CA2154107C - Light-resistant, solvent-free polyurethane coating compositions and their use for the production of coatings - Google Patents
Light-resistant, solvent-free polyurethane coating compositions and their use for the production of coatings Download PDFInfo
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- CA2154107C CA2154107C CA002154107A CA2154107A CA2154107C CA 2154107 C CA2154107 C CA 2154107C CA 002154107 A CA002154107 A CA 002154107A CA 2154107 A CA2154107 A CA 2154107A CA 2154107 C CA2154107 C CA 2154107C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D7/00—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs
Abstract
The present invention relates to solvent-free two-component polyurethane coating compositions containing A) a polyisocyanate component having a viscosity at 23°C of 500 to 12,000 mPa.cndot.s, an isocyanate content of 13 to 24% by weight and a content of monomeric diisocyanates of less than 0.5% by weight and containing a mixture of A1) 50 to 95% by weight of lacquer polyisocyanates prepared from 1,6-diisocyanatohexane and having a viscosity at 23°C of 100 to 4000 mPa.cndot.s and an isocyanate content of 16 to 24% by weight and A2) 5 to 50% by weight of isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates, and B) a polyol component containing one or more organic polyhydroxyl compounds, wherein components A) and B) are present in amounts corresponding to an NCO/OH equivalent ratio of 0.7:1 to 1.5:1. The invention also relates to the use of these two-component polyurethane coating compositions for the solvent-free coating of any substrates, in particular for the solvent-free sealing of balconies or roofs.
Description
Mo4229 LeA 30,464 -US
LIGHT-RESISTANT, SOLVENT-FREE POLYURETHANE
COATING COMPOSITIONS AND THEIR USE
FOR THE PRODUCTION OF COATINGS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to new solvent-free two-component polyurethane coating compositions and their use for the coating of any substrates, in particular for the sealing of balconies or roofs.
Background of the Invention Solvent-free two-component polyurethane (PU) coating compositions, unlike solvent-containing compositions, can be used to produce coatings of almost any thickness. They are currently used chiefly in the building sector for the production of thick coverings, for example, for coating areas subject to heavy mechanical use such as floors, for sealing balconies as well as for protection against corrosion.
Solvent-free two-component PU coatings require liquid co-reactants of low viscosity. While a number of suitable polyols of sufficiently low viscosity (for example, polyether polyols or slightly branched polyester polyols) are available, only limited polyisocyanates are available, i.e., in practice generally only liquid, non-distillable diphenylmethane diisocyanates (MDI) are employed. These low viscosity MDI polyisocyanates are highly reactive curing agents, but coatings prepared from these polyisocyanates tend, particularly on weathering, to become yellow and chalky. Therefore, they have only limited suitability for outdoor applications (Kunststoff Handbuch, Volume 7: Polyurethane, Second edition, Editor: G. Oertel; Hanser Publishing Company, Munich, Vienna, 1983, pages 556 to 558).
The preparation of two-component PU coatings resistant to light and weather is possible only with the use of (cyclo)aliphatic polyisocyanate curing agents. Solvent-free coating compositions which Mo4229 -2-exclusively aliphatically or cycloaliphatically bound isocyanate groups are described in DE-AS 2,304,893. Biuret polyisocyanates based on 1,6-diisocyanatohexane (HDI) and also HDI polyisocyanates having uretdione groups or isocyanurate groups are mentioned as examples of suitable curing agents. However, these coating compositions also cannot meet all the demands made in practice.
Highly elastic, light-resistant coatings can be prepared from polyisocyanates based on linear aliphatic diisocyanates, such as HDI, but the low hardness and inadequate abrasion resistance of the films obtained, and their excessively slow drying, are obstacles to their widespread use in solvent-free coating systems.
On the other hand, coating films which are prepared from polyisocyanates based on cycloaliphatic diisocyanates are distinguished in general by great hardness, outstanding resistance to mechanical or chemical influences as well as very rapid physical drying. But at the same time they have proved to be too brittle and too non-elastic for a number of applications.
A further disadvantage of the known cycloaliphatic coating polyisocyanates of prior art (for example, those having a biuret structure and described in DE-OS 3,030,655, those having an isocyanurate structure and described in EP-A 0,003,765, EP-A 0,017,998 and EP-A 0,193,828, or those having an uretdione structure and optionally an isocyanurate structure and described in DE-OS 1,934,763, EP-A 0,045,998 or EP-A 0,317,744) is that at room temperature these polyisocyanates are highly viscous or solid resins which cannot be employed as curing agents in solvent-free form. For this reason DE-AS 2,304,893 describes polyisocyanates suitable for the preparation of solvent-free coating compositions as those which have cycloaliphatically bound isocyanate groups and which are also entirely monomeric, liquid _ 2154.1p7 Mo4229 -3-diisocyanates such as 1-methyl-2,4-diisocyanatocyclohexane and/or 1-methyl-2,6-diisocyanatocyclohexane, diisocyanatocyclohexanes or 3,3,5-trimethyl-5-isocyanatomethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI). However, the use of these monomeric low molecular weight diisocyanates in two-component polyurethane coating compositions is not possible in practice due to the known toxicity of these compounds.
An object of the present invention is to provide new two-component polyurethane coating compositions which contain toxicologically safe curing components, can be processed free of solvents and cure rapidly under a very wide variety of environmental conditions to form light-resistant and weather-resistant coatings that combine the good elasticity of coatings cured using HDI polyisocyanates with the great hardness and abrasion-resistance of those based on cycloaliphatic polyisocyanates.
This object can be achieved with the two-component polyurethane coating compositions according to the invention described in more detail below. These coating compositions are based on the surprising observation that by using a mixture of polyisocyanates containing low viscosity HDI-based polyisocyanates and isocyanurate polyisocyanates based on cycloaliphatic diisocyanates, it is possible to prepare light-resistant, weather-resistant coatings having excellent hardness and abrasion resistance that surpass even the outstanding mechanical properties, i.e., elasticity and tear resistance, of coatings cured using pure HDI polyisocyanates.
These results were surprising since it is generally known that the hardness of polyurethane coatings can be increased with the use of cycloaliphatic curing agents, but that the elasticity is thereby simultaneously reduced. Therefore, it was not expected that the use of mixtures of low viscosity HDI polyisocyanates and isocyanurate Mo4229 -4-polyisocyanates based on cycloaliphatic diisocyanates would result in coatings which not only have great hardness but at the same time exhibit increased elasticity compared with coatings cured with pure HDI
polyisocyanates.
The use of low viscosity HDI uretdiones as reactive diluents for other more highly viscous or solid polyisocyanate components and the employment of the resulting mixtures in solvent-free polyurethane coating systems has already been disclosed in a general manner in DE-OS
3,437,635. However, the person skilled in the art could not predict from this publication that the use of particular mixtures of low viscosity HDI
polyisocyanates, e.g., those having the uretdione structure, and cycloaliphatic isocyanurate polyisocyanates would result in solvent-free two-component polyurethane coatings which surpass even the high standard of coatings cured using pure HDI polyisocyanates with regard to elasticity and tear resistance.
SUMMARY OF THE INVENTION
The present invention relates to solvent-free two-component polyurethane coating compositions containing A) a polyisocyanate component having a viscosity at 23 C of 500 to 12,000 mPa.s, an isocyanate content of 13 to 24% by weight and a content of monomeric diisocyanates of less than 0.5% by weight and containing a mixture of Al) 50 to 95% by weight of lacquer polyisocyanates prepared from 1,6-diisocyanatohexane and having a viscosity at 23 C
of 100 to 4000 mPa-s and an isocyanate content of 16 to 24% by weight and A2) 5 to 50% by weight of isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates, and _2154107 Mo4229 -5-B) a polyol component containing one or more organic polyhydroxyl compounds, wherein components A) and B) are present in amounts corresponding to an NCO/OH equivalent ratio of 0.7:1 to 1.5:1.
The invention also relates to the use of these two-component polyurethane coating compositions for the solvent-free coating of any substrates, in particular for the solvent-free sealing of balconies or roofs.
DETAILED DESCRIPTION OF THE INVENTION
The polyisocyanate component A) present in the coating compositions according to the invention consists of a mixture of 50 to 95% by weight of polyisocyanates based on 1,6-diisocyanatohexane Al) and 5 to 50% by weight of isocyanurate group-containing polyisocyanates and based on cycloaliphatic diisocyanates A2).
Polyisocyanates Al) are the known lacquer polyisocyanates based on HDI and having a viscosity at 23 C of 100 to 4000 mPa=s, a content of isocyanate groups of 15 to 24% by weight and a content of monomeric HDI of less than 0.5% by weight.
"Lacquer polyisocyanates based on HDI" means in particular the known derivatives of HDI containing allophanate groups, biuret groups, isocyanurate groups, oxadiazine trione groups, uretdione groups and/or urethane groups and having the required viscosity, isocyanate content and free monomer content. Suitable compounds for use as component Al) include polyisocyanates having uretdione groups and/or isocyanurate groups as described in EP-A 0,010,589, EP-A 0,089,297, EP-A
0,173,252, EP-A 0,178,520, EP-A 0,330,966, EP-A 0,337,116, EP-A 0,377,177, EP-A 0,456,062 and EP-A 0,495,307 and in DE-OS 3,219,608 and DE-OS 3,810,908; polyisocyanates having biuret groups as described in EP-A 0,150,769 and EP-A 0,320,703, in United States patents 3,903,127, 3,976,622 and 4,028,392 and in DE-OS
LIGHT-RESISTANT, SOLVENT-FREE POLYURETHANE
COATING COMPOSITIONS AND THEIR USE
FOR THE PRODUCTION OF COATINGS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to new solvent-free two-component polyurethane coating compositions and their use for the coating of any substrates, in particular for the sealing of balconies or roofs.
Background of the Invention Solvent-free two-component polyurethane (PU) coating compositions, unlike solvent-containing compositions, can be used to produce coatings of almost any thickness. They are currently used chiefly in the building sector for the production of thick coverings, for example, for coating areas subject to heavy mechanical use such as floors, for sealing balconies as well as for protection against corrosion.
Solvent-free two-component PU coatings require liquid co-reactants of low viscosity. While a number of suitable polyols of sufficiently low viscosity (for example, polyether polyols or slightly branched polyester polyols) are available, only limited polyisocyanates are available, i.e., in practice generally only liquid, non-distillable diphenylmethane diisocyanates (MDI) are employed. These low viscosity MDI polyisocyanates are highly reactive curing agents, but coatings prepared from these polyisocyanates tend, particularly on weathering, to become yellow and chalky. Therefore, they have only limited suitability for outdoor applications (Kunststoff Handbuch, Volume 7: Polyurethane, Second edition, Editor: G. Oertel; Hanser Publishing Company, Munich, Vienna, 1983, pages 556 to 558).
The preparation of two-component PU coatings resistant to light and weather is possible only with the use of (cyclo)aliphatic polyisocyanate curing agents. Solvent-free coating compositions which Mo4229 -2-exclusively aliphatically or cycloaliphatically bound isocyanate groups are described in DE-AS 2,304,893. Biuret polyisocyanates based on 1,6-diisocyanatohexane (HDI) and also HDI polyisocyanates having uretdione groups or isocyanurate groups are mentioned as examples of suitable curing agents. However, these coating compositions also cannot meet all the demands made in practice.
Highly elastic, light-resistant coatings can be prepared from polyisocyanates based on linear aliphatic diisocyanates, such as HDI, but the low hardness and inadequate abrasion resistance of the films obtained, and their excessively slow drying, are obstacles to their widespread use in solvent-free coating systems.
On the other hand, coating films which are prepared from polyisocyanates based on cycloaliphatic diisocyanates are distinguished in general by great hardness, outstanding resistance to mechanical or chemical influences as well as very rapid physical drying. But at the same time they have proved to be too brittle and too non-elastic for a number of applications.
A further disadvantage of the known cycloaliphatic coating polyisocyanates of prior art (for example, those having a biuret structure and described in DE-OS 3,030,655, those having an isocyanurate structure and described in EP-A 0,003,765, EP-A 0,017,998 and EP-A 0,193,828, or those having an uretdione structure and optionally an isocyanurate structure and described in DE-OS 1,934,763, EP-A 0,045,998 or EP-A 0,317,744) is that at room temperature these polyisocyanates are highly viscous or solid resins which cannot be employed as curing agents in solvent-free form. For this reason DE-AS 2,304,893 describes polyisocyanates suitable for the preparation of solvent-free coating compositions as those which have cycloaliphatically bound isocyanate groups and which are also entirely monomeric, liquid _ 2154.1p7 Mo4229 -3-diisocyanates such as 1-methyl-2,4-diisocyanatocyclohexane and/or 1-methyl-2,6-diisocyanatocyclohexane, diisocyanatocyclohexanes or 3,3,5-trimethyl-5-isocyanatomethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI). However, the use of these monomeric low molecular weight diisocyanates in two-component polyurethane coating compositions is not possible in practice due to the known toxicity of these compounds.
An object of the present invention is to provide new two-component polyurethane coating compositions which contain toxicologically safe curing components, can be processed free of solvents and cure rapidly under a very wide variety of environmental conditions to form light-resistant and weather-resistant coatings that combine the good elasticity of coatings cured using HDI polyisocyanates with the great hardness and abrasion-resistance of those based on cycloaliphatic polyisocyanates.
This object can be achieved with the two-component polyurethane coating compositions according to the invention described in more detail below. These coating compositions are based on the surprising observation that by using a mixture of polyisocyanates containing low viscosity HDI-based polyisocyanates and isocyanurate polyisocyanates based on cycloaliphatic diisocyanates, it is possible to prepare light-resistant, weather-resistant coatings having excellent hardness and abrasion resistance that surpass even the outstanding mechanical properties, i.e., elasticity and tear resistance, of coatings cured using pure HDI polyisocyanates.
These results were surprising since it is generally known that the hardness of polyurethane coatings can be increased with the use of cycloaliphatic curing agents, but that the elasticity is thereby simultaneously reduced. Therefore, it was not expected that the use of mixtures of low viscosity HDI polyisocyanates and isocyanurate Mo4229 -4-polyisocyanates based on cycloaliphatic diisocyanates would result in coatings which not only have great hardness but at the same time exhibit increased elasticity compared with coatings cured with pure HDI
polyisocyanates.
The use of low viscosity HDI uretdiones as reactive diluents for other more highly viscous or solid polyisocyanate components and the employment of the resulting mixtures in solvent-free polyurethane coating systems has already been disclosed in a general manner in DE-OS
3,437,635. However, the person skilled in the art could not predict from this publication that the use of particular mixtures of low viscosity HDI
polyisocyanates, e.g., those having the uretdione structure, and cycloaliphatic isocyanurate polyisocyanates would result in solvent-free two-component polyurethane coatings which surpass even the high standard of coatings cured using pure HDI polyisocyanates with regard to elasticity and tear resistance.
SUMMARY OF THE INVENTION
The present invention relates to solvent-free two-component polyurethane coating compositions containing A) a polyisocyanate component having a viscosity at 23 C of 500 to 12,000 mPa.s, an isocyanate content of 13 to 24% by weight and a content of monomeric diisocyanates of less than 0.5% by weight and containing a mixture of Al) 50 to 95% by weight of lacquer polyisocyanates prepared from 1,6-diisocyanatohexane and having a viscosity at 23 C
of 100 to 4000 mPa-s and an isocyanate content of 16 to 24% by weight and A2) 5 to 50% by weight of isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates, and _2154107 Mo4229 -5-B) a polyol component containing one or more organic polyhydroxyl compounds, wherein components A) and B) are present in amounts corresponding to an NCO/OH equivalent ratio of 0.7:1 to 1.5:1.
The invention also relates to the use of these two-component polyurethane coating compositions for the solvent-free coating of any substrates, in particular for the solvent-free sealing of balconies or roofs.
DETAILED DESCRIPTION OF THE INVENTION
The polyisocyanate component A) present in the coating compositions according to the invention consists of a mixture of 50 to 95% by weight of polyisocyanates based on 1,6-diisocyanatohexane Al) and 5 to 50% by weight of isocyanurate group-containing polyisocyanates and based on cycloaliphatic diisocyanates A2).
Polyisocyanates Al) are the known lacquer polyisocyanates based on HDI and having a viscosity at 23 C of 100 to 4000 mPa=s, a content of isocyanate groups of 15 to 24% by weight and a content of monomeric HDI of less than 0.5% by weight.
"Lacquer polyisocyanates based on HDI" means in particular the known derivatives of HDI containing allophanate groups, biuret groups, isocyanurate groups, oxadiazine trione groups, uretdione groups and/or urethane groups and having the required viscosity, isocyanate content and free monomer content. Suitable compounds for use as component Al) include polyisocyanates having uretdione groups and/or isocyanurate groups as described in EP-A 0,010,589, EP-A 0,089,297, EP-A
0,173,252, EP-A 0,178,520, EP-A 0,330,966, EP-A 0,337,116, EP-A 0,377,177, EP-A 0,456,062 and EP-A 0,495,307 and in DE-OS 3,219,608 and DE-OS 3,810,908; polyisocyanates having biuret groups as described in EP-A 0,150,769 and EP-A 0,320,703, in United States patents 3,903,127, 3,976,622 and 4,028,392 and in DE-OS
2,808,801, DE-OS 3,030,655 and DE-OS 3,133,865; polyisocyanates : ! 1 1 i I
Mo4229 -6-having allophanate groups and optionally isocyanurate groups as described in EP-A 0,000,194, EP-A 0,496,208, EP-A 0,524,500, EP-A 0,524,501 and EP-A 0,566,037; polyisocyanates having oxadiazine trione groups as described in DE-OS 1,670,666; and mixtures of these polyisocyanates.
Preferred polyisocyanates Al) are lacquer polyisocyanates which contain isocyanurate groups and either uretdione or allophanate and/or isocyanurate groups and have a viscosity at 23 C of 100 to 1500 mPa-s and an isocyanate content of 17 to 24% by weight.
More preferably polyisocyanates Al) are lacquer polyisocyanates having uretdione groups and isocyanurate groups, a viscosity at 23 C of 100 to 300 mPa-s and an isocyanate content of 19 to 23% by weight, as described in EP-A 0,337,116, EP-A 0,377,177 (U.S. Patent 4,994,541) and EP-A 0,495,307, or lacquer polyisocyanates having allophanate groups and isocyanurate groups, a viscosity at 23 C of 100 to 1200 mPa-s and an isocyanate content of 17 to 21 % by weight as described in EP-A 0,496,208 (U.S. Patent 5,124,427), EP-A 0,524,500, EP-A 0,524,501 and EP-A
0,566,037.
Polyisocyanates A2) are isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates such as 1-isocyanato-3,3,5-trimethyi-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 4,4'-diisocyanatodicyclohexylmethane, 1,3- and 1,4-diisocyanatocyclohexane, 2(4)-methyl-1,3-diisocyanato-cyclohexane, 1,4-diisocyanatomethylcyclohexane, 1-isocyanato-l-methyl-4(3)-isocyanatomethylcyclohexane and mixtures of these diisocyanates.
Polyisocyanates A2) have an isocyanate content of 10 to 25 by weight and a monomeric diisocyanate content of less than 0.5% by weight, and are either solid at 23 C or have a viscosity of greater than 200,000 mPa=s.
Mo4229 -7-The preparation of isocyanurate group-containing polyisocyanates from cycloaliphatic diisocyanates is known and described, for example, in EP-A 0,003,765, EP-A 0,017,998 or EP-A 193,828 or in DE-OS
1,934,763 and DE-OS 2,644,684. Polyisocyanates A2) are preferably prepared from IPDI and/or 4,4'-diisocyanatocyclohexylmethane and have an isocyanate content of 12 to 20% by weight. More preferably polyisocyanates A2) are prepared from IPDI and have an isocyanate content of 15 to 18% by weight.
Polyisocyanate component A) is prepared by simple mixing of the individual components Al) and A2), optionally preheated to temperatures of 30 to 240 C, in the proportions previously set forth, preferably maintaining an Al):A2) weight ratio of 1.5:1 to 8:1, more preferably 2:1 to 4:1. After mixing the components are stirred until homogeneous with the temperature of the mixture optionally being maintained by further heating at a temperature of 30 to 140 C, preferably of 40 to 100 C.
Because polyisocyanate component A2) is highly viscous or solid at 23 C, it is a preferred embodiment to prepare polyisocyanate component A) in the following manner. Immediately after preparing this component by catalytic trimerization of cycloaliphatic diisocyanates and separating the monomers by thin-film distillation, it is introduced while still heated, for example at temperatures of 100 to 240 C, into the optionally heated polyisocyanate Al) and is stirred, optionally with further heating, until the mixture is homogeneous.
In another preferred embodiment for preparing polyisocyanate component A), polyisocyanate component Al) is stirred into the crude solution present after completion of the trimerization reaction used to prepare polyisocyanate component A2), but prior to the thin-film distillation, and then the excess monomeric cycloaliphatic diisocyanates are separated.
Mo4229 -8-Polyisocyanate component A) has a viscosity at 23 C of 500 to 12000 mPa=s, preferably 1000 to 10000 mPa=s and more preferably 2000 to 8000 mPa.s; an isocyanate content of 13 to 24% by weight, preferably 15 to 23% by weight and more preferably 18 to 22% by weight; and a content of monomeric diisocyanates of less than 0.5% by weight.
Polyol component B) has an average OH functionality of 2 to 4 and a viscosity at 23 C of less than 30,000 mPa.s, preferably less than 10,000 mPa=s.
Compounds for use as polyol component B) or as a constituent of the polyol component B) are selected from the known polyhydroxy polyesters, polyethers, polycarbonates or polyester carbonates, castor oil or mixtures of castor oil with ketone-formaldehyde condensates as described in GB-PS 1,182,884 or EP-A 0,364,738, and mixtures of these polyhydroxy compounds.
Suitable polyester polyols include those having an average molecular weight, which may be calculated from the functionality and hydroxyl number, of 200 to 3000, preferably 250 to 2500, and a hydroxyl group content of 1 to 21 % by weight, preferably 2 to 18% by weight. The polyester are prepared in known manner by reacting polyhydric alcohols with excess quantities of polybasic carboxylic acids, the corresponding carboxylic anhydrides, the corresponding polycarboxylic esters of lower alcohols or lactones.
Polyhydric alcohols suitable for the preparation of these polyester polyols are those having a molecular weight of 62 to 400 such as 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexane-dimethanol, 4,4'-(1-methylethylidene)-biscyclohexanol, 1,2,3-propanetriol, 1, 1, 1 -trim ethylolethane, 1,2,6-hexane-triol, 1,1,1-trimethylolpropane, 2,2-bis(hydroxymethyl)-1,3-propanediol and 1,3,5-tris(2-hydroxyethyl)-isocyanurate.
Mo4229 -9-The acids or acid derivatives employed for the preparation of the polyester polyols may be aliphatic, cycloaliphatic and/or heteroaromatic and can optionally be unsaturated or substituted, for example, by halogen atoms. Examples of suitable acids are polybasic carboxylic acids having a molecular weight of 118 to 300 or derivatives thereof such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
Any mixtures of these starting materials can also be used for the preparation of the polyester polyols.
Preferred polyester polyols are those prepared in known manner from lactones and the previously described polyhydric alcohols with opening of the lactone ring. Examples of suitable lactones for the preparation of these polyester polyols include 13-propiolactone, y-butyrolactone, y-valerolactone and 5-valerolactone, c-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone and mixtures of these lactones.
The preparation is generally carried out in the presence of catalysts such as Lewis or Bronsted acids, organotin compounds or organotitanium compounds at temperatures of 20 to 200 C, preferably 50 to 160 C.
Suitable polyether polyols for use as polyol component B) are selected from those having an average molecular weight, which may be calculated from the functionality and hydroxyl number, of 200 to 6000, preferably 250 to 4000, and a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. The polyethers may be prepared in known manner by the alkoxylation of suitable starter molecules such as those having a molecular weight of 62 to 400 which were previously set forth for the preparation of polyester polyols.
Mo4229 -10-Alkylene oxides suitable for the alkoxylation reaction are in particular ethylene oxide and propylene oxide, which may be used in the alkoxylation reaction in any order or as a mixture.
Preferred polyether polyols are those wherein at least 80 mol-%, preferably 100 mol-% of the alkylene oxide units are propylene oxide units.
Suitable polycarbonate polyols suitable for use as polyol component B) are selected from the known polycarbonate diols which have a molecular weight, which may be calculated from the functionality and hydroxyl number, of 250 to 1000. The polycarbonate diols may be prepared in known manner by reacting of dihydric alcohols (such as those having a molecular weight of 62 to 400 which were previously set forth for the preparation of polyester polyols) with phosgene or diaryl carbonates such as diphenyl carbonate.
Suitable polyester carbonate polyols suitable for use as polyol component B) are selected from the known diols containing ester groups and carbonate groups which have a molecular weight, which may be calculated from the functionality and hydroxyl number, of 500 to 3000.
These polyols may be obtained as described in DE-AS 1,770,245 by reacting dihydric alcohols with the previously described lactones, preferably s-caprolactone, and subsequently reacting the resulting polyester diols with diphenyl carbonate.
In order to adjust the viscosity of the two-component coating compositions according to the invention, polyol component B) may also contain up to 50% by weight, preferably up to 20% by weight, based on the total weight of polyol component B), of polyhydric alcohols having a molecular weight of 62 to 199 and optionally containing ether oxygen atoms. Examples include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol and mixtures of these polyhydric alcohols.
Mo4229 -11-Components A) and B) are present in the coating compositions according to the invention in amounts sufficient to provide an NCO/OH
equivalent ratio of 0.7:1 to 1.5:1.
The individual components are preferably selected so that the binder mixture obtained by mixing individual components A) and B) has, immediately after mixing, a viscosity at 23 C of less than 30,000, preferably less than 10,000, and more preferably less than 8000 mPa-s.
Suitable selection of the starting materials and in particular of the optionally used additives (in particular catalysts) provides the coating compositions with a pot life of 20 minutes to 10 hours, preferably at least 40 minutes. In this regard the pot life is the time it takes for the initial viscosity to double.
In addition to the above-mentioned two-component binders, the coating compositions according to the invention may contain additives C), which are selected from the known fillers, pigments, plasticizers, curing catalysts, ultraviolet stabilizers, antioxidants, microbicides, algicides, water absorbers, thixotropic agents, wetting agents, levelling agents, flatting agents, antiskidding agents, de-airing agents or extenders.
Additives C) are incorporated into the components A) and B) according to the requirements of the particular application of the coating and on their compatibility. For example, additives which contain water or which are strongly alkaline should be mixed with component B) and not with component A).
Examples of suitable fillers include ground stone or granulated plastics, glass spheres, sand or cork, which may optionally be added in quantities of up to 800% by weight, based on the weight of the binder components A) and B).
Examples of suitable pigments include titanium dioxide, zinc oxide, iron oxides, chromium oxides or carbon blacks. A detailed discussion of pigments for coating compositions may be found in "Lehrbuch der Lacke Mo4229 -12-und Beschichtungen, Volume II, Pigmente, Fullstoffe, Farbstoffe", H.
Kittel, Publishing Company W.A. Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1974, pages 17-265. The pigments are used in quantities of up to 100% by weight, based on the weight of the binder components A) and B).
Plasticizers may be used to adjust the viscosity of the ready-for-use coating compositions. Suitable plasticizers include phthalate esters, adipate esters, or phosphate esters of C4 C,$ alkanols and/or vinyl esters of alkarylsulphonic acids. The plasticizers are used in quantities of up to 30% by weight, based on the weight of the binder components A) and B).
The coating compositions according to the invention may also contain the catalysts known from polyurethane chemistry, such as the known lead or bismuth compounds, preferably tin compounds, and the known tertiary amines, which are described in more detail in "Kunststoff Handbuch 7, Polyurethane", Carl Hanser Publishing Company, Munich, Vienna, 1984, pages 97 to 98. The catalysts are used in quantities of up to 2% by weight, based on the weight of the binder components A) and B).
The other previously described additives which may optionally be used in the coating compositions according to the invention are described, for example, in "Lehrbuch der Lacke und Beschichtungen, Volume III, Losemittel, Weichmacher, Additive, Zwischenprodukte", H. Kittel, Publishing Company W.A. Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1976, pages 237-398. Desiccants which act as water absorbers are described in more detail, for example, in "Kunststoff Handbuch 7, Polyurethane", Carl Hanser Publishing Company, Munich, Vienna, 1983, page 545. The total quantity of these additional additives is preferably 0 to 25% by weight, based on the weight of the binder components A) and B).
_2154107 Mo4229 -13-The coating compositions according to the invention are prepared by mixing the individual components, for example, using well-known dissolvers or vacuum dissolvers, which are frequently preferred in order to achieve thorough degassing of the coating compositions.
The solvent-free two-component polyurethane coating compositions according to the invention are suitable for coating any substrates, for example, concrete, metal, plastics or wood, and can be applied in generous layer thicknesses, for example, of up to 5 mm, by known methods such as spraying, rolling or filling.
The coating compositions cure, free of voids, at room temperature to form coatings which are resistant to light and weather and are distinguished by great hardness and abrasion resistance and have a higher elasticity and tear resistance than coatings prepared from known aliphatic coating systems based on pure HDI polyisocyanates.
The coating compositions according to the invention are particularly suitable for coating mineral substrates, for example, for the production of highly abrasion-resistant floor coatings or balcony coatings, as liquid plastics for roof sealing or concrete renovation and as binders for decorative stucco.
In addition to their use for the production of coatings, the coating compositions according to the invention can be also employed as solvent-free two-component polyurethane systems, for example, for the production of light-resistant, hard casting materials.
The following examples serve as a further explanation of the invention. All parts and percentages are by weight, unless otherwise indicated.
Mo4229 -14-EXAMPLES
Starting components Polyisocyanate 1 An HDI polyisocyanate prepared in accordance with Example 2 of EP-A 0,377,177 (U.S. Patent 4,994,541), containing uretdione groups and isocyanurate groups and having an NCO content of 22.5%, a viscosity at 23 C of 170 mPa.s and a content of monomeric HDI of 0.2%.
Polyisocyanate 2 An HDI polyisocyanate prepared in accordance with Example 4 of EP-A 0,496,208 (U.S. Patent 5,124,427), containing allophanate groups and isocyanurate groups and having an NCO content of 19.8%, a viscosity at 23 C of 520 mPa.s and a content of monomeric HDI of 0.3%.
Polyisocyanate 3 An HDI polyisocyanate prepared in accordance with Example 7 of EP-A 0,330,966, containing isocyanurate groups and having an NCO
content of 21.7%, a viscosity at 23 C of 3000 mPa=s and a content of monomeric HDI of 0.1%.
Polyisocyanate component 1 1332 g (6 moles) of IPDI were placed in a three-necked flask and warmed to 50 C. A catalyst based on 10 ml of a 6% solution of 2-hydroxyethyl-trimethylammonium hydroxide in a mixture of 2-ethylhexanol and methanol (volume ratio equal to 4:1) was added from a dropping funnel. The temperature rose to 75 C within approximately 30 min. The reaction mixture was heated to 80 C and stirring was continued at this temperature for 30 min until the NCO content had fallen to 31.1 %.
Then 970 g of polyisocyanate 1 was homogeneously stirred into the crude solution of the isocyanurate group-containing polyisocyanate prepared from IPDI. The excess monomeric IPDI was separated off by thin-film distillation at a temperature of 170 C and a pressure of 0.1 mbar. 1450 g of a virtually colorless polyisocyanate mixture was Mo4229 -15- -obtained, having an isocyanate content of 20.4%, a viscosity at 23 C of 3400 mPa=s, a content of monomeric IPDI of 0.2% and a content of monomeric HDI of 0.1 %. The product contained about 67% of HDI
polyisocyanate and 33% of IPDI polyisocyanate.
Polyisocyanate component 2 1332 g of IPDI were trimerized as described in polyisocyanate component 1 until an NCO content of 31.2% was obtained. Then 970 g of polyisocyanate 2 was homogeneously stirred into the crude solution and the excess monomeric IPDI was separated off by thin-film distillation at a temperature of 170 C and a pressure of 0.1 mbar. 1443 g of a virtually colorless polyisocyanate mixture was obtained, having an isocyanate content of 18.7%, a viscosity at 23 C of 6800 mPa.s, a content of monomeric IPDI of 0.3% and a content of monomeric HDI of 0.1 %. The product contained about 67% of HDI polyisocyanate and 33%
of IPDI polyisocyanate.
Polyisocyanate component 3 (Comparison) 1000 g of polyisocyanate 1 was added at room temperature to 500 g of polyisocyanate 3 and the mixture was then stirred until it was homogeneous. The polyisocyanate mixture obtained had an NCO content of 22.2%, a viscosity at 23 C of 500 mPa=s and a content of monomeric HDI of 0.2%. The mixture exclusively contained HDI polyisocyanates.
Polyol component 1 A mixture of 75 mol-% castor oil and 25 mol-% of a cyclohexanone-formaldehyde condensation product having a viscosity at 23 C of approx. 3500 mPa=s and an OH content of 4.8%.
Polyol component 2 A mixture of 60 mol-% castor oil, 20 mol-% of a cyclohexanone-formaldehyde condensation product and 20 mol-% of a polyether polyol prepared by the propoxylation of 1,1,1-trimethylolpropane (TMP) and Mo4229 -16-having an average molecular weight of 305, a viscosity at 23 C of approx.
3000 mPa-s and an OH content of 7.1%.
Polyol component 3 A polyether polyol prepared by the propoxylation of TMP and having an average molecular weight of 450, a viscosity at 23 C of approx. 600 mPa-s and an OH content of 11.7%.
Polyol component 4 A poly-e-caprolactone polyol started on TMP and having a viscosity at 23 C of approx. 3000 mPa-s and an OH content of 17%.
Polyol component 5 A poIy-E-caprolactone diol started on 1,4-butanediol and having a viscosity at 23 C of 2800 mPa.s and an OH content of 8.5%.
Example 1 100 parts by weight of polyol component 1 were mixed with 0.02 parts by weight of dibutyltin dilaurate (DBTL) as catalyst and 1 part by weight of a commercially available defoaming agent (Bevaloid* 6420, available from Erbsloh, Krefeld) in a dissolver for 5 minutes at a speed of rotation of 15 to ms"'. 58 parts by weight of polyisocyanate component 1(corresponding 20 to an NCO:OH equivalent ratio of 1:1) were then added and mixing in the dissolver was continued for 5 minutes. The solvent-free coating composition according to the invention, which had an initial viscosity at 23 C of 4000 mPa-s and a pot life of 30 minutes, was poured onto an aluminum plate treated with a separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula.
"trade-mark _ 21541a7 Mo4229 -17-After curing for 8 hours at room temperature, a transparent coating having the following properties was obtained:
Hardness, Shore A: 74 Elongation at tear: 142 %
Tear resistance: 7.8 N/mm2 Resistance to tear propagation 9.7 N/mm Example 2 (Comparison) In accordance with the method described in Example 1, a solvent-free coating composition having an initial viscosity at 23 C of 3500 mPa.s and a pot life of 20 min was prepared from 100 parts by weight of polyol component 1, 0.02 parts by weight of DBTL, 1 part by weight of the commercially available defoaming agent described in Example 1 and 53 parts by weight of polyisocyanate component 3 (corresponding to an NCO:OH equivalent ratio of 1:1). The coating composition was poured onto an aluminum plate treated with a separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula.
After curing for 8 hours at room temperature, a transparent coating having the following properties was obtained:
Hardness, Shore A: 62 Elongation at tear: 65 %
Tear resistance: 3.1 N/mm2 Resistance to tear propagation 3.8 N/mm The comparison demonstrates that the coating obtained using the coating composition according to the invention was markedly superior with regard to both hardness and elasticity when compared to a coating similarly prepared but exclusively using HDI polyisocyanates.
Examples 3 to 6 In accordance with the method described in Example 1, solvent-free coating compositions were prepared having the following _ 21541Q7 Mo4229 -18-compositions (parts by weight) and properties (in each case the NCO:OH
equivalent ratio was 1:1).
Example 3 4 (Comp) 5 6 (Comp) Polyisocyanate - - 142 -Component 1 Component 2 94 - - 0 Component 3 - 79 - 130 Polyol Component 2 100 100 - -Polyol Component 3 - - 100 100 DBTL 0.02 0.02 0.02 0.02 Bevaloid 6420 1 1 1 1 Initial viscosity (23 C) 4800 2200 2300 600 Pot Life (Min) 45 25 60 35 The coating compositions were each poured onto an aluminum plate treated with separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula. After curing for 8 hours at room temperature, transparent coatings having the following physical properties were obtained:
Example 3 4 (Comp) 5 6 (Comp) Hardness Shore A/D 83/27 77/21 -/50 -/37 Elongation at tear (%) 127 80 94 68 Tear resistance (N/m2) 13.4 6.5 13.2 7.3 Resistance to tear 18.1 8.6 40.8 17.5 propagation (N/mm) Mo4229 -19-Example 7 (Coating of balcony) 12.0 parts by weight each of polyol components 4 and 5 were mixed for 10 minutes in a vacuum dissolver together with 27.3 parts by weight of heavy spar (EWO*, available from Deutsche Barytindustrie, Bad Laufenberg) as filler, 5.0 parts by weight of a commercially available desiccant (Baylith*
L
paste, available from Bayer AG, Leverkusen), 0.2 parts by weight of a 10%
catalyst solution of DBTL in methoxypropyl acetate and 0.3 parts by weight of the commercially available defoaming agent described in Example 1. 41.0 parts by weight of polyisocyanate component 1 were then added and mixing in the dissolver was continued for 5 minutes.
The solvent-free coating composition according to the invention, which had a pot life of 40 minutes, was poured onto concrete and spread by means of a toothed spatula. After curing for 8 hours at room temperature, the following physical properties were found at a layer thickness of approx.
2 mm:
Hardness, Shore D: 60 Elongation at tear: 87%
Tear resistance: 33 N/mm2 Resistance to tear propagation 64 N/mm 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 of the spirit and scope of the invention except as it may be limited by the claims.
*trade-mark
Mo4229 -6-having allophanate groups and optionally isocyanurate groups as described in EP-A 0,000,194, EP-A 0,496,208, EP-A 0,524,500, EP-A 0,524,501 and EP-A 0,566,037; polyisocyanates having oxadiazine trione groups as described in DE-OS 1,670,666; and mixtures of these polyisocyanates.
Preferred polyisocyanates Al) are lacquer polyisocyanates which contain isocyanurate groups and either uretdione or allophanate and/or isocyanurate groups and have a viscosity at 23 C of 100 to 1500 mPa-s and an isocyanate content of 17 to 24% by weight.
More preferably polyisocyanates Al) are lacquer polyisocyanates having uretdione groups and isocyanurate groups, a viscosity at 23 C of 100 to 300 mPa-s and an isocyanate content of 19 to 23% by weight, as described in EP-A 0,337,116, EP-A 0,377,177 (U.S. Patent 4,994,541) and EP-A 0,495,307, or lacquer polyisocyanates having allophanate groups and isocyanurate groups, a viscosity at 23 C of 100 to 1200 mPa-s and an isocyanate content of 17 to 21 % by weight as described in EP-A 0,496,208 (U.S. Patent 5,124,427), EP-A 0,524,500, EP-A 0,524,501 and EP-A
0,566,037.
Polyisocyanates A2) are isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates such as 1-isocyanato-3,3,5-trimethyi-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 4,4'-diisocyanatodicyclohexylmethane, 1,3- and 1,4-diisocyanatocyclohexane, 2(4)-methyl-1,3-diisocyanato-cyclohexane, 1,4-diisocyanatomethylcyclohexane, 1-isocyanato-l-methyl-4(3)-isocyanatomethylcyclohexane and mixtures of these diisocyanates.
Polyisocyanates A2) have an isocyanate content of 10 to 25 by weight and a monomeric diisocyanate content of less than 0.5% by weight, and are either solid at 23 C or have a viscosity of greater than 200,000 mPa=s.
Mo4229 -7-The preparation of isocyanurate group-containing polyisocyanates from cycloaliphatic diisocyanates is known and described, for example, in EP-A 0,003,765, EP-A 0,017,998 or EP-A 193,828 or in DE-OS
1,934,763 and DE-OS 2,644,684. Polyisocyanates A2) are preferably prepared from IPDI and/or 4,4'-diisocyanatocyclohexylmethane and have an isocyanate content of 12 to 20% by weight. More preferably polyisocyanates A2) are prepared from IPDI and have an isocyanate content of 15 to 18% by weight.
Polyisocyanate component A) is prepared by simple mixing of the individual components Al) and A2), optionally preheated to temperatures of 30 to 240 C, in the proportions previously set forth, preferably maintaining an Al):A2) weight ratio of 1.5:1 to 8:1, more preferably 2:1 to 4:1. After mixing the components are stirred until homogeneous with the temperature of the mixture optionally being maintained by further heating at a temperature of 30 to 140 C, preferably of 40 to 100 C.
Because polyisocyanate component A2) is highly viscous or solid at 23 C, it is a preferred embodiment to prepare polyisocyanate component A) in the following manner. Immediately after preparing this component by catalytic trimerization of cycloaliphatic diisocyanates and separating the monomers by thin-film distillation, it is introduced while still heated, for example at temperatures of 100 to 240 C, into the optionally heated polyisocyanate Al) and is stirred, optionally with further heating, until the mixture is homogeneous.
In another preferred embodiment for preparing polyisocyanate component A), polyisocyanate component Al) is stirred into the crude solution present after completion of the trimerization reaction used to prepare polyisocyanate component A2), but prior to the thin-film distillation, and then the excess monomeric cycloaliphatic diisocyanates are separated.
Mo4229 -8-Polyisocyanate component A) has a viscosity at 23 C of 500 to 12000 mPa=s, preferably 1000 to 10000 mPa=s and more preferably 2000 to 8000 mPa.s; an isocyanate content of 13 to 24% by weight, preferably 15 to 23% by weight and more preferably 18 to 22% by weight; and a content of monomeric diisocyanates of less than 0.5% by weight.
Polyol component B) has an average OH functionality of 2 to 4 and a viscosity at 23 C of less than 30,000 mPa.s, preferably less than 10,000 mPa=s.
Compounds for use as polyol component B) or as a constituent of the polyol component B) are selected from the known polyhydroxy polyesters, polyethers, polycarbonates or polyester carbonates, castor oil or mixtures of castor oil with ketone-formaldehyde condensates as described in GB-PS 1,182,884 or EP-A 0,364,738, and mixtures of these polyhydroxy compounds.
Suitable polyester polyols include those having an average molecular weight, which may be calculated from the functionality and hydroxyl number, of 200 to 3000, preferably 250 to 2500, and a hydroxyl group content of 1 to 21 % by weight, preferably 2 to 18% by weight. The polyester are prepared in known manner by reacting polyhydric alcohols with excess quantities of polybasic carboxylic acids, the corresponding carboxylic anhydrides, the corresponding polycarboxylic esters of lower alcohols or lactones.
Polyhydric alcohols suitable for the preparation of these polyester polyols are those having a molecular weight of 62 to 400 such as 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexane-dimethanol, 4,4'-(1-methylethylidene)-biscyclohexanol, 1,2,3-propanetriol, 1, 1, 1 -trim ethylolethane, 1,2,6-hexane-triol, 1,1,1-trimethylolpropane, 2,2-bis(hydroxymethyl)-1,3-propanediol and 1,3,5-tris(2-hydroxyethyl)-isocyanurate.
Mo4229 -9-The acids or acid derivatives employed for the preparation of the polyester polyols may be aliphatic, cycloaliphatic and/or heteroaromatic and can optionally be unsaturated or substituted, for example, by halogen atoms. Examples of suitable acids are polybasic carboxylic acids having a molecular weight of 118 to 300 or derivatives thereof such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
Any mixtures of these starting materials can also be used for the preparation of the polyester polyols.
Preferred polyester polyols are those prepared in known manner from lactones and the previously described polyhydric alcohols with opening of the lactone ring. Examples of suitable lactones for the preparation of these polyester polyols include 13-propiolactone, y-butyrolactone, y-valerolactone and 5-valerolactone, c-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone and mixtures of these lactones.
The preparation is generally carried out in the presence of catalysts such as Lewis or Bronsted acids, organotin compounds or organotitanium compounds at temperatures of 20 to 200 C, preferably 50 to 160 C.
Suitable polyether polyols for use as polyol component B) are selected from those having an average molecular weight, which may be calculated from the functionality and hydroxyl number, of 200 to 6000, preferably 250 to 4000, and a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. The polyethers may be prepared in known manner by the alkoxylation of suitable starter molecules such as those having a molecular weight of 62 to 400 which were previously set forth for the preparation of polyester polyols.
Mo4229 -10-Alkylene oxides suitable for the alkoxylation reaction are in particular ethylene oxide and propylene oxide, which may be used in the alkoxylation reaction in any order or as a mixture.
Preferred polyether polyols are those wherein at least 80 mol-%, preferably 100 mol-% of the alkylene oxide units are propylene oxide units.
Suitable polycarbonate polyols suitable for use as polyol component B) are selected from the known polycarbonate diols which have a molecular weight, which may be calculated from the functionality and hydroxyl number, of 250 to 1000. The polycarbonate diols may be prepared in known manner by reacting of dihydric alcohols (such as those having a molecular weight of 62 to 400 which were previously set forth for the preparation of polyester polyols) with phosgene or diaryl carbonates such as diphenyl carbonate.
Suitable polyester carbonate polyols suitable for use as polyol component B) are selected from the known diols containing ester groups and carbonate groups which have a molecular weight, which may be calculated from the functionality and hydroxyl number, of 500 to 3000.
These polyols may be obtained as described in DE-AS 1,770,245 by reacting dihydric alcohols with the previously described lactones, preferably s-caprolactone, and subsequently reacting the resulting polyester diols with diphenyl carbonate.
In order to adjust the viscosity of the two-component coating compositions according to the invention, polyol component B) may also contain up to 50% by weight, preferably up to 20% by weight, based on the total weight of polyol component B), of polyhydric alcohols having a molecular weight of 62 to 199 and optionally containing ether oxygen atoms. Examples include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol and mixtures of these polyhydric alcohols.
Mo4229 -11-Components A) and B) are present in the coating compositions according to the invention in amounts sufficient to provide an NCO/OH
equivalent ratio of 0.7:1 to 1.5:1.
The individual components are preferably selected so that the binder mixture obtained by mixing individual components A) and B) has, immediately after mixing, a viscosity at 23 C of less than 30,000, preferably less than 10,000, and more preferably less than 8000 mPa-s.
Suitable selection of the starting materials and in particular of the optionally used additives (in particular catalysts) provides the coating compositions with a pot life of 20 minutes to 10 hours, preferably at least 40 minutes. In this regard the pot life is the time it takes for the initial viscosity to double.
In addition to the above-mentioned two-component binders, the coating compositions according to the invention may contain additives C), which are selected from the known fillers, pigments, plasticizers, curing catalysts, ultraviolet stabilizers, antioxidants, microbicides, algicides, water absorbers, thixotropic agents, wetting agents, levelling agents, flatting agents, antiskidding agents, de-airing agents or extenders.
Additives C) are incorporated into the components A) and B) according to the requirements of the particular application of the coating and on their compatibility. For example, additives which contain water or which are strongly alkaline should be mixed with component B) and not with component A).
Examples of suitable fillers include ground stone or granulated plastics, glass spheres, sand or cork, which may optionally be added in quantities of up to 800% by weight, based on the weight of the binder components A) and B).
Examples of suitable pigments include titanium dioxide, zinc oxide, iron oxides, chromium oxides or carbon blacks. A detailed discussion of pigments for coating compositions may be found in "Lehrbuch der Lacke Mo4229 -12-und Beschichtungen, Volume II, Pigmente, Fullstoffe, Farbstoffe", H.
Kittel, Publishing Company W.A. Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1974, pages 17-265. The pigments are used in quantities of up to 100% by weight, based on the weight of the binder components A) and B).
Plasticizers may be used to adjust the viscosity of the ready-for-use coating compositions. Suitable plasticizers include phthalate esters, adipate esters, or phosphate esters of C4 C,$ alkanols and/or vinyl esters of alkarylsulphonic acids. The plasticizers are used in quantities of up to 30% by weight, based on the weight of the binder components A) and B).
The coating compositions according to the invention may also contain the catalysts known from polyurethane chemistry, such as the known lead or bismuth compounds, preferably tin compounds, and the known tertiary amines, which are described in more detail in "Kunststoff Handbuch 7, Polyurethane", Carl Hanser Publishing Company, Munich, Vienna, 1984, pages 97 to 98. The catalysts are used in quantities of up to 2% by weight, based on the weight of the binder components A) and B).
The other previously described additives which may optionally be used in the coating compositions according to the invention are described, for example, in "Lehrbuch der Lacke und Beschichtungen, Volume III, Losemittel, Weichmacher, Additive, Zwischenprodukte", H. Kittel, Publishing Company W.A. Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1976, pages 237-398. Desiccants which act as water absorbers are described in more detail, for example, in "Kunststoff Handbuch 7, Polyurethane", Carl Hanser Publishing Company, Munich, Vienna, 1983, page 545. The total quantity of these additional additives is preferably 0 to 25% by weight, based on the weight of the binder components A) and B).
_2154107 Mo4229 -13-The coating compositions according to the invention are prepared by mixing the individual components, for example, using well-known dissolvers or vacuum dissolvers, which are frequently preferred in order to achieve thorough degassing of the coating compositions.
The solvent-free two-component polyurethane coating compositions according to the invention are suitable for coating any substrates, for example, concrete, metal, plastics or wood, and can be applied in generous layer thicknesses, for example, of up to 5 mm, by known methods such as spraying, rolling or filling.
The coating compositions cure, free of voids, at room temperature to form coatings which are resistant to light and weather and are distinguished by great hardness and abrasion resistance and have a higher elasticity and tear resistance than coatings prepared from known aliphatic coating systems based on pure HDI polyisocyanates.
The coating compositions according to the invention are particularly suitable for coating mineral substrates, for example, for the production of highly abrasion-resistant floor coatings or balcony coatings, as liquid plastics for roof sealing or concrete renovation and as binders for decorative stucco.
In addition to their use for the production of coatings, the coating compositions according to the invention can be also employed as solvent-free two-component polyurethane systems, for example, for the production of light-resistant, hard casting materials.
The following examples serve as a further explanation of the invention. All parts and percentages are by weight, unless otherwise indicated.
Mo4229 -14-EXAMPLES
Starting components Polyisocyanate 1 An HDI polyisocyanate prepared in accordance with Example 2 of EP-A 0,377,177 (U.S. Patent 4,994,541), containing uretdione groups and isocyanurate groups and having an NCO content of 22.5%, a viscosity at 23 C of 170 mPa.s and a content of monomeric HDI of 0.2%.
Polyisocyanate 2 An HDI polyisocyanate prepared in accordance with Example 4 of EP-A 0,496,208 (U.S. Patent 5,124,427), containing allophanate groups and isocyanurate groups and having an NCO content of 19.8%, a viscosity at 23 C of 520 mPa.s and a content of monomeric HDI of 0.3%.
Polyisocyanate 3 An HDI polyisocyanate prepared in accordance with Example 7 of EP-A 0,330,966, containing isocyanurate groups and having an NCO
content of 21.7%, a viscosity at 23 C of 3000 mPa=s and a content of monomeric HDI of 0.1%.
Polyisocyanate component 1 1332 g (6 moles) of IPDI were placed in a three-necked flask and warmed to 50 C. A catalyst based on 10 ml of a 6% solution of 2-hydroxyethyl-trimethylammonium hydroxide in a mixture of 2-ethylhexanol and methanol (volume ratio equal to 4:1) was added from a dropping funnel. The temperature rose to 75 C within approximately 30 min. The reaction mixture was heated to 80 C and stirring was continued at this temperature for 30 min until the NCO content had fallen to 31.1 %.
Then 970 g of polyisocyanate 1 was homogeneously stirred into the crude solution of the isocyanurate group-containing polyisocyanate prepared from IPDI. The excess monomeric IPDI was separated off by thin-film distillation at a temperature of 170 C and a pressure of 0.1 mbar. 1450 g of a virtually colorless polyisocyanate mixture was Mo4229 -15- -obtained, having an isocyanate content of 20.4%, a viscosity at 23 C of 3400 mPa=s, a content of monomeric IPDI of 0.2% and a content of monomeric HDI of 0.1 %. The product contained about 67% of HDI
polyisocyanate and 33% of IPDI polyisocyanate.
Polyisocyanate component 2 1332 g of IPDI were trimerized as described in polyisocyanate component 1 until an NCO content of 31.2% was obtained. Then 970 g of polyisocyanate 2 was homogeneously stirred into the crude solution and the excess monomeric IPDI was separated off by thin-film distillation at a temperature of 170 C and a pressure of 0.1 mbar. 1443 g of a virtually colorless polyisocyanate mixture was obtained, having an isocyanate content of 18.7%, a viscosity at 23 C of 6800 mPa.s, a content of monomeric IPDI of 0.3% and a content of monomeric HDI of 0.1 %. The product contained about 67% of HDI polyisocyanate and 33%
of IPDI polyisocyanate.
Polyisocyanate component 3 (Comparison) 1000 g of polyisocyanate 1 was added at room temperature to 500 g of polyisocyanate 3 and the mixture was then stirred until it was homogeneous. The polyisocyanate mixture obtained had an NCO content of 22.2%, a viscosity at 23 C of 500 mPa=s and a content of monomeric HDI of 0.2%. The mixture exclusively contained HDI polyisocyanates.
Polyol component 1 A mixture of 75 mol-% castor oil and 25 mol-% of a cyclohexanone-formaldehyde condensation product having a viscosity at 23 C of approx. 3500 mPa=s and an OH content of 4.8%.
Polyol component 2 A mixture of 60 mol-% castor oil, 20 mol-% of a cyclohexanone-formaldehyde condensation product and 20 mol-% of a polyether polyol prepared by the propoxylation of 1,1,1-trimethylolpropane (TMP) and Mo4229 -16-having an average molecular weight of 305, a viscosity at 23 C of approx.
3000 mPa-s and an OH content of 7.1%.
Polyol component 3 A polyether polyol prepared by the propoxylation of TMP and having an average molecular weight of 450, a viscosity at 23 C of approx. 600 mPa-s and an OH content of 11.7%.
Polyol component 4 A poly-e-caprolactone polyol started on TMP and having a viscosity at 23 C of approx. 3000 mPa-s and an OH content of 17%.
Polyol component 5 A poIy-E-caprolactone diol started on 1,4-butanediol and having a viscosity at 23 C of 2800 mPa.s and an OH content of 8.5%.
Example 1 100 parts by weight of polyol component 1 were mixed with 0.02 parts by weight of dibutyltin dilaurate (DBTL) as catalyst and 1 part by weight of a commercially available defoaming agent (Bevaloid* 6420, available from Erbsloh, Krefeld) in a dissolver for 5 minutes at a speed of rotation of 15 to ms"'. 58 parts by weight of polyisocyanate component 1(corresponding 20 to an NCO:OH equivalent ratio of 1:1) were then added and mixing in the dissolver was continued for 5 minutes. The solvent-free coating composition according to the invention, which had an initial viscosity at 23 C of 4000 mPa-s and a pot life of 30 minutes, was poured onto an aluminum plate treated with a separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula.
"trade-mark _ 21541a7 Mo4229 -17-After curing for 8 hours at room temperature, a transparent coating having the following properties was obtained:
Hardness, Shore A: 74 Elongation at tear: 142 %
Tear resistance: 7.8 N/mm2 Resistance to tear propagation 9.7 N/mm Example 2 (Comparison) In accordance with the method described in Example 1, a solvent-free coating composition having an initial viscosity at 23 C of 3500 mPa.s and a pot life of 20 min was prepared from 100 parts by weight of polyol component 1, 0.02 parts by weight of DBTL, 1 part by weight of the commercially available defoaming agent described in Example 1 and 53 parts by weight of polyisocyanate component 3 (corresponding to an NCO:OH equivalent ratio of 1:1). The coating composition was poured onto an aluminum plate treated with a separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula.
After curing for 8 hours at room temperature, a transparent coating having the following properties was obtained:
Hardness, Shore A: 62 Elongation at tear: 65 %
Tear resistance: 3.1 N/mm2 Resistance to tear propagation 3.8 N/mm The comparison demonstrates that the coating obtained using the coating composition according to the invention was markedly superior with regard to both hardness and elasticity when compared to a coating similarly prepared but exclusively using HDI polyisocyanates.
Examples 3 to 6 In accordance with the method described in Example 1, solvent-free coating compositions were prepared having the following _ 21541Q7 Mo4229 -18-compositions (parts by weight) and properties (in each case the NCO:OH
equivalent ratio was 1:1).
Example 3 4 (Comp) 5 6 (Comp) Polyisocyanate - - 142 -Component 1 Component 2 94 - - 0 Component 3 - 79 - 130 Polyol Component 2 100 100 - -Polyol Component 3 - - 100 100 DBTL 0.02 0.02 0.02 0.02 Bevaloid 6420 1 1 1 1 Initial viscosity (23 C) 4800 2200 2300 600 Pot Life (Min) 45 25 60 35 The coating compositions were each poured onto an aluminum plate treated with separating agent and spread out to a layer thickness of approx. 1 mm by means of a toothed spatula. After curing for 8 hours at room temperature, transparent coatings having the following physical properties were obtained:
Example 3 4 (Comp) 5 6 (Comp) Hardness Shore A/D 83/27 77/21 -/50 -/37 Elongation at tear (%) 127 80 94 68 Tear resistance (N/m2) 13.4 6.5 13.2 7.3 Resistance to tear 18.1 8.6 40.8 17.5 propagation (N/mm) Mo4229 -19-Example 7 (Coating of balcony) 12.0 parts by weight each of polyol components 4 and 5 were mixed for 10 minutes in a vacuum dissolver together with 27.3 parts by weight of heavy spar (EWO*, available from Deutsche Barytindustrie, Bad Laufenberg) as filler, 5.0 parts by weight of a commercially available desiccant (Baylith*
L
paste, available from Bayer AG, Leverkusen), 0.2 parts by weight of a 10%
catalyst solution of DBTL in methoxypropyl acetate and 0.3 parts by weight of the commercially available defoaming agent described in Example 1. 41.0 parts by weight of polyisocyanate component 1 were then added and mixing in the dissolver was continued for 5 minutes.
The solvent-free coating composition according to the invention, which had a pot life of 40 minutes, was poured onto concrete and spread by means of a toothed spatula. After curing for 8 hours at room temperature, the following physical properties were found at a layer thickness of approx.
2 mm:
Hardness, Shore D: 60 Elongation at tear: 87%
Tear resistance: 33 N/mm2 Resistance to tear propagation 64 N/mm 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 of the spirit and scope of the invention except as it may be limited by the claims.
*trade-mark
Claims (9)
1. A solvent-free, two-component polyurethane coating composition comprising A) a polyisocyanate component having a viscosity at 23°C of 500 to 12,000 mPa.cndot.s, an isocyanate content of 13 to 24% by weight and a content of monomeric diisocyanates of less than 0.5% by weight and consisting essentially of a mixture of Al) 50 to 95% by weight of one or more lacquer polyisocyanates prepared from 1,6-diisocyanatohexane, containing isocyanurate groups and uretdione or allophanate groups, and having a viscosity at 23°C of 100 to 1500 mPa.cndot.s and an isocyanate content of 17 to 24% by weight and A2) 5 to 50% by weight of one or more isocyanurate group-containing polyisocyanates prepared from cycloaliphatic diisocyanates, and B) a polyol component containing one or more organic polyhydroxyl compounds, wherein components A) and B) are present in amounts corresponding to an NCO/OH equivalent ratio of 0.7:1 to 1.5:1.
2. The coating composition of Claim 1 wherein component A1) consists essentially of a polyisocyanate having isocyanurate groups and allophanate groups.
3. The coating composition of Claim 1 wherein component A1) consists of a polyisocyanate based on 1,6-diisocyanatohexane and having uretdione groups and isocyanurate groups, a viscosity at 23°C of 100 to 300 mPa.cndot.s and an isocyanate content of 19 to 23% by weight.
4. The coating composition of Claim 1 wherein component A1) consists of a polyisocyanate based on 1,6-diisocyanatohexane and having allophanate groups and isocyanurate groups, a viscosity at 23°C of 100 to 1200 mPa.cndot.s and an isocyanate content of 17 to 21 % by weight.
5. The coating composition of Claim 1 wherein component A2) consists of an isocyanurate group-containing polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.
6. The coating composition of Claim 2 wherein component A2) consists of an isocyanurate group-containing polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.
7. The coating composition of Claim 3 wherein component A2) consists of an isocyanurate group-containing polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethytcyclohexane.
8. The coating composition of Claim 4 wherein component A2) consists of an isocyanurate group-containing polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.
9. A substrate which has been coated or sealed with the coating composition of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4426131.4 | 1994-07-22 | ||
| DE4426131A DE4426131A1 (en) | 1994-07-22 | 1994-07-22 | Non-fading, solvent-free polyurethane coating agents and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2154107A1 CA2154107A1 (en) | 1996-01-23 |
| CA2154107C true CA2154107C (en) | 2008-02-26 |
Family
ID=6523965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002154107A Expired - Fee Related CA2154107C (en) | 1994-07-22 | 1995-07-18 | Light-resistant, solvent-free polyurethane coating compositions and their use for the production of coatings |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0693512B1 (en) |
| JP (1) | JP3515240B2 (en) |
| KR (1) | KR100375468B1 (en) |
| AT (1) | ATE185360T1 (en) |
| CA (1) | CA2154107C (en) |
| DE (2) | DE4426131A1 (en) |
| DK (1) | DK0693512T3 (en) |
| ES (1) | ES2138120T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI724064B (en) * | 2015-11-23 | 2021-04-11 | 瑞士商亨斯邁先進材料授權（瑞士）有限公司 | A curable polyurethane composition for the preparation of outdoor articles, and the articles obtained therefrom |
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| DE29500706U1 (en) * | 1995-01-18 | 1995-03-30 | Coelan Chemie Produktionsgesel | Coating material with embedded particles |
| DE19603736A1 (en) * | 1996-02-02 | 1997-08-07 | Bayer Ag | Low viscosity polyisocyanate mixture |
| ZA9810037B (en) * | 1997-11-04 | 2000-05-03 | Rhodia Chimie Sa | A method for separating a compound obtained by polymerization of isocyanates from the corresponding non transformed monomers. |
| DE19828935A1 (en) * | 1998-06-29 | 1999-12-30 | Basf Ag | High viscosity polyisocyanate composition useful as a surface coating |
| ATE238246T1 (en) * | 1999-03-04 | 2003-05-15 | Adisa Service Ag | ELECTRICALLY CONDUCTIVE FLOORING AND METHOD FOR PRODUCING SAME |
| EP1033440B1 (en) * | 1999-03-04 | 2004-05-26 | Adisa Service und Entwicklungs AG | Leakproof floor covering and process of making the same |
| JP4766791B2 (en) * | 2001-07-25 | 2011-09-07 | 京セラ株式会社 | Display device device |
| DE10325669A1 (en) * | 2003-06-06 | 2004-12-23 | Bayer Materialscience Ag | Lightfast PUR clearcoats |
| DE10328663A1 (en) | 2003-06-26 | 2005-01-13 | Bayer Materialscience Ag | Polyisocyanate-modified polycarboxylic acids |
| JP4725850B2 (en) * | 2006-04-13 | 2011-07-13 | Ｄｉｃ株式会社 | Water-dispersible polyisocyanate composition, aqueous curable composition, aqueous paint and aqueous adhesive |
| EP2060593A1 (en) | 2007-11-13 | 2009-05-20 | Karl Nestler | Application of a sealant coating for producing a steam barrier layer |
| EP2085415A1 (en) | 2008-01-28 | 2009-08-05 | Karl Nestler | Composite system, method for its manufacture and multi-layered non-woven fabric |
| DE102009005711A1 (en) * | 2009-01-22 | 2010-07-29 | Bayer Materialscience Ag | Polyurethanvergussmassen |
| WO2010132858A2 (en) | 2009-05-14 | 2010-11-18 | Battelle Memorial Institute | Solventless methods of coating a carbon nanotube network and carbon nanotube networks coated with a polymer |
| DE102009060552A1 (en) | 2009-12-23 | 2011-06-30 | Bayer MaterialScience AG, 51373 | Polyurethane binder |
| DE102010031684A1 (en) | 2010-07-20 | 2012-01-26 | Bayer Materialscience Ag | Polyurethanes with high refraction of light |
| DE102010031681A1 (en) | 2010-07-20 | 2012-01-26 | Bayer Materialscience Ag | Polyurethanes with low volume shrinkage |
| DE102010031683A1 (en) | 2010-07-20 | 2012-01-26 | Bayer Materialscience Ag | polyisocyanate |
| WO2013160226A1 (en) | 2012-04-23 | 2013-10-31 | Bayer Materialscience Ag | Lightfast polyurethane composition |
| JP5946574B1 (en) * | 2015-08-25 | 2016-07-06 | サンユレック株式会社 | Polyurethane resin composition |
| EP3549990A1 (en) | 2018-04-04 | 2019-10-09 | Covestro Deutschland AG | Bicomponent system with improved adhesion |
| EP3660066A1 (en) | 2018-11-28 | 2020-06-03 | Covestro Deutschland AG | Polyisocyanate composition based on pentamethylendiisocyanate for coatings |
| JP7420646B2 (en) * | 2020-05-28 | 2024-01-23 | 日本特殊塗料株式会社 | A method of filling gaps, cracks, dents, electrical distribution boxes, and piping joints in structures with polyurethane clear filler. |
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-
1994
- 1994-07-22 DE DE4426131A patent/DE4426131A1/en not_active Withdrawn
-
1995
- 1995-07-10 DE DE59506974T patent/DE59506974D1/en not_active Expired - Lifetime
- 1995-07-10 DK DK95110707T patent/DK0693512T3/en active
- 1995-07-10 EP EP95110707A patent/EP0693512B1/en not_active Expired - Lifetime
- 1995-07-10 AT AT95110707T patent/ATE185360T1/en active
- 1995-07-10 ES ES95110707T patent/ES2138120T3/en not_active Expired - Lifetime
- 1995-07-18 CA CA002154107A patent/CA2154107C/en not_active Expired - Fee Related
- 1995-07-20 JP JP20505195A patent/JP3515240B2/en not_active Expired - Fee Related
- 1995-07-21 KR KR1019950021535A patent/KR100375468B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI724064B (en) * | 2015-11-23 | 2021-04-11 | 瑞士商亨斯邁先進材料授權（瑞士）有限公司 | A curable polyurethane composition for the preparation of outdoor articles, and the articles obtained therefrom |
| US11286387B2 (en) | 2015-11-23 | 2022-03-29 | Huntsman Advanced Materials (Switzerland) Gmbh | Curable polyurethane composition for the preparation of outdoor articles, and the articles obtained therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59506974D1 (en) | 1999-11-11 |
| DE4426131A1 (en) | 1996-01-25 |
| ES2138120T3 (en) | 2000-01-01 |
| KR100375468B1 (en) | 2003-08-25 |
| CA2154107A1 (en) | 1996-01-23 |
| DK0693512T3 (en) | 2000-04-10 |
| KR960004476A (en) | 1996-02-23 |
| EP0693512A1 (en) | 1996-01-24 |
| JPH0860095A (en) | 1996-03-05 |
| JP3515240B2 (en) | 2004-04-05 |
| ATE185360T1 (en) | 1999-10-15 |
| EP0693512B1 (en) | 1999-10-06 |
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| EEER | Examination request | ||
| MKLA | Lapsed |
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