting dispersion has a maximum solvent content of 22% by weight; a total content of dispersed polymers A) and B) of 30 to 60% by weight; and a ratio by weight between the polymers A) and B) of 80:20 to 20:80, preferably 60:40 to 40:60.
The polymer dispersions according to the invention ~- prepared in this way, without further additives, are valuable coating compositions for various substrates. However, they may also be blended with thP auxiliaries and additives typically ` 20 used in coatings technology such as pigments, foam inhibitors, pigment dispersant and flow control agents. Particularly interesting corrosion-inhibiting properties are obtained by the addition of bitumen emulsions maintaining a weight ratio of dispersed polymers to bitumen of from O,S:l to 3:1. Thus steel plates coated with a composi~ion containing . 25 a dispersion according to the inventionanda bitumen emulsion (ratio by weight of dispersed polymers to bitumen = 1:1) showed no visible change after 42 days in a :
salt spray test (3% NaCl).
`~ The following examples are intended to illustrate the invention. All parts and percentages are by weight unless i 30 otherwise indicated.
Examples The following starting materials were used in Examples 1 to 6 below:
Mo3485 2~2~6~7 Chlorinated rubber l:
Chlorinated synthetic rubber (poly-1,4-cis-isoprene), molecular we;ght 85,000, chlorine content: 66% by weight.
Chlorinated rubber II:
Chlorinated synthetic rubber (poly-1,4-cis-isoprene), molecular weight 135,000, chlorine content: 66% by weight.
Plasticizer:
Cl0 14 alkane sulfonic acid phenyl ester present as a homolog mixture.
Emulsifier:
Adduct of 13 moles of ethylene oxide with 1 mole of bis-(1-phenylethyl)-phenol.
Polvmer disDersion I:
A dispersion having a solids content of 42% by weight and based on a copolymer which is the reaction product of ; ~ 37.8% by weight styrene 55.9% by weight N-butyl acrylate 5.4% by weight methacrylic acid 0.9% by weight N-methoxymethyl methacrylamide - 20 . The dispersion was prepared by the process according to US-PS
2,978,432. The carboxyl groups were neutralized with ammonia.
PolYmer dispersion II:
A dispersion having a solids content of 50% by weight and based on a copolymer which is the reaction product of :~: 25 53.5% by weight N-butyl acrylate 5.0% by weight methacrylic acid 40.0% by weight styrene 1.5% by weight N-methoxymethyl methacrylamide.
The dispersion was prepared by the process according to US-PS
30 i 2,978,432. The carboxyl groups were neutralized with ammonia.
Foam Inhibitor:
Commercial foam inhibitor (Foamex 1488, a product of Th.
l~ Goldschmidt AG) ¦ Solvent naphtha 100:
Commercial solvent mixture containing aromatic alkyl-Mo3485 ` 2~2~677 g substituted hydrocarbons.
ExamDles 1 to 2 (Table 1) The chlorinated rubbers were d~ssolved in solvent naphtha 5 at room temperature to form a 47.5% by weight solution. The plasticizer was then stirred in, where indicated. The quantities of emulsifier and foam inhibitor set forth were then added and homogenized. The quantit1es of demineralized water shown were then introduced slowly and uniformly under the 0 effect of shear forces in a Pendraulik laboratory dissolver of Pendra~ik Maschinen und Apparate GmbH, Bad Munder, Germany. A w/o emulsion was formed. After adequate homogenization the polymer dispersion, -containing the amounts of emulsifier and foam inhibitor set forth, was added with continued stirring. The addition of the polymer dispersion resulted in phase reversal from w/o to o/w. --15 After a final emulsification period of about 20 minutes, the production was complete. The particle diameter of the dispersed phase was at most 500 nm. The dispersions obtained showed pseudo-plastic behavior and were white to pale yellowish in color. When dried through evaporation of the water and 20 . organic solvent, the dispersions formed light translucent films ~
having a matt-silk surface. They were especially suitable as -aqueous binders for the production of coating compositions for concrete or steel.
ExamDle 3 (Table 1) 2s This Example differs from Examples 1 and 2 in that the dissolving and emulsification process was carried out at a temperature of 60-C. The increase in temperature allowed the solids concentration of the chlorinated rubber solution to be increased to ~0% by weight and the organic solvent content to be reduced to 13% by weight.
ExamDle 4 (Table I) This Example differs from Examples 1 and ~ in that the dissolving and emulsification process was carried out at 60-C, which allowed a chlorinated rubber of higher molecular weight and also higher viscosity to be used.
Mo3485 202~77 Table 1 Formulat;ons for Examples 1 to 4 Chlorinated rubber I195.4 195.4 195.5 Chlorinated rubber II 195.4 Solvent naphtha 100216.0 216.2 130.1 216.0 Total parts 411.4 411.8 325.6 411.4 % Sol;ds 47.5 47.5 60.0 47.5 Operating temperature~C 23 23 60 60 Plasticizer 39.2 - 39.3 39.2 Emulsifier 22.5 19.6 22.5 22.5 Foam inhibitor 2.9 2.9 - 2.9 Incorporation by emulsification of Demineralized water 55.9 78.3 145.6 55.9 Foam inhibitor 1.9 After homogenization, incorporation by emulsification in the mixture of Polymer dispersion I465.2 464.2 465.1 465.2 Emulsifier 19.6 :-Foam inhibitor 2.9 2.9 2.9 Total parts 1000.0 1000.0 1000.0 1000.0 % Solids 45.4 43.2 45.4 45.4 % Solvent 21.6 21.6 13.0 21.6 % Water 33.0 35.2 41.6 33.0 ;:
Mo3485 202~67~
.:
Examples 5 and 6 (Table 2) Examples 5 and 6 differ from the preceding examples in that the chlorinated rubber solution was adjusted to a solids content of 60% by weight and the dissolving process and also 5 further processing were carried out at 80C. In the preceding examples a w/o emulsion was init;ally prepared by stirr;ng in water. The w/o emulsion underwent phase reversal to an o/w phase after the addition of the polyacrylate dispersion.
However, in Examples 5 and 6 the heated and also viscosity-reduced chlorinated rubber solution in an aqueous emulsifier solution was first emulsified to an o/w emulsion which underwent phase reversal to a w/o emulsion during the addition.
Phase reversal back to o/w occurred during the addition of the polymer dispersion. Dispersions having higher solids contents and reduced contents of organic solvents were obtained in this manner.
.
¦ Mo3485 ,.
~ :~,:.. ,. . . - : : .
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~"',`''.. ~'', ~' ` : '"
-12- 2~2~6~7 Table 2 ::
Formulations of Examples 5 and 6 Chlorinated rubber I 212.0 231.3 Solvent naphtha 100 141.0 153.8 Parts by weight 353.0 385.1 % Solids 60.0 60.0 lo . Operating temperature C 80 80 Plasticizer 42.8 46.7 ~:~ Emulsifier 24.3 26.5 Incorporation by emulsification of demineralized water 60.4 65.9 After homogenization, ;ncorporation by emulsification of Polymer dispersion I 519.5 ~: : Polymer dispersion II - 475.8 Total Parts 1000.01000.0 % Solids 49.7 54.2 ` ~ ~ 25 X Solvent 14.1 15.4 % Water 36.2 30.4 :
. .
~ Mo3485 ;`;~
.
2~2~677 Application ExamDles In the following Applica$ion Examples, the dispersions of Examples 1 to 6 were formulated with a pigment slurry and the other starting materials set forth in Table 3 to form 5 ready-to-use coat;ng compositions.
The pigment slurry contained a mixture of 95.23 parts Pigmentverteiler A ("Pigment Dispersant A", a product of BASF AG, Ludwigshafen), 3% in demineralized water 133.34 water : 791.90 titanium dioxide, rutile 9.53 Foam Inhibitor : 1000.00 total parts .
Table 3 (Composition of coating compositions) Products of Examples 0 P;gment slurry 1000 1000 1000 1000 1000 1000 :: Foam Inhibitor 2.8 2.8 2.8 2.8 2.8 2.8 : ~ Thickener 33.8 33.8 33.8 33.8 33.8 33.8 : Water 154.0 288.0 Dispersion1773 1773 1773 1773 1619 1485 Total Parts2809.62809.62809.6 2809.6 2809.6 2809.6 Acrysol RM 8, a product of Rohm & Haas, 10% in water : i `'~
..
Mo3485 ;:
.. ~. _ .. . .
~ ~ ;,~
14 202~77 Formulations of the coating compositions (Table 4) Table 4 (quantities in %) ; ~ 1 2 3 4 5 6 :
Binder incl. additives 29.0 27.6 29.0 29.0 29.0 29.0 Pigment 27.1 27.1 27.1 27.1 27.1 27.1 Total solids56.1 54.7 56.1 56.1 56.1 56.1 Org. solvent13.6 13.6 8.2 13.6 8.1 8.1 Water 30.3 31.7 35.7 30.3 35.8 35.8 Total 100.0 100.0 100.0 100.0 100.0 100.0 All the coating compositions thus prepared showed pseudo-plastic behavior and dried through evaporation of the water and ; ; the residual organic solvent to form a film with a homogeneous, matt-silk surface. The films adhered very firmly inter alia to steel, concrete and lightweight boards. They demonstrated good 0 corrosion-inhibiting behavior in accelerated salt-spray tests.
" ~ The good~result obtained after 2000 hours of accelerated weathering in a Xeno 1200 Weather-O-Meter suggests excellent weathering behavior.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can~be made therein by those skilled in the art ` without departing~from the spirit and scope of the invention ;
except as it~may be limited by the claims.
Mo3485 ' ; ..' ~
" '~'' ", .
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The chlorine-free polymers are generally copolymers produced by radical polymerization which are used in the form of aqueous dispersions having solids contents of 30 to 60% by weight in the process according to the invention. The carboxyl groups of the copolymers are generally present in the dispersions in amine-neutralized or, more particularly, ammonia-neutralized form. In addition, the dispersions generally contain external emulsifiers in quantities of about 0.2 to 2.0% by weight. Polymers which are particularly suitable as component B) include the aqueous polymer dispersions marketed by Bayer AG, Leverkusen, under the names Ercusol 160 and Ercusol AS 250.
In addition, suitable auxiliaries for carrying out the process according to the invention include:
- Inert solvents, preferably those which do not have to be 20......... identified by law as hazardous materials. Suitable solvents include aromatic hydrocarbon solvents which are commercially available as "solvent naphtha," esters (such as ethyl or butyl acetate)5 ketones (such as methyl ethyl ketone or methyl isobutyl ketone) or mixtures of such sol vents.
- Plasticizers for the chlorine-containing polymers A) such i as adipic acid dibutyl ester, phthalic acid dibutyl ester, phosphoric acid tributyl ester or trihexyl ester, chlorinated paraffins or C10 14 alkane sulfonic acid 30 i phenyl esters present and commercially available as homolog mixtures (e.g., the plasticizer marketed by Bayer AG, Leverkusen, under the name Mesamoll).
- Emulsifiers for the production of a w/o emulsion of the chlorinated polymers such as ethoxylation products of substituted phenols, for example isononyl phenol Dr Mo3485 s ~:
20~6~7 bis(phenylethyl)-phenol, in which 10 to 50, preferably 10 to 20 ethylene oxide units, in the form of polyether chains are present per molecule.
- Foam inhibitors such as "Entschaumer PA 49," a product of Bayer AG, or Fsamex I488, a product of Th. Goldschmidt AG.
The first step of the process according to the invention, i.e., preparation of the aqueous w/o emulsion of the chlorinated polymer, may be carried out in two ways.
In a first variant, a highly concentrated solution of a chlorinated polymer in which the solvent content corresponds to a maximum viscosity at 23C of 10,000, preferably at most 6000 mPa.s, is initially introduced and plasticizers, emulsifiers or other additives are optionally added thereto. Water9 preferably demineralized water, is then introduced into the dispersion with intensive stirring, an emulsifier optionally being added to the water in a quantity sufficient to emulsify the chlorinated~polymer unless such a quantity of emulsifier was incorporated in the organic solution beforehand. A w/o emulsion is formed through the uniform introduction of the :`: 20 water in the presence of shear forces. The introduction of water is stopped when the solids content of the w/o emulsion has fallen to 30 to 60% by weight, preferably 40 to 50% by weight.
In a second variant of the first step of the process according to the invention, a solution of a chlorinated polymer in~an inert solvent having a solids content of more than 50% by weight, preferably at least 60% by weight, is heated to approximately 60 to 80C and emulsified in water at that temperature. The emulsifier required for emulsifiability is ~` i 30 incorporated beforehand iniat least one of the two components.
In this variant, an o/w emulsion is initially formed. The phase reversil to w/o~only takes place during the continuing introduction of the solution of the chlorinated polymer and at the latest when the entire quantity of solution has been ~` 35 emulsified. The amount of solution corresponds to a solids Mo3485 20~677 content of the resulting w/o emulsion of at least 30% by weight, preferably at least 40% by weight.
Regardless of the method used to prepare the w/o emulsion formed as an intermediate stage, it is subsequently mixed with polymer dispersion B). The water content or polymer dispersion B) causes a phase reversal from w/o to o/w without the sollds content of the resulting dispersion being significantly reduced.
In accordance with the process of the present invention, the type of components and the ratios in which they are blended are selected such that the resulting dispersion has a maximum solvent content of 22% by weight; a total content of dispersed polymers A) and B) of 30 to 60% by weight; and a ratio by weight between the polymers A) and B) of 80:20 to 20:80, preferably 60:40 to 40:60.
The polymer dispersions according to the invention ~- prepared in this way, without further additives, are valuable coating compositions for various substrates. However, they may also be blended with thP auxiliaries and additives typically ` 20 used in coatings technology such as pigments, foam inhibitors, pigment dispersant and flow control agents. Particularly interesting corrosion-inhibiting properties are obtained by the addition of bitumen emulsions maintaining a weight ratio of dispersed polymers to bitumen of from O,S:l to 3:1. Thus steel plates coated with a composi~ion containing . 25 a dispersion according to the inventionanda bitumen emulsion (ratio by weight of dispersed polymers to bitumen = 1:1) showed no visible change after 42 days in a :
salt spray test (3% NaCl).
`~ The following examples are intended to illustrate the invention. All parts and percentages are by weight unless i 30 otherwise indicated.
Examples The following starting materials were used in Examples 1 to 6 below:
Mo3485 2~2~6~7 Chlorinated rubber l:
Chlorinated synthetic rubber (poly-1,4-cis-isoprene), molecular we;ght 85,000, chlorine content: 66% by weight.
Chlorinated rubber II:
Chlorinated synthetic rubber (poly-1,4-cis-isoprene), molecular weight 135,000, chlorine content: 66% by weight.
Plasticizer:
Cl0 14 alkane sulfonic acid phenyl ester present as a homolog mixture.
Emulsifier:
Adduct of 13 moles of ethylene oxide with 1 mole of bis-(1-phenylethyl)-phenol.
Polvmer disDersion I:
A dispersion having a solids content of 42% by weight and based on a copolymer which is the reaction product of ; ~ 37.8% by weight styrene 55.9% by weight N-butyl acrylate 5.4% by weight methacrylic acid 0.9% by weight N-methoxymethyl methacrylamide - 20 . The dispersion was prepared by the process according to US-PS
2,978,432. The carboxyl groups were neutralized with ammonia.
PolYmer dispersion II:
A dispersion having a solids content of 50% by weight and based on a copolymer which is the reaction product of :~: 25 53.5% by weight N-butyl acrylate 5.0% by weight methacrylic acid 40.0% by weight styrene 1.5% by weight N-methoxymethyl methacrylamide.
The dispersion was prepared by the process according to US-PS
30 i 2,978,432. The carboxyl groups were neutralized with ammonia.
Foam Inhibitor:
Commercial foam inhibitor (Foamex 1488, a product of Th.
l~ Goldschmidt AG) ¦ Solvent naphtha 100:
Commercial solvent mixture containing aromatic alkyl-Mo3485 ` 2~2~677 g substituted hydrocarbons.
ExamDles 1 to 2 (Table 1) The chlorinated rubbers were d~ssolved in solvent naphtha 5 at room temperature to form a 47.5% by weight solution. The plasticizer was then stirred in, where indicated. The quantities of emulsifier and foam inhibitor set forth were then added and homogenized. The quantit1es of demineralized water shown were then introduced slowly and uniformly under the 0 effect of shear forces in a Pendraulik laboratory dissolver of Pendra~ik Maschinen und Apparate GmbH, Bad Munder, Germany. A w/o emulsion was formed. After adequate homogenization the polymer dispersion, -containing the amounts of emulsifier and foam inhibitor set forth, was added with continued stirring. The addition of the polymer dispersion resulted in phase reversal from w/o to o/w. --15 After a final emulsification period of about 20 minutes, the production was complete. The particle diameter of the dispersed phase was at most 500 nm. The dispersions obtained showed pseudo-plastic behavior and were white to pale yellowish in color. When dried through evaporation of the water and 20 . organic solvent, the dispersions formed light translucent films ~
having a matt-silk surface. They were especially suitable as -aqueous binders for the production of coating compositions for concrete or steel.
ExamDle 3 (Table 1) 2s This Example differs from Examples 1 and 2 in that the dissolving and emulsification process was carried out at a temperature of 60-C. The increase in temperature allowed the solids concentration of the chlorinated rubber solution to be increased to ~0% by weight and the organic solvent content to be reduced to 13% by weight.
ExamDle 4 (Table I) This Example differs from Examples 1 and ~ in that the dissolving and emulsification process was carried out at 60-C, which allowed a chlorinated rubber of higher molecular weight and also higher viscosity to be used.
Mo3485 202~77 Table 1 Formulat;ons for Examples 1 to 4 Chlorinated rubber I195.4 195.4 195.5 Chlorinated rubber II 195.4 Solvent naphtha 100216.0 216.2 130.1 216.0 Total parts 411.4 411.8 325.6 411.4 % Sol;ds 47.5 47.5 60.0 47.5 Operating temperature~C 23 23 60 60 Plasticizer 39.2 - 39.3 39.2 Emulsifier 22.5 19.6 22.5 22.5 Foam inhibitor 2.9 2.9 - 2.9 Incorporation by emulsification of Demineralized water 55.9 78.3 145.6 55.9 Foam inhibitor 1.9 After homogenization, incorporation by emulsification in the mixture of Polymer dispersion I465.2 464.2 465.1 465.2 Emulsifier 19.6 :-Foam inhibitor 2.9 2.9 2.9 Total parts 1000.0 1000.0 1000.0 1000.0 % Solids 45.4 43.2 45.4 45.4 % Solvent 21.6 21.6 13.0 21.6 % Water 33.0 35.2 41.6 33.0 ;:
Mo3485 202~67~
.:
Examples 5 and 6 (Table 2) Examples 5 and 6 differ from the preceding examples in that the chlorinated rubber solution was adjusted to a solids content of 60% by weight and the dissolving process and also 5 further processing were carried out at 80C. In the preceding examples a w/o emulsion was init;ally prepared by stirr;ng in water. The w/o emulsion underwent phase reversal to an o/w phase after the addition of the polyacrylate dispersion.
However, in Examples 5 and 6 the heated and also viscosity-reduced chlorinated rubber solution in an aqueous emulsifier solution was first emulsified to an o/w emulsion which underwent phase reversal to a w/o emulsion during the addition.
Phase reversal back to o/w occurred during the addition of the polymer dispersion. Dispersions having higher solids contents and reduced contents of organic solvents were obtained in this manner.
.
¦ Mo3485 ,.
~ :~,:.. ,. . . - : : .
~?~
~"',`''.. ~'', ~' ` : '"
-12- 2~2~6~7 Table 2 ::
Formulations of Examples 5 and 6 Chlorinated rubber I 212.0 231.3 Solvent naphtha 100 141.0 153.8 Parts by weight 353.0 385.1 % Solids 60.0 60.0 lo . Operating temperature C 80 80 Plasticizer 42.8 46.7 ~:~ Emulsifier 24.3 26.5 Incorporation by emulsification of demineralized water 60.4 65.9 After homogenization, ;ncorporation by emulsification of Polymer dispersion I 519.5 ~: : Polymer dispersion II - 475.8 Total Parts 1000.01000.0 % Solids 49.7 54.2 ` ~ ~ 25 X Solvent 14.1 15.4 % Water 36.2 30.4 :
. .
~ Mo3485 ;`;~
.
2~2~677 Application ExamDles In the following Applica$ion Examples, the dispersions of Examples 1 to 6 were formulated with a pigment slurry and the other starting materials set forth in Table 3 to form 5 ready-to-use coat;ng compositions.
The pigment slurry contained a mixture of 95.23 parts Pigmentverteiler A ("Pigment Dispersant A", a product of BASF AG, Ludwigshafen), 3% in demineralized water 133.34 water : 791.90 titanium dioxide, rutile 9.53 Foam Inhibitor : 1000.00 total parts .
Table 3 (Composition of coating compositions) Products of Examples 0 P;gment slurry 1000 1000 1000 1000 1000 1000 :: Foam Inhibitor 2.8 2.8 2.8 2.8 2.8 2.8 : ~ Thickener 33.8 33.8 33.8 33.8 33.8 33.8 : Water 154.0 288.0 Dispersion1773 1773 1773 1773 1619 1485 Total Parts2809.62809.62809.6 2809.6 2809.6 2809.6 Acrysol RM 8, a product of Rohm & Haas, 10% in water : i `'~
..
Mo3485 ;:
.. ~. _ .. . .
~ ~ ;,~
14 202~77 Formulations of the coating compositions (Table 4) Table 4 (quantities in %) ; ~ 1 2 3 4 5 6 :
Binder incl. additives 29.0 27.6 29.0 29.0 29.0 29.0 Pigment 27.1 27.1 27.1 27.1 27.1 27.1 Total solids56.1 54.7 56.1 56.1 56.1 56.1 Org. solvent13.6 13.6 8.2 13.6 8.1 8.1 Water 30.3 31.7 35.7 30.3 35.8 35.8 Total 100.0 100.0 100.0 100.0 100.0 100.0 All the coating compositions thus prepared showed pseudo-plastic behavior and dried through evaporation of the water and ; ; the residual organic solvent to form a film with a homogeneous, matt-silk surface. The films adhered very firmly inter alia to steel, concrete and lightweight boards. They demonstrated good 0 corrosion-inhibiting behavior in accelerated salt-spray tests.
" ~ The good~result obtained after 2000 hours of accelerated weathering in a Xeno 1200 Weather-O-Meter suggests excellent weathering behavior.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can~be made therein by those skilled in the art ` without departing~from the spirit and scope of the invention ;
except as it~may be limited by the claims.
Mo3485 ' ; ..' ~
" '~'' ", .
' ~
Claims (9)
1. An aqueous polymer dispersion containing at most 22%
by weight of an organic solvent and 30 to 60% by weight of a dispersed polymer wherein said dispersed polymer comprises A) 20 to 80% by weight of a chlorinated natural or synthetic polymer containing 60 to 70% by weight chlorine and B) 20 to 80% by weight of a non-chlorinated polymer.
by weight of an organic solvent and 30 to 60% by weight of a dispersed polymer wherein said dispersed polymer comprises A) 20 to 80% by weight of a chlorinated natural or synthetic polymer containing 60 to 70% by weight chlorine and B) 20 to 80% by weight of a non-chlorinated polymer.
2. The aqueous polymer dispersion of Claim 1 wherein component A) comprises a chlorinated rubber having a molecular weight Mw of 60,000 to 185,000 and a chlorine content of 60 to 70% by weight.
3. The aqueous polymer dispersion of Claim 1 wherein said non-chlorinated polymer B) comprises a copolymer based on the reaction product of a) 20 to 50% by weight of styrene, b) 30 to 70% by weight of a C1-6 alkyl ester of acrylic or methacrylic acid, c) 0 to 10% by weight of methacrylic acid or acrylic acid and d) 0 to 20% by weight other unsaturated monomers, wherein the percentages add up to 100.
4. The aqueous polymer dispersion of Claim 2 wherein said non-chlorinated polymer B) comprises a copolymer based on the reaction product of a) 20 to 50% by weight of styrene, b) 30 to 70% by weight of a C1-6 alkyl ester of acrylic or methacrylic acid, c) 0 to 10% by weight of methacrylic acid or acrylic acid and d) a to 20% by weight other unsaturated monomers, wherein the percentages add up to 100.
5. The aqueous polymer dispersion of Claim 1 which additionally contains an aqueous bitumen dispersion.
6. A process for the production of an aqueous polymer dispersion which comprises i) mixing an at least 50% by weight solution in an inert solvent of a chlorinated, natural or synthetic polymer A) having a chlorine content of 60 to 70% by weight with water in the presence of external emulsifiers to form a water-in-oil emulsion and ii) subsequently combining said water-in-oil emulsion with an aqueous dispersion of a non-chlorinated polymer B) to form an oil-in-water dispersion, wherein the type of components and quantitative ratios between components are selected to provide an aqueous polymer dispersion which has a solvent content of at most 22% by weight, a dispersed polymer content of 30 to 60% by weight and a ratio by weight of chlorinated polymer A) to non-chlorinated polymer B) of 20:80 to 80:20.
7. The process of Claim 6 wherein component A) comprises a chlorinated rubber having a molecular weight Mw of 60,000 to 185,000 and a chlorine content of 60 to 70% by weight.
8. The process of Claim 6 wherein said non-chlorinated polymer B) comprises a copolymer based on the reaction product of a) 20 to 50% by weight of styrene, b) 30 to 70% by weight of a C1-6 alkyl ester of acrylic or methacrylic acid, c) 0 to 10% by weight of methacrylic acid or acrylic acid and d) 0 to 20% by weight other unsaturated monomers, wherein the percentages add up to 100.
9. The process of Claim 7 wherein said non-chlorinated polymer B) comprises a copolymer based on the reaction product of a) 20 to 50% by weight of styrene, b) 30 to 70% by weight of a C1-6 alkyl ester of acrylic or methacrylic acid, c) 0 to 10% by weight of methacrylic acid or acrylic acid and d) 0 to 20% by weight other unsaturated monomers, wherein the percentages add up to 100.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893938063 DE3938063A1 (en) | 1989-11-16 | 1989-11-16 | AQUEOUS POLYMER DISPERSIONS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF COATING AGENTS |
| DEP3938063.7 | 1989-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2028677A1 true CA2028677A1 (en) | 1991-05-17 |
Family
ID=6393614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2028677 Abandoned CA2028677A1 (en) | 1989-11-16 | 1990-10-26 | Aqueous polymer dispersions and a process for their production |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0429886A3 (en) |
| JP (1) | JPH03170538A (en) |
| CA (1) | CA2028677A1 (en) |
| DE (1) | DE3938063A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446083A (en) * | 1991-06-05 | 1995-08-29 | Zeneca Resins Bv | Aqueous coating compositions |
| CN104559486A (en) * | 2014-12-26 | 2015-04-29 | 江苏乘鹰新材料股份有限公司 | Woodware surface protecting coating composition and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03210336A (en) * | 1990-01-16 | 1991-09-13 | Nippon Paint Co Ltd | Production of crosslinked resin particle |
| DE19710382A1 (en) * | 1997-03-13 | 1998-09-17 | Buna Sow Leuna Olefinverb Gmbh | Redispersible dispersion powder, especially for use in tile cement |
| DE102006014092B4 (en) | 2006-03-24 | 2018-07-26 | Bostik Gmbh | Solvent-free, stable adhesives and sealants, use and process for the preparation of solvent-free, stable adhesives and sealants |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2192126B1 (en) * | 1972-07-07 | 1975-03-07 | Rhone Progil | |
| JPS5512148A (en) * | 1978-07-11 | 1980-01-28 | Osaka Soda Co Ltd | Asphalt emulsion modified with chlorinated polyethylene |
| AU6831481A (en) * | 1980-03-28 | 1981-10-01 | Imperial Chemical Industries Ltd. | Plasticised chlorinated rubber composition |
| JPH07122034B2 (en) * | 1986-11-27 | 1995-12-25 | サンスタ−技研株式会社 | Elastic finish coating primer composition |
| JPH01153777A (en) * | 1987-12-11 | 1989-06-15 | Chisso Corp | Aqueous adhesive composition |
-
1989
- 1989-11-16 DE DE19893938063 patent/DE3938063A1/en not_active Withdrawn
-
1990
- 1990-10-26 CA CA 2028677 patent/CA2028677A1/en not_active Abandoned
- 1990-11-03 EP EP19900121079 patent/EP0429886A3/en not_active Withdrawn
- 1990-11-13 JP JP30423390A patent/JPH03170538A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446083A (en) * | 1991-06-05 | 1995-08-29 | Zeneca Resins Bv | Aqueous coating compositions |
| US5637409A (en) * | 1991-06-05 | 1997-06-10 | Zeneca Limited | Aqueous coating compositions |
| CN104559486A (en) * | 2014-12-26 | 2015-04-29 | 江苏乘鹰新材料股份有限公司 | Woodware surface protecting coating composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0429886A3 (en) | 1991-12-27 |
| JPH03170538A (en) | 1991-07-24 |
| EP0429886A2 (en) | 1991-06-05 |
| DE3938063A1 (en) | 1991-05-23 |
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