CA1334230C - Process for the preparation of prepolymers containing isocyanate groups, the prepolymers obtainable by this process and their use as binders in one-component lacquers - Google Patents
Process for the preparation of prepolymers containing isocyanate groups, the prepolymers obtainable by this process and their use as binders in one-component lacquersInfo
- Publication number
- CA1334230C CA1334230C CA000539357A CA539357A CA1334230C CA 1334230 C CA1334230 C CA 1334230C CA 000539357 A CA000539357 A CA 000539357A CA 539357 A CA539357 A CA 539357A CA 1334230 C CA1334230 C CA 1334230C
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- CA
- Canada
- Prior art keywords
- component
- isocyanurate
- weight
- groups
- triisocyanato
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention is directed to a process for the preparation of prepolymers containing free isocyanate groups and having an isocyanate content of 1 to 16% by weight by the reaction of a) a polyisocyanate component with b) a polyhydroxyl component based on (i) at least one polyester polyol having a hydroxyl functionality (average) of about 1.8 to 5 and a hydroxyl number (average) of from 15 to 300 or (ii) mixtures of polyester polyols of the type mentioned under (i) with up to about 10% by weight, based on the weight of the mixture, of (cyclo)alkane polyols having a hydroxyl number above about 300 and optionally containing ester groups at an NCO/OH equivalent ratio above 2:1, characterized in that the compounds used as component (a) contain triisocyanato-isocyanurates having aliphatically or cycloaliphatically bound isocyanate groups. The present invention also relates to the prepolymers with free isocyanate groups obtainable by this process and their use as binders for moisture hardening one-component lacquers.
Description
PROCESS FOR THE PREPARATION OF PREPOLYMERS
CONTAINING ISOCYANATE GROUPS, THE PREPOLYMERS
OBTAINABLE BY THIS PROCESS AND THEIR USE AS
BINDERS IN ONE-COMPONENT LACQUERS
Field of the Invention This invention relates to new prepolymers containing free isocyanate groups obtained by the reaction of excess quantities of polyisocyanates con-10 taining isocyanurate groups with polyester polyols, to the prepolymers obtainable by this process and to their use as binders in moisture hardening one-component lacquers.
Description of the Prior Art 15Moisture hardening polyurethane lacquers based on aliphatic polyisocyanates, in particular on iso-cyanate prepolymers containing aliphatically bound isocyanate groups are already known and have been described, for example, by H. Kittel in "Lehrbuch der 20 Lacke und Beschichtungen", publishers W.A. Colomb, Berlin-Oberschwandorf 1973, Volume l, Part 2, page 574.
Polyisocyanates with a biuret structure prepared from hexamethylene diisocyanate have gained a position of particular commercial importance for the preparation of 25 such binders.
The previously known moisture hardening one-component PUR lacquers have various advantages over two-component PUR lacquers, e.g., simple, uncomplicated methods of working up, great hardness and rapid onset of 30 drying by the formation of high molecular weight poly-urethane ureas. However, the moisture hardening one-component lacquers of the state of the art based on aliphatic isocyanates also have certain disadvantages which manifest themselves in the lack of - 1 33~0 long-term stability of the lacquers. Pigmented lacquers based on the isocyanate prepolymers previously known, for example, frequently do not satisfy the requirements 5 for resistance to yellowing on exposure to light and for resistance to weathering. The insufficient resistance to weatherin~ leads to loss of gloss and to chalking of the coatings produced from the lacquers.
It was an object of the present invention to 10 provide new prepolymers containing isocyanate groups as binders for moisture hardening one-component lacquers which would be superior to the known prepolymers in the properties mentioned above.
This problem was solved by means of the process 15 according to the invention described below.
SUMMARY OF THE INVENTION
The invention is directed to a process for the preparation of prepolyme,s containing free isocyanate groups and having an isocyanate content of 1 to 16~ by 20 weight by the reaction of a) a polyisocyanate component with b) a polyhydroxyl component based on (i) at least one polyester polyol having a hydroxyl functionality (average) of about 1.8 to 5 and a hydroxyl number (average) of about 15 to 300 or (ii) mixtures of polyester polyols of the type mentioned under (i) with up to about 102 by weight, based on the weight of the mlxture, of (cyclo)alkane polyols having a hydroxyl number above about 300 and optionally containing ester groups at an NCO/OH equivalent ratio above 4:1, characterized in thct the compounds used as component a) are Mo-2933 - 2 -, .~ ~
(i) triisocyanato-isocyanurates corresponding to the formula ( ~
o (ii) mixtures of the triisocyanato-isocyanurates indicated under (i) with their higher homologues containing more than one isocyanurate ring or (iii) mixtures of the polyisocyanates indicated under (i) and (ii) with up to about 60 isocyanate equivalent percent, based on the total quantity of component a), of organic polyisocyanates free from isocyanurate groups, wherein 20 Xl, X2 and X3 in the above formula represent identical or different groups which are difunctional, aliphatic or cycloaliphatic hydrocarbon groups having a molecular weight of 84 to 206.
The present invention also relates to the 25 prepolymers with free isocyanate groups obtainable by this process and their use as binders for moisture hardening one-component lacquers.
DETAILED DESCRIPTION OF THE lNV~:NlION
Polyisocyanate component a) to be used in the 30 process according to the invention is based on polyiso-cyanates containing isocyanurate groups or mixtures of such polyisocyanates with polyisocyanates which are free from isocyanurate groups.
The polyisocyanates containing isocyanurate 35 groups may be both (i) triisocyanato-monoisocyanurates and (ii) mixtures thereof with their higher homologues.
Mo-2933 - 3 --- l 334230 The triisocyanato-monoisocyanurates correspond to the above general formula in which the symbols Xl, X2 and X3 have the meanings indicated above, but preferably represent identical or different hydrocarbon groups 5 linking the isocyanate groups of 1,6-diisocyanatohexane and/or of l-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane. The polyisocyanates containing isocyanurate groups used in the process according to the invention are thus preferably the trimerization products 10 of these two diisocyanates or of mixtures thereof although other polyisocyanates with isocyanurate groups conforming to the above definition of Xl, X2 and X3 are in principle also suitable, for example, those which have been prepared from isocyanates based entirely or 15 partly on aliphatic or cycloaliphatic diisocyanates such as 1,8-diisocyanato-octane, l,ll-diisocyanato-undecane, 4,4-diisocyanato-cyclohexane, 4,4'-diisocyanatodicyclo-hexylmethane or diisocyanates according to DE-OS
3,402,623 (US-P 4,613,685). The polyisocyanates con-20 taining isocyanurate groups may be prepared, forexample, according to DE-P 2,616,416, EP-OS 3,765, EP-OS
10,589, EP-OS 47,452, US-P 4,288,586, US-P 4,412,073, US-P 4,324,879, DE-OS 3,219,608, EP-OS 0,155,559, EP-OS
0,017,998, DE-OS 2,806,731, EP-OS 0,082,987, EP-OS
25 0,100,129 or EP-OS 0,047,452.
Whether the polyisocyanates containing iso-cyanurate groups consist for the most part of pure triisocyanato-monoisocyanurate (i) or of mixtures thereof (ii) with their higher homologues depends 30 primarily upon the nature of the starting diisocyanate used and on the degree of trimerization. Thus, for example, if the two isocyanate groups of the diiso-cyanate used differ greatly in their reactivity, as, for example in the aliphatic-cycloaliphatic diisocyanates Mo-2933 - 4 -according to DE-OS 3,402,623, then virtually pure triisocyanato-monoisocyanurates can be prepared from them even if their degree of trimerization is in the region of 50% (DE-OS 3,507,719). If the isocyanate 5 groups of the diisocyanates used as starting material are identical only or slightly different in their reactivity, the formation of higher homologues in the trimerization reaction can be kept within narrow limits by premature termination of the trimerization reaction 10 (followed by distillative removal of unreacted diiso-cyanate excess). In general, however, the proportion of higher homologues present in the polyisocyanates con-taining isocyanurate groups is not decisive in determin-ing whether these polyisocyanates are suitable for the 15 process according to the invention. Polyisocyanates with isocyanurate groups suitable as starting components (ii) for the process according to the invention may contain up to about 80% by weight of higher homologues containing more than one isocyanurate group. The 20 polyisocyanates (i) and (ii) containing isocyanurate groups generally have an isocyanate content of about 10 to 30Z by weight, preferably about 15 to 25Z by weight.
The polyisocyanate mixtures (iii) which may also be used as polyisocyanate component a) in the 25 process according to the invention are mixtures of polyisocyanates containing isocyanurate groups (i) or (ii) with up to about 60, preferably up to about 40 and most preferably up to about 20 isocyanate equivalent percent, based on the total quantity of component (iii), 30 of polyisocyanates which are free from isocyanurate groups, in particular diisocyanates such as 1,6-diiso-cyanatohexane, IPDI or in particular uretdione diiso-cyanates containing aliphatically and/or cyclo-aliphatically bound isocyanate groups and corresponding 35 to the formula Mo-2933 - 5 -\ CO
wherein Xl and X2 have the meaning or preferred meaning indicated above. Such uretdione diisocyanates are frequently formed in minor quantities (about 0.1 to 5, 10 in particular about 0.3 to 3 isocyanate equivalents percent) in addition to the polyisocyanates containing isocyanurate groups in the trimerization reaction of aliphatic and/or cycloaliphatic diisocyanates of the type exemplified above. In addition, the isocyanate 15 mixtures (iii) may also contain polyisocyanates free from isocyanurate groups in the form of the well-known "lacquer polyisocyanates" such as tris-(6-isocyanato-hexyl)-biuret and its higher homologues or polyiso-cyanates containing urethane groups such as those 20 obtained, for example, from the reaction of excess quantities of IPDI with polyhydric alcohols such as trimethylolpropane.
Component a) preferably contains at least about 40 isocyanate equivalent percent of triisocyanato-mono-25 isocyanurates corresponding to the above generalformula.
Component b) is based on (i) polyester polyols or mixtures of various polyester polyols having a hydroxyl functionality (average) of about 1.8 to 5, 30 preferably 2 to 3, and a hydroxyl number (average) of about 15 to 300, preferably about 40 to 150, or (ii) mixtures of such polyester polyols with up to about 10%
by weight, based on the weight of the mixture, of (cyclo)alkane polyols having a hydroxyl number above 35 about 300 and optionally containing ester groups.
Mo-2933 - 6 -The polyester polyols (i) are esterification products of di- and/or polycarboxylic acids with excess quantities of (cyclo)alkane polyols known from poly-urethane chemistry. Suitable acids for use in preparing 5 the esterification products include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, hexahydroterephthalic acid 10 and/or 1-methyl-cyclohexane-2,5-dicarboxylic acid or intramolecular anhydrides of the acids are capable of intramolecular anhydride formation. Suitable (cyclo)-alkane polyols include (cyclo)alkane diols such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, 15 diethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, 2-methyl-propane-1,3-diol, 1,4- and 1,3-bis-(hydroxymethyl)-cyclohexane, trimethylolpropane, glycerol, pentaerythritol, 1,2-, 1,3- or 1,4-cyclohexane diol, 2,2-bis-(4-hydroxycyclo-20 hexyl)-propane and/or 2-methyl-2,4-bis-(4-hydroxycyclo-hexyl)-pentane. In the preparation of polyester polyols from the starting materials exemplified above, a pro-portion of monocarboxylic acids such as benzoic acid or hexane carboxylic acids or of monohydric alcohols such 25 as n-butanol or n-hexanol may also be included provided the conditions mentioned above concerning the hydroxyl functionality are observed. The inclusion of such monofunctional starting components is, however, by no means preferred.
The polyester polyols (i) also include the polylactones known from polyurethane chemistry, e.g. the polymers of ~-caprolactone started on polyhydric alcohols of the type exemplified.
Mo-2933 - 7 -In addition, the polyester polyols (i) include the hydroxyl-containing polycarbonates known from polyurethane chemistry such as those obtained, for example, from the reaction of the diols exemplified 5 above with phosgene or diarylcarbonates, in particular diphenylcarbonate.
However, particularly preferred polyester polyols (i) include those which contain at least about lOZ by weight, preferably about 15 to 50Z by weight, of 10 1,2-, 1,3- and/or 1,4-difunctional cycloaliphatic groups corresponding to the formula R
~
incorporated in the molecule. In this formula, R represents hydrogen or an alkyl group with 1 to 4 carbon atoms, preferably hydrogen or a methyl group, most preferably hydrogen.
These cyclohexylene groups may be incorporated by using those dicarboxylic acids or diols of the type exemplified above which contain cyclohexylene groups for the preparation of the above-mentioned esterification products of polycarboxylic acids with polyhydric 25 alcohols, or the polylactones or polycarbonates.
Instead of using polyester polyols (i), mixtures (ii) of such polyester polyols with (cyclo)-alkane polyols having a hydroxyl number above about 300 and optionally containing ester groups may be used as 30 polyhydroxyl component b) in the process according to the invention. When such mixtures are used, the pro-portion of the last-mentioned polyols in the mixture should be at the most 10% by weight, based on the total weight of component (ii). Examples of such components 35 for the mixture include the above-mentioned simple (cyclo)alkane polyols as well as low molecular weight Mo-2933 - 8 -polyols containing ester groups such as adipic acid-bis-(2-hydroxyethyl)-ester.
The use of polyester polyols (i) is preferred over the use of the above-mentioned mixture (ii).
The process according to the invention, i.e.
the reaction of component a) with component b) may be carried out without solvents although it is preferred to use solvents of the kind commonly used for producing polyurethane lacquers. Preferred solvents include 10 aromatic hydrocarbons such as toluene, xylene and higher alkylbenzene mixtures; aliphatic hydrocarbons such as cyclohexane; and polar solvents such as ethyl acetate, n-butyl acetate and i-butyl acetate, ethyl glycol acetate, methoxy propylene glycol acetate, methyl ethyl 15 ketone, methyl-i-amyl ketone, cyclohexanone or mixtures of the above solvents.
For the preparation of the prepolymers con-taining isocyanate groups, polyisocyanate component a) or solutions thereof are generally introduced into the 20 reaction vessel under an inert gas such as nitrogen and mixed with polyol component b) or solutions thereof and reacted under an inert gas at about 20 to 160C, prefer-ably about 60 to 120C, until the isocyanate content has fallen to the calculated level or slightly below and 25 remains constant. The quantitative proportions of the reactants are chosen so that the NCO/OH equivalent ratio is greater than 2:1, preferably greater than about 4:1 and most preferably about 7:1 to 15:1.
Based on the solids content, the resulting 30 products of the process have an isocyanate content of about 1 to 16% by weight, preferably about 4 to 12Z by weight.
If solvents of the type exemplified above have already been used for the preparation of the isocyanate Mo-2933 - 9 -prepolymers, binder solutions for moisture hardening one-component lacquers are obtained directly and may be used for their particular purpose after the addition of the usual auxiliary agents and additives. When isocyanate prepolymers are prepared without solvents of the type exemplified above, the reaction product obtained may be dissolved in such a solvent to form a binder solution.
As may be seen from the figures given above concerning the NCO/OH equivalent ratio and the isocyanate 1~ content, the products obtained from the process according to the invention may be either true isocyanate prepolymers, i.e.
free from monomers, or mixtures of isocyanate prepolymers with excess unreacted starting polyisocyanates a), also known as "isocyanate semi-prepolymers." The term "prepolymers containing isocyanate groups" used in the context of this invention includes both "true" isocyanate prepolymers and isocyanate semi-prepolymers.
The binder solutions according to the invention may be mixed with the usual additives used in polyurethane lacquer ~ technology. These include catalysts for the isocyanate/water reaction such as dibutyl tin dilaurate; levelling agents such as acrylate polymers, e.g. Modaflow* from Monsanto, fillers such as talcum or heavy spar and the usual inorganic or organic pigments.
The one-component lacquers based on the products of the process according to the invention are suitable for all high quality top coat lacquers which are required to be long lasting. The following applications are mentioned as examples:
wood lacquering (clear lacquers for parquet flooring, lacquers 3~ for painting boats, furniture lacquers); impregnating agents for brickwork, concrete, asbestos cement and stone flooring;
Mo-2933 - 10 -*Trademark ~A
and synthetic lacquers containing lightfast and color stable pigments or the like. Moisture hardening one-component lacquers based on the products according to the invention are particularly suitable for decorative 5 weather-resistant and color stable lacquers used out-doors which are required to have very good gloss re-tention and resistance to chalking as well as high resistance to solvents, abrasion and chemicals. Impreg-nation with clear lacquers based on the products 10 according to the invention protect the coated surfaces against the action of W light, moisture, oils, fuels and corrosive chemicals. The products of the process according to the invention are also suitable for use as binders for corrosion protective lacquers or pigmented 15 or unpigmented top coat lacquers for heavy goods vehicles such as buses or rail coaches.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless 20 otherwise specified.
EXAMPLES
The following starting components are used in the examples.
Polyisocyanate I:
A thin layered polyisocyanate containing isocyanurate groups based on 1,6-hexane diisocyanate, prepared according to Example 1 of EP-A 10,589 (U.S.
Patent 4,324,879) and having an isocyanate content of 21.4Z, a viscosity (25C) of 2100 mPas, a monomeric 30 1,6-diisocyanatohexane content of O.lZ and a triiso-cyanato-monoisocyanurate content of about 49Z.
Mo-2933 - 11 -Polyester I: 1 3 3 4 2 3 0 Starting materials:
3.48 kg trimethylolpropane 26.0 mol 25.83 kg 1,4-bis-(hydroxymethyl)-cyclohexane 179.4 "
5 2.1 kg ethylene glycol 33.8 "
15.14 kg neopentyl glycol 145.6 "
49.25 kg phthalic acid anhydride 332.8 "
3.0 kg SnC12 2 H2O as catalyst.
Preparation of the polyester:
The starting products (without catalyst) were weighed into a 100 1 tank and melted by heating to a temperature of 140C under nitrogen. After one hour at this temperature, water was distilled off and at the same time the temperature was raised to 200C in the 15 course of 5 to 6 hours.
After a further 2 hours, the catalyst was added and the vacuum phase was begun. The final vacuum of 15 mbar was reached after about 6 hours. Condensation was continued until the acid number was below 3 (about 20 12 hours).
The resulting polyester was a solid resin which had the following properties:
Acid number: '3 OH number: 48.2 25 Iodine color number:
Proportion of cyclohexylene segments (C6Hlo): 15.85%.
Polyester II:
Starting materials:
9.6 mol hexahydrophthalic acid anhydride 30 1.9 mol trimethylolpropane 4.8 mol hexane-1,6-diol 4.3 mol perhydrobisphenol A
The polyester was prepared by the method employed for polyester I.
Mo-2933 - 12 -Characteristic data:
Acid number: 8 OH number: 63 Iodine color value:
Content in cyclohexylene segments (C6H1o): 47.25%.
PolYester III:
Starting materials:
3.00 mol neopentyl glycol 0.75 mol ethane diol 3.75 mol 1,4-bis-(hydroxymethyl)cyclohexane 6.5 mol phthalic acid anhydride.
Polyester III was prepared by a method analogous to that employed for polyester I.
Characteristic data:
Acid number: 2.9 OH number: 59.6 Iodine color value:
Content in cyclohexylene segments (C6H1o): 17.64%.
Example 1 Reaction mixture 700 g polyisocyanate I
429 g of a 70% solution in Solvesso** 100* and 2-methoxypropyl-acetate (4:1) of polyester I
240 9 Solvesso 100*
60 g 2-methoxypropyl-acetate Method:
The polyisocyanate was introduced into the reaction vessel at room temperature and homogeneously mixed with the polyester solution. The mixture was then diluted with the solvents and heated to 100C and stirred at this temperature until the isocyanate content of the solution was 9.6% (about 5 to 6 hours). After * Solvesso 100 is a commercially available mixture of alkyl aromatic compounds in the boiling point range of 161 to 179C.
**Trademark Mo-2933 - 13 -~`
A
cooling, the product in the form of a 70~ solution had a - viscosity of 1600 mPas (25C).
Further characteristic data of the product:
NCO/OH = 13.7 5 NCO content of the solution: 9.6Z
Monomeric diisocyanate content of the solution: below 0.01%
Color value (DIN 53 409): <20.
Example 2 The procedure was as indicated in Example 1 and the following compounds were reacted together:
1,400 g polyisocyanate I
986 g polyester III
1,617 g Solvesso 100 The resulting product had the data given below.
60~ solution in Solvesso 100 Viscosity: 600 mPas (25C) NCO/OH: 7.2 NCO content of the solution: 6.3%
20 Color value (DIN 53 409): <20 Monomeric diisocyanate content: <0.01%.
Example 3 The procedure was the same as in Example 1 and the following components were reacted:
25 2,000 g polyisocyanate I
889 g polyester II
963 g xylene 963 g butyl acetate.
Characteristic data of the reaction product:
30 NCO/OH = 10 60% solution in xylene/butyl acetate (1:1) NCO content of the solution: 7.2 Viscosity of the solution: 800 mPas (25C).
Mo-2933 - 14 -Example 4 1 334230 This examples illustrates the preparation of clear lacquer films obtained from the isocyanate pre-polymers of Examples 1, 2 and 3 and their properties.
The solution of the given prepolymer was diluted with a mixture of xylene and 2-methoxypropyl-acetate (4:1) to a working concentration of 40Z and O.lZ
of dibutyl tin dilaurate was added as a catalyst. Clear lacquer films were applied by means of a coating roller 10 system (width of gap 0.12 mm) to clean, degreased glass plates and steel plates. The plates were stored at ambient temperature (20 to 25C) at a relative humidity of 60Z. Glossy, colorless clear lacquer films were obtained. The lacquer films attained their final 15 properties after about 7 days. The tests were then carried out. The results of the measurements are summarized in the Table.
Example Example Example 20 Sand drying (DIN 53 150) 4 h 5 h 4 h Pendulum hardness K~nig (DIN 53 157) 236 219 227 Solvent attack* after 7 days' storage 25 Action (1 min) of Ethyl glycol acetate 0 0 0 Ethyl acetate 0 0 0 Acetone 0 1 0 Super grade petrol 0 0 0 30 Abrasion according to DIN 53 109 (load 10 N, 1000 revolutions) 16 18 11 Erichsen cupping (DIN 53 156) 10.0 10.0 9.9 (Layer thickness of films: 45-55 ~m) Mo-2933 - 15 -*The solvent attack was.measured in 5 stages:
0, 1, 2, 3, 4.
0 = film completely unchanged 4 = film dissolves.
The results of the lacquer film tests showed that the binders according to the invention harden to form very high quality polyurethane layers which are hard but also tough and elastic.
The drying process may be accelerated if 10 necessary by the addition of a higher proportion of catalyst.
Example 5 In this example, the isocyanate prepolymers according to the invention were used for the preparation 15 of pigmented lacquers and the durability of the films obtained from the lacquers was examined. To simplify the assessment, only white lacquers were prepared. For this purpose, pigments and additives were added to the 70Z or 60Z solutions of the isocyanate prepolymers from 20 Examples 1, 2 and 3 and the solutions were adjusted to a lower concentration by the addition of a solvent mixture of xylene/butyl acetate (3:1) so that the outflow time (DIN 53 211, 4 mm nozzle) was 40 seconds. The pigment was titrated on a three-roller mixer.
The compositions of the triturates are entered in the following Table.
Mo-2933 - 16 -Components Parts bY weight Polyisocyanate solution from Example 1 50 - -from Example 2 - 58.3 from Example 3 - - 58.3 Solvent mixture:
Xylene/butyl acetate (3:1) 20.5 60.5 63.4 Silicone oil as levelling agent (10% in methoxypropylene glycol acetate) 0.4 0.4 0.4 Catalyst (dibutyl tin dilaurate) 0.1 0.1 0.1 Titanium dioxide (rutile type) 22 22 22 Agent for preventing settling of the pigment* 0.2 0.2 0.2 *highly disperse silica (Aerosil* 300 of Degussa).
The lacquer compositions shown in the Table were completely stable for at least 3 months when stored in closed containers with careful exclusion of moisture.
Samples of the lacquers ready for spraying were sprayed on mild steel plates at a thickness of 0.5 mm and the samples were stored for 14 days at about 23C and a relative humidity of 60%.
The impact strength (ASTM-D 2794), rocking hardness of Konig (DIN 53 157) and bonding strength in crosscut (DIN 53 151) of the lacquer films were then tested. The test results are summarized in the Table below.
Impact strength Hardness Bond strength Example (kg x cm) (sec) (Gt 0-4) To test the durability of the lacquers prepared from the isocyanate prepolymers according to the invention under permanent exposure, the steel plates Mo-2933 - 17 -*Trademark were subjected to a weathering test in Florida. The plates were laid out at an angle of 45 and the change of gloss with time was assessed. The gloss was assessed according to the Gardner hardness scale at 60C
5 (DIN 67 530) at intervals of 3 months over a period of 18 months. The results were summarized in the Table below.
Gloss reading after Lacquer sample from 0 36 9 12 15 18 months 10 Example 1 98 90 90 85 80 75 70 Example 2 97 93 90 85 78 75 72 Example 3 98 93 93 89 85 80 75 The lacquers on the weathered plates were mechanically tested again after they had been cleaned.
15 Only a very slight, virtually negligible deterioration in their properties could be detected.
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 20 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.
Mo-2933 - 18 -
CONTAINING ISOCYANATE GROUPS, THE PREPOLYMERS
OBTAINABLE BY THIS PROCESS AND THEIR USE AS
BINDERS IN ONE-COMPONENT LACQUERS
Field of the Invention This invention relates to new prepolymers containing free isocyanate groups obtained by the reaction of excess quantities of polyisocyanates con-10 taining isocyanurate groups with polyester polyols, to the prepolymers obtainable by this process and to their use as binders in moisture hardening one-component lacquers.
Description of the Prior Art 15Moisture hardening polyurethane lacquers based on aliphatic polyisocyanates, in particular on iso-cyanate prepolymers containing aliphatically bound isocyanate groups are already known and have been described, for example, by H. Kittel in "Lehrbuch der 20 Lacke und Beschichtungen", publishers W.A. Colomb, Berlin-Oberschwandorf 1973, Volume l, Part 2, page 574.
Polyisocyanates with a biuret structure prepared from hexamethylene diisocyanate have gained a position of particular commercial importance for the preparation of 25 such binders.
The previously known moisture hardening one-component PUR lacquers have various advantages over two-component PUR lacquers, e.g., simple, uncomplicated methods of working up, great hardness and rapid onset of 30 drying by the formation of high molecular weight poly-urethane ureas. However, the moisture hardening one-component lacquers of the state of the art based on aliphatic isocyanates also have certain disadvantages which manifest themselves in the lack of - 1 33~0 long-term stability of the lacquers. Pigmented lacquers based on the isocyanate prepolymers previously known, for example, frequently do not satisfy the requirements 5 for resistance to yellowing on exposure to light and for resistance to weathering. The insufficient resistance to weatherin~ leads to loss of gloss and to chalking of the coatings produced from the lacquers.
It was an object of the present invention to 10 provide new prepolymers containing isocyanate groups as binders for moisture hardening one-component lacquers which would be superior to the known prepolymers in the properties mentioned above.
This problem was solved by means of the process 15 according to the invention described below.
SUMMARY OF THE INVENTION
The invention is directed to a process for the preparation of prepolyme,s containing free isocyanate groups and having an isocyanate content of 1 to 16~ by 20 weight by the reaction of a) a polyisocyanate component with b) a polyhydroxyl component based on (i) at least one polyester polyol having a hydroxyl functionality (average) of about 1.8 to 5 and a hydroxyl number (average) of about 15 to 300 or (ii) mixtures of polyester polyols of the type mentioned under (i) with up to about 102 by weight, based on the weight of the mlxture, of (cyclo)alkane polyols having a hydroxyl number above about 300 and optionally containing ester groups at an NCO/OH equivalent ratio above 4:1, characterized in thct the compounds used as component a) are Mo-2933 - 2 -, .~ ~
(i) triisocyanato-isocyanurates corresponding to the formula ( ~
o (ii) mixtures of the triisocyanato-isocyanurates indicated under (i) with their higher homologues containing more than one isocyanurate ring or (iii) mixtures of the polyisocyanates indicated under (i) and (ii) with up to about 60 isocyanate equivalent percent, based on the total quantity of component a), of organic polyisocyanates free from isocyanurate groups, wherein 20 Xl, X2 and X3 in the above formula represent identical or different groups which are difunctional, aliphatic or cycloaliphatic hydrocarbon groups having a molecular weight of 84 to 206.
The present invention also relates to the 25 prepolymers with free isocyanate groups obtainable by this process and their use as binders for moisture hardening one-component lacquers.
DETAILED DESCRIPTION OF THE lNV~:NlION
Polyisocyanate component a) to be used in the 30 process according to the invention is based on polyiso-cyanates containing isocyanurate groups or mixtures of such polyisocyanates with polyisocyanates which are free from isocyanurate groups.
The polyisocyanates containing isocyanurate 35 groups may be both (i) triisocyanato-monoisocyanurates and (ii) mixtures thereof with their higher homologues.
Mo-2933 - 3 --- l 334230 The triisocyanato-monoisocyanurates correspond to the above general formula in which the symbols Xl, X2 and X3 have the meanings indicated above, but preferably represent identical or different hydrocarbon groups 5 linking the isocyanate groups of 1,6-diisocyanatohexane and/or of l-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane. The polyisocyanates containing isocyanurate groups used in the process according to the invention are thus preferably the trimerization products 10 of these two diisocyanates or of mixtures thereof although other polyisocyanates with isocyanurate groups conforming to the above definition of Xl, X2 and X3 are in principle also suitable, for example, those which have been prepared from isocyanates based entirely or 15 partly on aliphatic or cycloaliphatic diisocyanates such as 1,8-diisocyanato-octane, l,ll-diisocyanato-undecane, 4,4-diisocyanato-cyclohexane, 4,4'-diisocyanatodicyclo-hexylmethane or diisocyanates according to DE-OS
3,402,623 (US-P 4,613,685). The polyisocyanates con-20 taining isocyanurate groups may be prepared, forexample, according to DE-P 2,616,416, EP-OS 3,765, EP-OS
10,589, EP-OS 47,452, US-P 4,288,586, US-P 4,412,073, US-P 4,324,879, DE-OS 3,219,608, EP-OS 0,155,559, EP-OS
0,017,998, DE-OS 2,806,731, EP-OS 0,082,987, EP-OS
25 0,100,129 or EP-OS 0,047,452.
Whether the polyisocyanates containing iso-cyanurate groups consist for the most part of pure triisocyanato-monoisocyanurate (i) or of mixtures thereof (ii) with their higher homologues depends 30 primarily upon the nature of the starting diisocyanate used and on the degree of trimerization. Thus, for example, if the two isocyanate groups of the diiso-cyanate used differ greatly in their reactivity, as, for example in the aliphatic-cycloaliphatic diisocyanates Mo-2933 - 4 -according to DE-OS 3,402,623, then virtually pure triisocyanato-monoisocyanurates can be prepared from them even if their degree of trimerization is in the region of 50% (DE-OS 3,507,719). If the isocyanate 5 groups of the diisocyanates used as starting material are identical only or slightly different in their reactivity, the formation of higher homologues in the trimerization reaction can be kept within narrow limits by premature termination of the trimerization reaction 10 (followed by distillative removal of unreacted diiso-cyanate excess). In general, however, the proportion of higher homologues present in the polyisocyanates con-taining isocyanurate groups is not decisive in determin-ing whether these polyisocyanates are suitable for the 15 process according to the invention. Polyisocyanates with isocyanurate groups suitable as starting components (ii) for the process according to the invention may contain up to about 80% by weight of higher homologues containing more than one isocyanurate group. The 20 polyisocyanates (i) and (ii) containing isocyanurate groups generally have an isocyanate content of about 10 to 30Z by weight, preferably about 15 to 25Z by weight.
The polyisocyanate mixtures (iii) which may also be used as polyisocyanate component a) in the 25 process according to the invention are mixtures of polyisocyanates containing isocyanurate groups (i) or (ii) with up to about 60, preferably up to about 40 and most preferably up to about 20 isocyanate equivalent percent, based on the total quantity of component (iii), 30 of polyisocyanates which are free from isocyanurate groups, in particular diisocyanates such as 1,6-diiso-cyanatohexane, IPDI or in particular uretdione diiso-cyanates containing aliphatically and/or cyclo-aliphatically bound isocyanate groups and corresponding 35 to the formula Mo-2933 - 5 -\ CO
wherein Xl and X2 have the meaning or preferred meaning indicated above. Such uretdione diisocyanates are frequently formed in minor quantities (about 0.1 to 5, 10 in particular about 0.3 to 3 isocyanate equivalents percent) in addition to the polyisocyanates containing isocyanurate groups in the trimerization reaction of aliphatic and/or cycloaliphatic diisocyanates of the type exemplified above. In addition, the isocyanate 15 mixtures (iii) may also contain polyisocyanates free from isocyanurate groups in the form of the well-known "lacquer polyisocyanates" such as tris-(6-isocyanato-hexyl)-biuret and its higher homologues or polyiso-cyanates containing urethane groups such as those 20 obtained, for example, from the reaction of excess quantities of IPDI with polyhydric alcohols such as trimethylolpropane.
Component a) preferably contains at least about 40 isocyanate equivalent percent of triisocyanato-mono-25 isocyanurates corresponding to the above generalformula.
Component b) is based on (i) polyester polyols or mixtures of various polyester polyols having a hydroxyl functionality (average) of about 1.8 to 5, 30 preferably 2 to 3, and a hydroxyl number (average) of about 15 to 300, preferably about 40 to 150, or (ii) mixtures of such polyester polyols with up to about 10%
by weight, based on the weight of the mixture, of (cyclo)alkane polyols having a hydroxyl number above 35 about 300 and optionally containing ester groups.
Mo-2933 - 6 -The polyester polyols (i) are esterification products of di- and/or polycarboxylic acids with excess quantities of (cyclo)alkane polyols known from poly-urethane chemistry. Suitable acids for use in preparing 5 the esterification products include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, hexahydroterephthalic acid 10 and/or 1-methyl-cyclohexane-2,5-dicarboxylic acid or intramolecular anhydrides of the acids are capable of intramolecular anhydride formation. Suitable (cyclo)-alkane polyols include (cyclo)alkane diols such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, 15 diethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, 2-methyl-propane-1,3-diol, 1,4- and 1,3-bis-(hydroxymethyl)-cyclohexane, trimethylolpropane, glycerol, pentaerythritol, 1,2-, 1,3- or 1,4-cyclohexane diol, 2,2-bis-(4-hydroxycyclo-20 hexyl)-propane and/or 2-methyl-2,4-bis-(4-hydroxycyclo-hexyl)-pentane. In the preparation of polyester polyols from the starting materials exemplified above, a pro-portion of monocarboxylic acids such as benzoic acid or hexane carboxylic acids or of monohydric alcohols such 25 as n-butanol or n-hexanol may also be included provided the conditions mentioned above concerning the hydroxyl functionality are observed. The inclusion of such monofunctional starting components is, however, by no means preferred.
The polyester polyols (i) also include the polylactones known from polyurethane chemistry, e.g. the polymers of ~-caprolactone started on polyhydric alcohols of the type exemplified.
Mo-2933 - 7 -In addition, the polyester polyols (i) include the hydroxyl-containing polycarbonates known from polyurethane chemistry such as those obtained, for example, from the reaction of the diols exemplified 5 above with phosgene or diarylcarbonates, in particular diphenylcarbonate.
However, particularly preferred polyester polyols (i) include those which contain at least about lOZ by weight, preferably about 15 to 50Z by weight, of 10 1,2-, 1,3- and/or 1,4-difunctional cycloaliphatic groups corresponding to the formula R
~
incorporated in the molecule. In this formula, R represents hydrogen or an alkyl group with 1 to 4 carbon atoms, preferably hydrogen or a methyl group, most preferably hydrogen.
These cyclohexylene groups may be incorporated by using those dicarboxylic acids or diols of the type exemplified above which contain cyclohexylene groups for the preparation of the above-mentioned esterification products of polycarboxylic acids with polyhydric 25 alcohols, or the polylactones or polycarbonates.
Instead of using polyester polyols (i), mixtures (ii) of such polyester polyols with (cyclo)-alkane polyols having a hydroxyl number above about 300 and optionally containing ester groups may be used as 30 polyhydroxyl component b) in the process according to the invention. When such mixtures are used, the pro-portion of the last-mentioned polyols in the mixture should be at the most 10% by weight, based on the total weight of component (ii). Examples of such components 35 for the mixture include the above-mentioned simple (cyclo)alkane polyols as well as low molecular weight Mo-2933 - 8 -polyols containing ester groups such as adipic acid-bis-(2-hydroxyethyl)-ester.
The use of polyester polyols (i) is preferred over the use of the above-mentioned mixture (ii).
The process according to the invention, i.e.
the reaction of component a) with component b) may be carried out without solvents although it is preferred to use solvents of the kind commonly used for producing polyurethane lacquers. Preferred solvents include 10 aromatic hydrocarbons such as toluene, xylene and higher alkylbenzene mixtures; aliphatic hydrocarbons such as cyclohexane; and polar solvents such as ethyl acetate, n-butyl acetate and i-butyl acetate, ethyl glycol acetate, methoxy propylene glycol acetate, methyl ethyl 15 ketone, methyl-i-amyl ketone, cyclohexanone or mixtures of the above solvents.
For the preparation of the prepolymers con-taining isocyanate groups, polyisocyanate component a) or solutions thereof are generally introduced into the 20 reaction vessel under an inert gas such as nitrogen and mixed with polyol component b) or solutions thereof and reacted under an inert gas at about 20 to 160C, prefer-ably about 60 to 120C, until the isocyanate content has fallen to the calculated level or slightly below and 25 remains constant. The quantitative proportions of the reactants are chosen so that the NCO/OH equivalent ratio is greater than 2:1, preferably greater than about 4:1 and most preferably about 7:1 to 15:1.
Based on the solids content, the resulting 30 products of the process have an isocyanate content of about 1 to 16% by weight, preferably about 4 to 12Z by weight.
If solvents of the type exemplified above have already been used for the preparation of the isocyanate Mo-2933 - 9 -prepolymers, binder solutions for moisture hardening one-component lacquers are obtained directly and may be used for their particular purpose after the addition of the usual auxiliary agents and additives. When isocyanate prepolymers are prepared without solvents of the type exemplified above, the reaction product obtained may be dissolved in such a solvent to form a binder solution.
As may be seen from the figures given above concerning the NCO/OH equivalent ratio and the isocyanate 1~ content, the products obtained from the process according to the invention may be either true isocyanate prepolymers, i.e.
free from monomers, or mixtures of isocyanate prepolymers with excess unreacted starting polyisocyanates a), also known as "isocyanate semi-prepolymers." The term "prepolymers containing isocyanate groups" used in the context of this invention includes both "true" isocyanate prepolymers and isocyanate semi-prepolymers.
The binder solutions according to the invention may be mixed with the usual additives used in polyurethane lacquer ~ technology. These include catalysts for the isocyanate/water reaction such as dibutyl tin dilaurate; levelling agents such as acrylate polymers, e.g. Modaflow* from Monsanto, fillers such as talcum or heavy spar and the usual inorganic or organic pigments.
The one-component lacquers based on the products of the process according to the invention are suitable for all high quality top coat lacquers which are required to be long lasting. The following applications are mentioned as examples:
wood lacquering (clear lacquers for parquet flooring, lacquers 3~ for painting boats, furniture lacquers); impregnating agents for brickwork, concrete, asbestos cement and stone flooring;
Mo-2933 - 10 -*Trademark ~A
and synthetic lacquers containing lightfast and color stable pigments or the like. Moisture hardening one-component lacquers based on the products according to the invention are particularly suitable for decorative 5 weather-resistant and color stable lacquers used out-doors which are required to have very good gloss re-tention and resistance to chalking as well as high resistance to solvents, abrasion and chemicals. Impreg-nation with clear lacquers based on the products 10 according to the invention protect the coated surfaces against the action of W light, moisture, oils, fuels and corrosive chemicals. The products of the process according to the invention are also suitable for use as binders for corrosion protective lacquers or pigmented 15 or unpigmented top coat lacquers for heavy goods vehicles such as buses or rail coaches.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless 20 otherwise specified.
EXAMPLES
The following starting components are used in the examples.
Polyisocyanate I:
A thin layered polyisocyanate containing isocyanurate groups based on 1,6-hexane diisocyanate, prepared according to Example 1 of EP-A 10,589 (U.S.
Patent 4,324,879) and having an isocyanate content of 21.4Z, a viscosity (25C) of 2100 mPas, a monomeric 30 1,6-diisocyanatohexane content of O.lZ and a triiso-cyanato-monoisocyanurate content of about 49Z.
Mo-2933 - 11 -Polyester I: 1 3 3 4 2 3 0 Starting materials:
3.48 kg trimethylolpropane 26.0 mol 25.83 kg 1,4-bis-(hydroxymethyl)-cyclohexane 179.4 "
5 2.1 kg ethylene glycol 33.8 "
15.14 kg neopentyl glycol 145.6 "
49.25 kg phthalic acid anhydride 332.8 "
3.0 kg SnC12 2 H2O as catalyst.
Preparation of the polyester:
The starting products (without catalyst) were weighed into a 100 1 tank and melted by heating to a temperature of 140C under nitrogen. After one hour at this temperature, water was distilled off and at the same time the temperature was raised to 200C in the 15 course of 5 to 6 hours.
After a further 2 hours, the catalyst was added and the vacuum phase was begun. The final vacuum of 15 mbar was reached after about 6 hours. Condensation was continued until the acid number was below 3 (about 20 12 hours).
The resulting polyester was a solid resin which had the following properties:
Acid number: '3 OH number: 48.2 25 Iodine color number:
Proportion of cyclohexylene segments (C6Hlo): 15.85%.
Polyester II:
Starting materials:
9.6 mol hexahydrophthalic acid anhydride 30 1.9 mol trimethylolpropane 4.8 mol hexane-1,6-diol 4.3 mol perhydrobisphenol A
The polyester was prepared by the method employed for polyester I.
Mo-2933 - 12 -Characteristic data:
Acid number: 8 OH number: 63 Iodine color value:
Content in cyclohexylene segments (C6H1o): 47.25%.
PolYester III:
Starting materials:
3.00 mol neopentyl glycol 0.75 mol ethane diol 3.75 mol 1,4-bis-(hydroxymethyl)cyclohexane 6.5 mol phthalic acid anhydride.
Polyester III was prepared by a method analogous to that employed for polyester I.
Characteristic data:
Acid number: 2.9 OH number: 59.6 Iodine color value:
Content in cyclohexylene segments (C6H1o): 17.64%.
Example 1 Reaction mixture 700 g polyisocyanate I
429 g of a 70% solution in Solvesso** 100* and 2-methoxypropyl-acetate (4:1) of polyester I
240 9 Solvesso 100*
60 g 2-methoxypropyl-acetate Method:
The polyisocyanate was introduced into the reaction vessel at room temperature and homogeneously mixed with the polyester solution. The mixture was then diluted with the solvents and heated to 100C and stirred at this temperature until the isocyanate content of the solution was 9.6% (about 5 to 6 hours). After * Solvesso 100 is a commercially available mixture of alkyl aromatic compounds in the boiling point range of 161 to 179C.
**Trademark Mo-2933 - 13 -~`
A
cooling, the product in the form of a 70~ solution had a - viscosity of 1600 mPas (25C).
Further characteristic data of the product:
NCO/OH = 13.7 5 NCO content of the solution: 9.6Z
Monomeric diisocyanate content of the solution: below 0.01%
Color value (DIN 53 409): <20.
Example 2 The procedure was as indicated in Example 1 and the following compounds were reacted together:
1,400 g polyisocyanate I
986 g polyester III
1,617 g Solvesso 100 The resulting product had the data given below.
60~ solution in Solvesso 100 Viscosity: 600 mPas (25C) NCO/OH: 7.2 NCO content of the solution: 6.3%
20 Color value (DIN 53 409): <20 Monomeric diisocyanate content: <0.01%.
Example 3 The procedure was the same as in Example 1 and the following components were reacted:
25 2,000 g polyisocyanate I
889 g polyester II
963 g xylene 963 g butyl acetate.
Characteristic data of the reaction product:
30 NCO/OH = 10 60% solution in xylene/butyl acetate (1:1) NCO content of the solution: 7.2 Viscosity of the solution: 800 mPas (25C).
Mo-2933 - 14 -Example 4 1 334230 This examples illustrates the preparation of clear lacquer films obtained from the isocyanate pre-polymers of Examples 1, 2 and 3 and their properties.
The solution of the given prepolymer was diluted with a mixture of xylene and 2-methoxypropyl-acetate (4:1) to a working concentration of 40Z and O.lZ
of dibutyl tin dilaurate was added as a catalyst. Clear lacquer films were applied by means of a coating roller 10 system (width of gap 0.12 mm) to clean, degreased glass plates and steel plates. The plates were stored at ambient temperature (20 to 25C) at a relative humidity of 60Z. Glossy, colorless clear lacquer films were obtained. The lacquer films attained their final 15 properties after about 7 days. The tests were then carried out. The results of the measurements are summarized in the Table.
Example Example Example 20 Sand drying (DIN 53 150) 4 h 5 h 4 h Pendulum hardness K~nig (DIN 53 157) 236 219 227 Solvent attack* after 7 days' storage 25 Action (1 min) of Ethyl glycol acetate 0 0 0 Ethyl acetate 0 0 0 Acetone 0 1 0 Super grade petrol 0 0 0 30 Abrasion according to DIN 53 109 (load 10 N, 1000 revolutions) 16 18 11 Erichsen cupping (DIN 53 156) 10.0 10.0 9.9 (Layer thickness of films: 45-55 ~m) Mo-2933 - 15 -*The solvent attack was.measured in 5 stages:
0, 1, 2, 3, 4.
0 = film completely unchanged 4 = film dissolves.
The results of the lacquer film tests showed that the binders according to the invention harden to form very high quality polyurethane layers which are hard but also tough and elastic.
The drying process may be accelerated if 10 necessary by the addition of a higher proportion of catalyst.
Example 5 In this example, the isocyanate prepolymers according to the invention were used for the preparation 15 of pigmented lacquers and the durability of the films obtained from the lacquers was examined. To simplify the assessment, only white lacquers were prepared. For this purpose, pigments and additives were added to the 70Z or 60Z solutions of the isocyanate prepolymers from 20 Examples 1, 2 and 3 and the solutions were adjusted to a lower concentration by the addition of a solvent mixture of xylene/butyl acetate (3:1) so that the outflow time (DIN 53 211, 4 mm nozzle) was 40 seconds. The pigment was titrated on a three-roller mixer.
The compositions of the triturates are entered in the following Table.
Mo-2933 - 16 -Components Parts bY weight Polyisocyanate solution from Example 1 50 - -from Example 2 - 58.3 from Example 3 - - 58.3 Solvent mixture:
Xylene/butyl acetate (3:1) 20.5 60.5 63.4 Silicone oil as levelling agent (10% in methoxypropylene glycol acetate) 0.4 0.4 0.4 Catalyst (dibutyl tin dilaurate) 0.1 0.1 0.1 Titanium dioxide (rutile type) 22 22 22 Agent for preventing settling of the pigment* 0.2 0.2 0.2 *highly disperse silica (Aerosil* 300 of Degussa).
The lacquer compositions shown in the Table were completely stable for at least 3 months when stored in closed containers with careful exclusion of moisture.
Samples of the lacquers ready for spraying were sprayed on mild steel plates at a thickness of 0.5 mm and the samples were stored for 14 days at about 23C and a relative humidity of 60%.
The impact strength (ASTM-D 2794), rocking hardness of Konig (DIN 53 157) and bonding strength in crosscut (DIN 53 151) of the lacquer films were then tested. The test results are summarized in the Table below.
Impact strength Hardness Bond strength Example (kg x cm) (sec) (Gt 0-4) To test the durability of the lacquers prepared from the isocyanate prepolymers according to the invention under permanent exposure, the steel plates Mo-2933 - 17 -*Trademark were subjected to a weathering test in Florida. The plates were laid out at an angle of 45 and the change of gloss with time was assessed. The gloss was assessed according to the Gardner hardness scale at 60C
5 (DIN 67 530) at intervals of 3 months over a period of 18 months. The results were summarized in the Table below.
Gloss reading after Lacquer sample from 0 36 9 12 15 18 months 10 Example 1 98 90 90 85 80 75 70 Example 2 97 93 90 85 78 75 72 Example 3 98 93 93 89 85 80 75 The lacquers on the weathered plates were mechanically tested again after they had been cleaned.
15 Only a very slight, virtually negligible deterioration in their properties could be detected.
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 20 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.
Mo-2933 - 18 -
Claims (9)
1. A process for the preparation of a pre-polymer containing free isocyanate groups and having an isocyanate content of 1 to 16% by weight which comprises reacting at an NCO/OH equivalent ratio above 4:1 a) a polyisocyanate component comprising (i) a triisocyanato-isocyanurate corresponding to the formula (ii) a mixture of the triisocyanato-isocyanurate mentioned under (i) with its higher homologues containing more than one isocyanurate ring, or (iii) a mixture of the polyisocyanate mentioned under (i) or (ii) with up to 60 isocyanate equivalent percent, based on the total quantity of component (a), of an organic polyisocyanate which is free from isocyanurate groups, wherein X1, X2 and X3 are identical or different and represent difunctional, aliphatic or cycloaliphatic hydrocarbon groups having a molecular weight of 84 to 206 with b) a polyhydroxyl component comprising (i) at least one polyester polyol having a hydroxyl functionality (average) of about 1.8 to 5 and a hydroxyl number (average) of about 15 to 300, or (ii) a mixture of the polyester polyol mentioned under (i) with up to about 10% by weight, based on the weight of the mixture, of a (cyclo)alkane polyol having a hydroxyl number above about 300, a (cyclo)alkane polyol having a hydroxyl number above about 300 and containing ester groups or mixtures of these (cyclo)alkane polyols.
2. The process of Claim 1 wherein component (a) comprises at least about 40 NCO equivalent percent of the triisocyanato-isocyanurate set forth in component (a)(i).
3. The process of Claim 1 wherein (b)(i) contains about 15 to 50% by weight of a cyclohexylene group corresponding to the formula chemically incorporated into said at least one polyester polyol wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
4. The process of Claim 3 wherein component (a) comprises at least about 40 NCO equivalent percent of the triisocyanato-isocyanurate set forth in component (a)(i).
5. A prepolymer containing free isocyanate groups and having an isocyanate content of 1 to 16% by weight which is prepared by a process which comprises reacting at an NCO/OH equivalent ratio above 4:1 a) a polyisocyanate component comprising (i) a triisocyanato-isocyanurate corresponding to the formula (ii) a mixture of the triisocyanato-isocyanurate mentioned under (i) with its higher homologues containing more than one isocyanurate ring, or (iii) a mixture of the polyisocyanate mentioned under (i) or (ii) with up to 60 isocyanate equivalent percent, based on the total quantity of component (a), of an organic polyisocyanate which is free from isocyanurate groups, wherein X1, X2 and X3 are identical or different and represent difunctional, aliphatic or cycloaliphatic hydrocarbon groups having a molecular weight of 84 to 206 with b) a polyhydroxyl component comprising (i) at least one polyester polyol having a hydroxyl functionality (average) of about 1.8 to 5 and a hydroxyl number (average) of about 15 to 300, or (ii) a mixture of the polyester polyol mentioned under (i) with up to about 10% by weight, based on the weight of the mixture, of a (cyclo)alkane polyol having a hydroxyl number above about 300, a (cyclo)alkane polyol having a hydroxyl number above about 300 and containing ester groups or mixtures of these (cyclo)alkane polyols.
6. The prepolymer of Claim 5 wherein component (a) comprises at least about 40 NCO equivalent percent of the triisocyanato-isocyanurate set forth in component (a)(i).
7. The prepolymer of Claim 5 wherein (b)(i) contains about 15 to 50% by weight of a cyclohexylene group corresponding to the formula chemically incorporated into said at least one polyester polyol wherein R represents hydrogen or an alkyl group with 1 to 4 carbon atoms.
8. The prepolymer of Claim 7 wherein component (a) comprises at least about 40 NCO equivalent percent of the triisocyanato-isocyanurate set forth in component (a)(i).
9. A one-component, moisture-curing lacquer which comprises the prepolymer of Claim 5, 6, 7 or 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3621706.9 | 1986-06-28 | ||
| DE19863621706 DE3621706A1 (en) | 1986-06-28 | 1986-06-28 | METHOD FOR THE PREPARATION OF PREPOLYMERS HAVING ISOCYANATE GROUPS, THE PREPOLYMERS AVAILABLE ACCORDING TO THIS METHOD AND THE USE THEREOF AS BINDERS IN COMPONENT LACQUERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334230C true CA1334230C (en) | 1995-01-31 |
Family
ID=6303916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539357A Expired - Fee Related CA1334230C (en) | 1986-06-28 | 1987-06-10 | Process for the preparation of prepolymers containing isocyanate groups, the prepolymers obtainable by this process and their use as binders in one-component lacquers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4801675A (en) |
| EP (1) | EP0252346B1 (en) |
| JP (1) | JP2678443B2 (en) |
| AT (1) | ATE67220T1 (en) |
| CA (1) | CA1334230C (en) |
| DE (2) | DE3621706A1 (en) |
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|---|---|---|---|---|
| JPH02157255A (en) * | 1988-12-07 | 1990-06-18 | Daicel Huels Ltd | Urethane curing agent |
| US6191212B1 (en) * | 1990-10-11 | 2001-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Moisture-curing hotmelt adhesives |
| US5115071A (en) * | 1991-04-09 | 1992-05-19 | Air Products And Chemicals, Inc. | High performance polyurethane coating compositions and processes for making same |
| DE4302266A1 (en) * | 1993-01-28 | 1994-08-04 | Bayer Ag | Two-component polyurethane coating compositions and their use |
| US5360642A (en) * | 1993-05-24 | 1994-11-01 | Olin Corporation | Low VOC, moisture curable, one-component coating compositions based on organic polyisocyanate prepolymers |
| ATE183530T1 (en) * | 1996-02-29 | 1999-09-15 | Synthopol Chemie Dr Koch | NEW POLYESTER POLYOLS AND THEIR USE AS POLYOL COMPONENTS IN TWO-COMPONENT POLYURETHANE PAINTS |
| JP4106093B2 (en) * | 1996-10-16 | 2008-06-25 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Film-forming binder for coating composition and coating composition comprising the same |
| CN1057308C (en) * | 1997-01-27 | 2000-10-11 | 天津石油化工公司研究所 | Method for preparing heat resistant polyurethane elastomer |
| US6096835A (en) * | 1997-10-15 | 2000-08-01 | Akzo Nobel N.V. | Film forming binder for coating compositions and coating compositions comprising same |
| DE19961926A1 (en) * | 1999-12-22 | 2001-07-05 | Basf Coatings Ag | Mixtures of substances curable thermally with actinic radiation and their use |
| DE10013187A1 (en) | 2000-03-17 | 2001-10-11 | Basf Ag | Highly functional polyisocyanates |
| DE10041634C2 (en) * | 2000-08-24 | 2002-10-17 | Basf Coatings Ag | Aqueous dispersion and its use for the production of coating materials, adhesives and sealants curable thermally and with actinic radiation |
| DE10139262C1 (en) | 2001-08-09 | 2003-01-02 | Basf Coatings Ag | A rheological adjuvant, useful for coating materials, adhesives, and sealing compositions, contains a urea derivative obtained by reaction of isocyanate with sterically hindered primary and secondary monoamines |
| DE102004054348A1 (en) * | 2004-11-09 | 2006-05-11 | Hsb Selbstbausysteme Gmbh | Method for producing a laminated glass and laminated glass |
| WO2006127568A2 (en) * | 2005-05-23 | 2006-11-30 | Ashland Licensing And Intellectual Property Llc | One-step process for rapid structure repair |
| WO2007016053A2 (en) * | 2005-07-27 | 2007-02-08 | Ashland Licensing And Intellectual Property Llc | One-step process for rapid structure repair |
| DE102005045150A1 (en) * | 2005-09-22 | 2007-04-05 | Basf Coatings Ag | Use of phosphonic diesters and diphosphonic diesters and thermally curable mixtures containing phosphonic diester and Diphosphonsäurediester |
| DE102005045228A1 (en) * | 2005-09-22 | 2007-04-05 | Basf Coatings Ag | Use of phosphonic diesters and diphosphonic diesters, and silane-containing, curable mixtures containing phosphonic and Diphosphonsäurediester |
| DE102005053663A1 (en) * | 2005-11-10 | 2007-05-16 | Basf Coatings Ag | Radical polymerization curable, aqueous powder dispersions, process for their preparation and their use |
| DE102005053661A1 (en) * | 2005-11-10 | 2007-05-16 | Basf Coatings Ag | Repair films and their use |
| FR2893940B1 (en) * | 2005-11-28 | 2008-01-04 | Rhodia Recherches & Tech | ISOCYANATE FUNCTIONALITY COMPOUND, PREPARATION THEREOF AND USE THEREOF IN A COATING PREPARATION PROCESS |
| US20070231577A1 (en) * | 2006-03-30 | 2007-10-04 | Basf Corporation | Coatings for polycarbonate windows |
| WO2007134736A2 (en) * | 2006-05-19 | 2007-11-29 | Basf Coatings Ag | Powder coating materials with high-functionality, highly branched or hyperbranched polycarbonates |
| DE102006024823A1 (en) * | 2006-05-29 | 2007-12-06 | Basf Coatings Ag | Use of curable mixtures containing silane-containing compounds and phosphonic or Diphosphonsäurediester as adhesion promoters |
| DE102006030059A1 (en) * | 2006-06-29 | 2008-01-17 | Basf Coatings Ag | Process for producing multicoat color and / or effect paint systems |
| DE102007014720A1 (en) * | 2007-03-23 | 2008-09-25 | Basf Coatings Japan Ltd., Yokohama | Phosphonate-containing two-component paint system, its preparation and use |
| US20100104769A1 (en) * | 2008-10-23 | 2010-04-29 | Boisseau John E | Automotive coating surface enhancement using a plasma treatment technique |
| JP5741951B2 (en) * | 2010-12-17 | 2015-07-01 | 荒川化学工業株式会社 | Paint composition |
| WO2019046679A1 (en) * | 2017-08-31 | 2019-03-07 | The University Of Massachusetts | Method for deblocking a blocked isocyanate and method of making a polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1343812A (en) * | 1961-10-26 | 1963-11-22 | Ici Ltd | Polyurethane surface plasters and their manufacture |
| GB966338A (en) * | 1961-10-26 | 1964-08-12 | Ici Ltd | Polyurethane surface coatings |
| US3748315A (en) * | 1971-07-06 | 1973-07-24 | Allied Chem | Heat resistant urethane coatings |
| GB1412432A (en) * | 1972-03-15 | 1975-11-05 | Ici Ltd | Polyurethane coating compositions |
| GB1494930A (en) * | 1974-06-06 | 1977-12-14 | Bayer Ag | Process for the production of isocyanate-based polymers |
| DE2725589A1 (en) * | 1977-06-07 | 1978-12-21 | Bayer Ag | PROCESS FOR THE PRODUCTION OF Aqueous POLYURETHANE DISPERSIONS AND SOLUTIONS |
| DE3010719A1 (en) * | 1980-03-20 | 1981-09-24 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING METAL EFFECT PAINTINGS AND WEATHER-RESISTANT METAL EFFECT MULTI-LAYER PAINT PAINTINGS |
| JPS5783560A (en) * | 1980-11-13 | 1982-05-25 | Nippon Polyurethan Kogyo Kk | Resin composition for polyurethane coating |
| US4359541A (en) * | 1981-01-19 | 1982-11-16 | Basf Wyandotte Corporation | Process for the preparation of polyisocyanurate dispersions and compositions prepared therefrom |
| JPS58162581A (en) * | 1982-03-19 | 1983-09-27 | Nippon Polyurethan Kogyo Kk | Preparation of isocyanurate compound and useful composition of product produced thereby |
| JPS5953522A (en) * | 1982-09-20 | 1984-03-28 | Dainippon Ink & Chem Inc | Manufacture of isocyanate group-terminated prepolymer |
| US4413111A (en) * | 1982-09-29 | 1983-11-01 | Mobay Chemical Corporation | Isocyanate-terminated prepolymers with low free monomer contents |
| DE3322723A1 (en) * | 1983-06-24 | 1985-01-03 | Chemische Werke Hüls AG, 4370 Marl | MOISTURIZING VARNISHES BASED ON ISOCYANATE RESIN |
| DE3322830A1 (en) * | 1983-06-24 | 1985-01-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING COVERS |
| JPS6036524A (en) * | 1983-08-10 | 1985-02-25 | Asahi Denka Kogyo Kk | Urethane-urea composition |
| FR2574396B1 (en) * | 1984-12-06 | 1987-01-02 | Saint Gobain Vitrages Sa | COATING LAYER HAVING SELF-HEALING PROPERTIES FOR WINDOWS ESPECIALLY EXPOSED TO ATMOSPHERIC AGENTS |
| US4560494A (en) * | 1984-12-27 | 1985-12-24 | The Sherwin-Williams Company | Isocyanate functional prepolymers and coating materials based thereon |
| DE3527531A1 (en) * | 1985-08-01 | 1987-02-12 | Bayer Ag | METHOD FOR PRODUCING URETHANE-MODIFIED POLYISOCYANATE PREPARATIONS, THE POLYISOCYANATE PREPARATIONS OBTAINED BY THIS METHOD AND THEIR USE IN THE PRODUCTION OF PLASTICS BASED ON POLYISOCYANATE |
| JPS6253322A (en) * | 1985-09-03 | 1987-03-09 | Mitsui Toatsu Chem Inc | Polyurethane elastomer composition |
-
1986
- 1986-06-28 DE DE19863621706 patent/DE3621706A1/en not_active Withdrawn
-
1987
- 1987-06-10 CA CA000539357A patent/CA1334230C/en not_active Expired - Fee Related
- 1987-06-10 US US07/060,782 patent/US4801675A/en not_active Expired - Lifetime
- 1987-06-19 AT AT87108743T patent/ATE67220T1/en not_active IP Right Cessation
- 1987-06-19 EP EP87108743A patent/EP0252346B1/en not_active Expired - Lifetime
- 1987-06-19 DE DE8787108743T patent/DE3772873D1/en not_active Expired - Lifetime
- 1987-06-26 JP JP62157997A patent/JP2678443B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3772873D1 (en) | 1991-10-17 |
| DE3621706A1 (en) | 1988-01-07 |
| EP0252346B1 (en) | 1991-09-11 |
| US4801675A (en) | 1989-01-31 |
| EP0252346A1 (en) | 1988-01-13 |
| ATE67220T1 (en) | 1991-09-15 |
| JPS6333408A (en) | 1988-02-13 |
| JP2678443B2 (en) | 1997-11-17 |
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| MKLA | Lapsed |