CA2163591A1 - High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositions - Google Patents
High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositionsInfo
- Publication number
- CA2163591A1 CA2163591A1 CA 2163591 CA2163591A CA2163591A1 CA 2163591 A1 CA2163591 A1 CA 2163591A1 CA 2163591 CA2163591 CA 2163591 CA 2163591 A CA2163591 A CA 2163591A CA 2163591 A1 CA2163591 A1 CA 2163591A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- monoalcohol
- polyisocyanate mixture
- groups
- starting material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention is directed to a polyisocyanate mixture which i) is prepared from a monomeric starting material containing a) 30 to 100% by weight, based on the weight of a) and b), of an aliphatic diisocyanate having 4 to 18 carbons in the hydrocarbon chain and b) 0 to 70% by weight, based on the weight of a) and b), of a diisocyanate other component a), ii) has an equivalent weight that is at least 30% greater than the average molecular weight of the monomeric starting material and a viscosity of greater than 10,000 to 100,000 mPa.s when determined at 25°C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
The present invention also relates to the use of these polyisocyanate mixtures, optionally in blocked form, as an isocyanate component in one- or two-component coating compositions.
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
The present invention also relates to the use of these polyisocyanate mixtures, optionally in blocked form, as an isocyanate component in one- or two-component coating compositions.
Description
21~3~91 `~ Mo4193 MD-93-136-lC
HIGH VISCOSITY, HIGH EQUIVALENT WEIGHT
POLYISOCYANATE MIXTURES CONTAINING
ALLOPHANATE AND ISOCYANURATE GROUPS
AND THEIR USE IN COATING COMPOSITIONS
Field of the Invention The present invention is directed to high viscosity, high equivalent weight polyisocyanate mixtures which contain allophanate groups and 10 isocyanurate groups, and to their use in one- and two-component coating compositions.
Des~ iUtiGl I of the Prior Art Presently, there are an increasing number of government regulations which limit the amount of volatile solvents which may be 15 present in coating composilions. In order to reduce the viscosity of the coating compositions, many attempts have been made to reduce the viscosily of the individual components of the coating compositions, particularly the isocyanate component. By reducing the viscosity of the coating composition, less solvent will be necessary to attain the required 20 processing viscosity.
The viscosity of the polyisocyanate component has been reduced by developing products which have lower equivalent weights and, thus, lower viscosities, e.g., U.S. Patents 3,903,127; 4,801,663; and 5,124,427.
Because of their lower viscosilies, less solvent is needed to reduce the 25 viscosity of the resulting coating composition to the viscosity required for subsequent processing.
Despite the efforts to develop high solids coating compositions by reducing the viscosities of polyisocyanates, there is a need to further reduce the amount of organic solvents present in coating compositions in 30 order to meet government regulations. The Applicants have discovered that it is possible to reduce the amount of solvent that is necess~ry to /vjt/121494 -2- 216359l attain the required processing viscosity for two-componenl coating compositions by the use of polyisocyanates containing isocyanurate groups which have high viscosities and high equivalent weights. It is totally unexpected in view of the literature available on coatings that it would be possible to increase the solids content of a coating composition by increasing the equivalent weight and, thus, the viscosity of the polyisocyanate component.
One of the disadvantages of these isocyanurate group-containing polyisocyanates is that to increase their viscosity requires a lengthy reaction procedure which c~ ses the polyisocyanate component to yellow and renders it unsuitable for many coating applicalions. ACCG~dj~YIY, it is an object of the present invention to provide coating compositions which retain the advantages of the coating compositions based on isocyanurate-group containing polyisocyanates, but which may be used to prepare coatings with improved yellowness properties.
This object may be achieved with the coating compositions of the present invention in which the polyisocyanate component COII~;;IIS a mixture of isocyanurate groups and allopllanale groups.
SUMMARY OF THE INVENTION
The present invention is directed to a polyisocyanate mixture which i) is prepared from a monomeric ~lal ling material containing a) 30 to 100% by weight, based on the weight of a) and b), of an aliphatic diisocyanate having 4 to 18 carbons in the hydlocarL,on chain and b) 0 to 70% by weight, based on the weight of a) and b), of a diisocyanate other component a), ii) has an equivalent weight that is at least 30% greater than the average molecular weight of the monomeric starting material and a Mo41 93 ~3- 216 3591 viscosily of greater than 10,000 to 100,000 mPa.s when determined at 25C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanale groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from u,~ll,ane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
The present invention also relates to the use of these polyisocyanate mixtures, optionally in blocked form, as an isocyanate component in one- or two-component coating compositions.
DETAILED DESCRIPTION OF THE INVENTION
In a ,ureferled embodiment of the present invention the 15 polyisocyanate mixtures are prepared from a) 30 to 100%, prer~rably 60 to 100%, more preferably 90 to 100%
and most prererably 100% by weight of one or more organic diisocyanates represented by the formula R'(NCO)2 wherein R' represents a divalent aliphatic hydrocarbon group having 4 to 18 carbon atoms and b) 0 to 70% by weight, prererably 0 to 40% by weight, more prererably O to 10% by weight and most prererably 0% by weight of one more orga,1ic diisocyanates represented by the formula R''(NC0)2 Mo41 93 216359~
wherein R" represents a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
Examples of suitable aliphatic diisocyanates a) include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate. Examples of suitable diisocyanates b) include cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyal1ato",ethyl-3,5,5-trimethylcyclo-hexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 2,4'-diisocyanato-dicyclohexyl methane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, xylylene diisocyanate, a,a,a',a'-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3-and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4- and/or 4,4'-diphenylmethane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
The prerer,ed diisocyanate a) is 1,6-hexamethylene diisocyanate.
Preferred diisocyanates b) are isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4- and/or 2,6-toluylene diisocyanate and 2,4- and/or 4,4'-diphenylmethane diisocyanate. Most prererably 1,6-hexamethylene diisocyanate is used as the sole starting material.
It is also possible in accordance with the present invention to use blends of the previously mentioned diisocyanates with monoisocyanates or polyisocyanates having 3 or more isocyanate groups.
Suitable methods and catalysts for the preparation of polyisocyanates containing isocyanurate groups and allophanate groups Mo41 93 2163~91 are known and described in U.S. Patents 5,124,427, 5,208,334 and 5,235,018, the disclosures of which are herein i,lco"uoraled by refere"ce.
The trimeri~alio,) of the starting diisocyanate mixture may be carried out in the absence or in the presence of solvents which are inert to 5 isocyanate groups. Depending on the area of app' ~tion of the products accordi"g to the invention, low to medium-boiling solvents or high-boiling solvents can be used. Suitable solvents include esters such as ethyl acetale or butyl acetate; ketones such as acetone or butanone; aromatic compounds such as toluene or xylene; halogenated hydrocarbons such 10 as methylene chloride and l,icl1loroell,ylene; ethers such as diisopropylether; and alkanes such as cyclohexane, petroleum ether or ligroin.
In accordance with the present invention urethane groups and sl lhse~ ~ently allophanate groups are incG, ,uorated into the polyiso-15 cyanates by the use of ali~ l IdLiC, cycloaliphatic, araliphatic or aromaticmo,1oalcol,ols, i.e., alcohols in which the hydroxyl group is attached to aliphatic, cycloali,uhalic, araliphatic or aromatic group. The monoalcohols may be linear, bra"ched or cyclic, contain at least one carbon atom and have a molecular weight of up to 2500. The monoalcohols may 20 optionally contain other hetero atoms in the form of, e.g., ether groups.
The molar ratio of monoalcohol to diisocyanate is about 0.01:1 to 0.60:1, preferably about 0.02:1 to 0.50:1 and more prererdbly about 0.05:1 to 0.50:1. P,efe"~d monoalcohols are hydrocarbon monoalcohols.
The hyd~ocdrbon monoalcohols prererably contain 1 to 36, more 25 preferably 1 to 20 and most preferdbly 1 to 8 carbon atoms. Examples of suitable mG"oalcol,ols include methanol, ethanol, n-propanol, isopropa,1ol, n-butanol, isobutanol and tert. butanol, n-pentanol, 2-hydroxy pentane, 3-hydroxy pentane, the isomeric methyl butyl alcohols, the isomeric dimethyl propyl alcohols, neopentyl alcohol, n-hexanol, n-Mo4193 2163~9l heptanol, n-octanol, n-nonanol, 2-ethyl hexanol, trimethyl hexanol, cyclohexanol, benzyl alcohol, phenol, the cresols, the xylenols, the trimethyl,ul,enols, decanol, dodecanol, tetradecanol, hexadecanol, oct.adec~nol, 2,6,8-trimethylno,1al1ol, 2-t-butyl-cyclohexanol, 4-cyclohexyl-5 1-butanol, 2,4,6,-trimethyl benzyl alcohol, branched chain primary alcohols and mixtures thereof (which are available from Henkel under to Standamul trademark) and mixtures of linear primary alcohols (which are available from Shell under the Neodol trademark).
~,ererled ether~ontaining monoalcohols include ethoxy methanol, 10 methoxy ethanol, ethoxy ethanol, the isomeric methoxy or ethoxy propanols, the isomeric propoxy methanols and ethanols, the isomeric methoxy butanols, the isomeric butoxy methanols, furfuralcohol and other monoalcohols which have a molecular weight of up to 2500 and are based on ethylene oxide, propylene oxide and/or butylene oxide.
It is also possible in accorda,1ce with the present invention to use mixtures of the previously described monoalcohols.
When the polyisocyanates co"lai"ing isocyanurate groups and allopha"aLe groups accorcli.,gly to the invention are prepared from monoalcohols containing ethylene oxide units, the polyisocyanates may be dispersed in water as described in U.S. Patent 5,200,489, the disclosure of which is herein incorporated by reference.
The reaction temperature for isocyanurate and allophanate formation in accordance with the present invention is about 40 to 180C, prerera~ly about 80 to 150C and more preferably about 90 to 120C.
The process accordi, lg to the invention may take place either batchwise or continuously, for example, as described below. The starting diisocyanate is introduced with the exclusion of moisture and optionally with an inert gas into a suitable stirred vessel or tube and optionally mixed with a solvent which is inert to isocyanate groups such as toluene, Mo4193 216~91.
butyl acetate, diisopropylether or cyclohexane. The previously described monoalcohol may be introduced into the reaction vessel in accorda"ce with several embodiments. The monoalcohol may be prereacted with the starting diisocyanate to form urethane groups prior to introducing the 5 diisocyanates into the reaction vessel; the monoalcohol may be mixed with the diisocyanates and introduced into the reaction vessel; the monoalcohol may be separately added to the reaction vessel either before or after, preferably after, the diisocyanates are added; or the catalyst may be dissolved in the monoalcohol prior to introducing the 10 solution into the reaction vessel.
In accorda"ce with another embodiment of the present invention the polyisocyanates may be prepared by blending polyisocyanates containing isocyanurate groups with polyisocyanates containing allophanate groups.
At a temperature of about 40C and in the presence of the required catalyst or catalyst solution the trimeri,alion begins and is indicated by an exothermic reaction. As the reaction temperature increases the conversion rate of urell~a~1e groups to allophanate groups increases faster than the formation of isocyanurate groups. Accordingly, 20 at some temperature for a given degree of trime,i dlion, the urethane groups are substantially converted to allopl,anale groups, while at some lower temperature unreacted urethane groups remain. The progress of the reaction is followed by determining the NC0 col,lenl by a suitable method such as lil,dlion, ~er,~cli,/e index or IR analysis. Thus, the 25 reaction may be terminated at the desired degree of trimeri,dlion. The trimerization reaction is generally terminated when 40 to 90%, preferably 45 to 65%, of the isocyanate groups have reacted. When using 1,6-hexamethylene diisocyanate as the sole monomeric starting material, Mo41 93 these perce,1lages correspond to an NC0 cor,le"l for the reaction mixture of 5 to 30%, preferably 18 to 28%.
By terminating the reaction at a lower NC0 content than is conventionally done to prepare low viscosity polyisocyanates, higher 5 viscosity polyisocyanates are obtained due to the formation of polyisocyanurates, polyallophanates and other higher molecular weight polyisocyanates COI ,lai"ing both isocyanurate groups and allophanate groups.
The termination of the trimeli~alion reaction can take place, for 10 example, by the addition of a catalyst poison of the type named by way of example in the above-mentioned literature references. For example, when using basic catalysts the reaction is terminated by the addition of a quantity, which is at least equivalent to the catalyst quantity, of an acid chloride such as benzoyl chloride. When using heat-labile catalysts, for 15 example, the previously described qualer"ary ammonium hydroxides, it is possible, though not pr~ferled, to dispense with the addition of a catalyst poison since these catalysts decompose during the course of the reaction. When using such catalysts, the catalyst quantity and the reaction temperature are preferably selected such that the catalyst, which 20 continuously decomposes, is totally decomposed when the desired degree of trime, i~alion is reached. The quantity of catalyst or reaction temperature which is necessary to achieve this decomposition can be determined by a preliminary experiment. It is also possible initially to use a lesser quantity of a heat sensitive catalyst than is necessary to achieve 25 the desired degree of trimerization and to subsequently catalyze the reaction by a further incremental addition of catalyst, whereby the quantity of catalyst added later is calculated such that when the desired degree of trimeri~dlion is achieved, the total quantity of catalyst is spent.
The use of suspended catalysts is also possible. These catalysts are Mo41 93 g removed after achieving the desired degree of trimeri~aliG" by filtering the reaction mixture.
The working-up of the reaction mixture, optionally after previous separalio" of insoluble catalyst constituents, may take place in various 5 ways depending upon how the reaction was conducted and the area of application for the isocyanates. Any unreacted monomer present in the polyisocyanate product and opliollally any solvent used during the trimeli~alio,l reaction may be removed by distillation in known manner.
The product obtained after distillation generally contains a total of less 10 than 2% by weight, prerer;ably less than 1 % by weight, based on the solids content of the polyisocyanate mixture, of free (unreacted) monomeric diisocyanates. The products accorcli"g to the invention are generally viscous liquids having a minimum viscosity of greater than 10,000, preferably gredler than 12,000 and more preferably greater than 15,000 and a maximum viscosity of 100,000, preferably 90,000 and more preferably 70,000, when determined at 25C on a sample having a solids content of 100% and containing less than 2% by weight of unreacted diisocyanates a) and b).
The polyisocyanate mixtures accordi, lg to the invention are almost 20 colorless, i.e., they have a yellowness index as measured on the APHA
color scale of 10 to 150, preferably 10 to 100 and more prererably 10 to 50. The polyisocyanate mixtures have an average functionality of at least 2, preferably 2 to 7 and more preferably 2.5 to 5; and an equivalent weight which is at least 30% greater, preferably 40% greater and more 25 preferably 50% greater, than the average molecular weight of the monomeric starting material used to prepare the polyisocyanate mixture.
The products accordi, lg to the present invention are polyiso-cyanates containing isocyanurate groups and allophanate groups. The products may also conlai.) residual urethane groups which have not been Mo4193 21fi3591 converted to allopl ,a"ale groups depending upon the temperature maintained during the reaction and the degree of isocyanate group consumption. However, the content of urethane groups (c.~'cl~l~ted as NHCOO, MW 59) should be less than 10% by weight, preferably less 5 than 5% by weight and more prererably less than 2%, based on the solids co"le,ll of the polyisocyanate mixture. The ratio of isocyanurate groups to al'o~.l ,anale groups in the polyisocyanates according to the invention is about 10:1 to 1 :10, preferably about 5:1 to 1:7. These values may be determined spectroscopically or by gel permeation 10 chromatography (GPC) using a standard.
The products according to the invention are valuable starting materials for use in two-component coating compositions for the production of polyisocyanate polyaddition products. Polyisocyanate component A) is used in combination with compounds containing at least 15 two isocyanate-reactive groups, such as hydroxyl groups and/or amino groups, preferably hydroxyl groups. The isocyanate-reactive component preferat.ly has a viscosity (at 25C and a solids cGnle"l of 100%) which is greater, I.rerelal,ly 20% greater and more preferably 50% greater than the viscosity of polyisocyanate component A). The products according to 20 the invention may also be used as moisture-cure resins.
P,eferred reaction partners for the products according to the invention, which may optionally be present in blocked form, are the polyhydroxy polyesters, polyhydroxy polyethers, polyhydroxy poly-acrylates, polyhydroxy polylactones, polyhydroxy polyurethanes, 25 polyhydroxy polyepoxides and optionally low molecular weight, polyhydric alcohols known from polyurethane coatings technology. Polyamines, particularly in blocked form, for example as polyketimines, oxazolidines or polyaldimines are also suitable reaction partners for the products accordi"g to the invention. Also suitable are polyaspartic acid derivatives Mo41 93 11 2J 635~1 (aspa,lales) co"lai"ing secondary amino groups, which also function as reactive diluents.
To prepare the coating compositions the amount of the polyiso-cyanate component and the isocyanate reactive component are selected 5 to provide equivalent ratios of isocyanate groups (whether present in blocked or unblocked form) to isocyanate-reactive groups of about 0.5 to 20, prererably 0.8 to 3 and more preferably about 0.9 to 1.5.
To accelerate hardening, the coating compositions may contain known polyurethane catalysts, e.g., tertiary amines such as triethylamine, 10 pyridine, methyl pyridine, benzyl dimethylamine, N,N-dimethylamino cyclohexane, N-methyl-piperidine, pentamethyl diethylene triamine, 1,4-diazabicyclo[2,2,2]-octane and N,N'-dimethyl piperazine; or metal salts such as iron(lll)-chloride, zinc chloride, zinc-2-ethyl caproate, tin(ll)-ethyl caproale, dibutyltin(lV)-dilaurate and molybdenum glycolate.
The products according to the invention are also valuable starting materials for two-component polyurethane stoving enamels in which the isocyanate groups are used in a form blocked by known blocking agents.
The blocking reaction is carried out in known manner by reacting the isocyanate groups with suitable blocking agents, ~JrereraL,ly at an 20 elevated temperature (e.g. about 40 to 160C), and optionally in the presence of a suitable catalyst, for example, the previously desc,ibed tertiary amines or metal salts.
Suitable blocking agents include monophenols such as phenol, the cresols, the trimethylphenols and the tert. butyl phenols; tertiary alcohols 25 such as tert. butanol, tert. amyl alcohol and dimethylphenyl carbinol;
compounds which easily form enols such as acetoacetic ester, acetyl acetone and malonic acid derivatives, e.g. malonic acid diethylester;
secondary aromatic amines such as N-methyl aniline, the N-methyl toluidine, N-phenyl toluidine and N-phenyl xylidine; imides such as Mo41 93 succinimide; lactams such as ~-caprolactam and ~-valerolactam; oximes such as butanone oxime, methyl amyl ketoxime and cyclohexanone oxime; mercaptans such as methyl mercaptal" ethyl mercaptan, butyl mercapta,l, 2-merca~.tobe"~lhiazole, a-naphthyl mercaptan and dodecyl 5 mercapta"; and triazoles such as 1 H-1 ,2,4-triazole.
The coating compositions may also contain other additives such as pigments, dyes, fillers, levelling agents and solvents. The coating compositions may be applied to the substrate to be coated in solution or from the melt by conventional methods such as painting, rolling, pouring 10 or spraying.
Due to their high equivalent weights, the products according to the invention, when blended with a suitable isocyanate reactive component will need less solvent to obtain a particular processing viscosity than a similar coating composition prepared from a corresponding low viscosity, 15 low equivalent weight polyisocyanate and the same isocyanate reactive component when both coating compositions are prepared at the same equivalent ratio of isocyanate groups to isocyanate reactive groups.
The coating compositions containing the polyisocyanates according to the invention provide coatings which have improved dry 20 times, adhere surprisingly well to a metallic base, and are particularly light-fast, color-stable in the presence of heat and very resistant to abrasion. Furthermore, they are characteli~ed by high hardness, elasticity, very good resistance to chemicals, high gloss, good weather resislal,ce, good environmental etch resistance and good pigmenting 25 qualities. The polyisocyanates according to the invention also possess good compatibility with highly branched polyester resins.
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 otherwise specified.
Mo41 93 -- -13- 21~35 EXAMPLES
Polyisocyanate 1 - According to the invention To a reactor equipped with a gas bubbler, stirrer, thermometer and dropping funnel were added 100 parts of hexamethylene diisocyanate 5 (HDI). The stirred HDI was heated to 90C while dry nitrogen was bubbled through the HDI. To the stirred HDI were added 4.4 parts of n-butanol containing 0.0068 parts of trimethylbenzyl ammonium hydroxide at such a rate that the 90C temperature was maintained. After the addition was complete the reaction mixture was held at 90C for an 10 additional 15 minutes followed by the addition of 0.0068 parts of di-(2-ethylhexyl) phosphate to terminate the reaction. The reaction mixture had an NCO w,lt~"l of 21.9%. The excess monomer was removed by wiped thin film evaporation to provide a clear liquid having an APHA of c50, a viscosity of 53,100 mPa.s (25C), an NC0 cGnLelll of 15.8%, and 15 a free monomer (HDI) c~nlellt of <0.1%.
Using the procedure described in Example 1, additional polyisocyanates were prepared using the reactants and conditions set in in Table 1.
Mo41 93 FlNAL PRODUCT2 DExample #Alcohol Parts Parts Crude % % NCOEquiv. wt. % Visc. @ APHA
Alcohol perCatalyst' NCO Increase in 25C Color 100 parts Equiv. wt.3 mPas HDI
2 1-BuOH 4.4 0.0050 25.1 17.3 243 44.5 18,000 ~ 25 3 1-BuOH 4.4 0.0052 24.1 16.7 251 49.7 24,600 < 25 4 1-BuOH 4.4 0.0064 23.3 16.4 256 52.4 41,200 1-BuOH 6.0 0.0040 23.0 15.8 266 58.2 20,100 ~ 25 6 1-BuOH 6.0 0.0045 20.1 14.9 282 67.8 83,400 c 25 7 1-BuOH 10.0 0.0040 20.6 13.6 309 83.8 51,800 < 25 8 Isocetyl 14.4 0.0075 18.6 13.7 307 82.5 50,600 9 Cyclohexanol 5.9 0.0050 25.7 17.1 246 46.2 20,000 Cyclohexanol 5.9 0.0060 24.2 16.5 255 51.5 49,400 11 Cyclohexanol 5.9 0.0090 21.9 16.0 263 56.3 99,000 12(Comp) 1-BuOH 0.12 0.0060 26.5 18.4 228 35.7 54,800 75 1 - the same amount of di(2-ethylhexyl)phosphd~e was added. C~
2 - the final product contained <0.1% free HDI Monomer.
3 - % increase in equivalent weight coll,par~d to monomeric starting material.
In the preparation of the polyisocyanate of Comparison Example 12, a minor amount of alcohol was used to dissolve the catalyst.
However, this amount was outside the scope of the present invention.
The resulting product, which did not contain the amount of allophanate groups required by the present invention, had an APHA color of 75, while the polyisocyanates accordi~y to the invention, which did contain allophanate groups, had an APHA color of less than 25. It is apparent from the yellowness values that the presence of allophanate groups su".risi"gly improves the color of the high equivalent weight, high viscosity polyisocyanates.
To demonstrate that high solids coating compositions can be pre~ared with the high viscosil~ polyisocyanates accordi"g to the invention, coating compositions were prepared from the-following ingredients. One coating composition contained Polyisocyanate 4 as the polyisocyanate component, while the other contained a commercially available isocyanurate group-contai"ing polyisocyanate prepared from 1,6-hexamethylene diisocyanate (HDI) and having an isocyanate conle"l of 21.6%, a conlenl of monomeric diisocyanate of ~0.2% and a viscosity at 20C of 3000 mPa.s (available from Miles Inc. as Desmodur N 3300).
In both compositions the NCO/OH equivalent ratio was 1.1:1.0, the solids content was 38.4% by weight and the VOC content was 5.0 Ibs/gal. The coating compositions contained the following ingredients:
Mo4193 2163~91 Composition accordi"g Compariso"
to the invention Composition Component 1 Polyol A4 37.19 39.61 Additives 0.24 0.24 Catalyst A6 0.12 0.12 Butyl acetale 21.29 20.03 Total Solvent 39.89 39.84 Component 2 Polyisocyanate from Example 4 6.16 Commercial Polyisocyanate - 5.0 4 - an acrylic polyol having a solids colltellt of 50% (available from Miles as Desmophen A-450).
HIGH VISCOSITY, HIGH EQUIVALENT WEIGHT
POLYISOCYANATE MIXTURES CONTAINING
ALLOPHANATE AND ISOCYANURATE GROUPS
AND THEIR USE IN COATING COMPOSITIONS
Field of the Invention The present invention is directed to high viscosity, high equivalent weight polyisocyanate mixtures which contain allophanate groups and 10 isocyanurate groups, and to their use in one- and two-component coating compositions.
Des~ iUtiGl I of the Prior Art Presently, there are an increasing number of government regulations which limit the amount of volatile solvents which may be 15 present in coating composilions. In order to reduce the viscosity of the coating compositions, many attempts have been made to reduce the viscosily of the individual components of the coating compositions, particularly the isocyanate component. By reducing the viscosity of the coating composition, less solvent will be necessary to attain the required 20 processing viscosity.
The viscosity of the polyisocyanate component has been reduced by developing products which have lower equivalent weights and, thus, lower viscosities, e.g., U.S. Patents 3,903,127; 4,801,663; and 5,124,427.
Because of their lower viscosilies, less solvent is needed to reduce the 25 viscosity of the resulting coating composition to the viscosity required for subsequent processing.
Despite the efforts to develop high solids coating compositions by reducing the viscosities of polyisocyanates, there is a need to further reduce the amount of organic solvents present in coating compositions in 30 order to meet government regulations. The Applicants have discovered that it is possible to reduce the amount of solvent that is necess~ry to /vjt/121494 -2- 216359l attain the required processing viscosity for two-componenl coating compositions by the use of polyisocyanates containing isocyanurate groups which have high viscosities and high equivalent weights. It is totally unexpected in view of the literature available on coatings that it would be possible to increase the solids content of a coating composition by increasing the equivalent weight and, thus, the viscosity of the polyisocyanate component.
One of the disadvantages of these isocyanurate group-containing polyisocyanates is that to increase their viscosity requires a lengthy reaction procedure which c~ ses the polyisocyanate component to yellow and renders it unsuitable for many coating applicalions. ACCG~dj~YIY, it is an object of the present invention to provide coating compositions which retain the advantages of the coating compositions based on isocyanurate-group containing polyisocyanates, but which may be used to prepare coatings with improved yellowness properties.
This object may be achieved with the coating compositions of the present invention in which the polyisocyanate component COII~;;IIS a mixture of isocyanurate groups and allopllanale groups.
SUMMARY OF THE INVENTION
The present invention is directed to a polyisocyanate mixture which i) is prepared from a monomeric ~lal ling material containing a) 30 to 100% by weight, based on the weight of a) and b), of an aliphatic diisocyanate having 4 to 18 carbons in the hydlocarL,on chain and b) 0 to 70% by weight, based on the weight of a) and b), of a diisocyanate other component a), ii) has an equivalent weight that is at least 30% greater than the average molecular weight of the monomeric starting material and a Mo41 93 ~3- 216 3591 viscosily of greater than 10,000 to 100,000 mPa.s when determined at 25C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanale groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from u,~ll,ane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
The present invention also relates to the use of these polyisocyanate mixtures, optionally in blocked form, as an isocyanate component in one- or two-component coating compositions.
DETAILED DESCRIPTION OF THE INVENTION
In a ,ureferled embodiment of the present invention the 15 polyisocyanate mixtures are prepared from a) 30 to 100%, prer~rably 60 to 100%, more preferably 90 to 100%
and most prererably 100% by weight of one or more organic diisocyanates represented by the formula R'(NCO)2 wherein R' represents a divalent aliphatic hydrocarbon group having 4 to 18 carbon atoms and b) 0 to 70% by weight, prererably 0 to 40% by weight, more prererably O to 10% by weight and most prererably 0% by weight of one more orga,1ic diisocyanates represented by the formula R''(NC0)2 Mo41 93 216359~
wherein R" represents a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
Examples of suitable aliphatic diisocyanates a) include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate. Examples of suitable diisocyanates b) include cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyal1ato",ethyl-3,5,5-trimethylcyclo-hexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 2,4'-diisocyanato-dicyclohexyl methane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, xylylene diisocyanate, a,a,a',a'-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3-and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4- and/or 4,4'-diphenylmethane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
The prerer,ed diisocyanate a) is 1,6-hexamethylene diisocyanate.
Preferred diisocyanates b) are isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4- and/or 2,6-toluylene diisocyanate and 2,4- and/or 4,4'-diphenylmethane diisocyanate. Most prererably 1,6-hexamethylene diisocyanate is used as the sole starting material.
It is also possible in accordance with the present invention to use blends of the previously mentioned diisocyanates with monoisocyanates or polyisocyanates having 3 or more isocyanate groups.
Suitable methods and catalysts for the preparation of polyisocyanates containing isocyanurate groups and allophanate groups Mo41 93 2163~91 are known and described in U.S. Patents 5,124,427, 5,208,334 and 5,235,018, the disclosures of which are herein i,lco"uoraled by refere"ce.
The trimeri~alio,) of the starting diisocyanate mixture may be carried out in the absence or in the presence of solvents which are inert to 5 isocyanate groups. Depending on the area of app' ~tion of the products accordi"g to the invention, low to medium-boiling solvents or high-boiling solvents can be used. Suitable solvents include esters such as ethyl acetale or butyl acetate; ketones such as acetone or butanone; aromatic compounds such as toluene or xylene; halogenated hydrocarbons such 10 as methylene chloride and l,icl1loroell,ylene; ethers such as diisopropylether; and alkanes such as cyclohexane, petroleum ether or ligroin.
In accordance with the present invention urethane groups and sl lhse~ ~ently allophanate groups are incG, ,uorated into the polyiso-15 cyanates by the use of ali~ l IdLiC, cycloaliphatic, araliphatic or aromaticmo,1oalcol,ols, i.e., alcohols in which the hydroxyl group is attached to aliphatic, cycloali,uhalic, araliphatic or aromatic group. The monoalcohols may be linear, bra"ched or cyclic, contain at least one carbon atom and have a molecular weight of up to 2500. The monoalcohols may 20 optionally contain other hetero atoms in the form of, e.g., ether groups.
The molar ratio of monoalcohol to diisocyanate is about 0.01:1 to 0.60:1, preferably about 0.02:1 to 0.50:1 and more prererdbly about 0.05:1 to 0.50:1. P,efe"~d monoalcohols are hydrocarbon monoalcohols.
The hyd~ocdrbon monoalcohols prererably contain 1 to 36, more 25 preferably 1 to 20 and most preferdbly 1 to 8 carbon atoms. Examples of suitable mG"oalcol,ols include methanol, ethanol, n-propanol, isopropa,1ol, n-butanol, isobutanol and tert. butanol, n-pentanol, 2-hydroxy pentane, 3-hydroxy pentane, the isomeric methyl butyl alcohols, the isomeric dimethyl propyl alcohols, neopentyl alcohol, n-hexanol, n-Mo4193 2163~9l heptanol, n-octanol, n-nonanol, 2-ethyl hexanol, trimethyl hexanol, cyclohexanol, benzyl alcohol, phenol, the cresols, the xylenols, the trimethyl,ul,enols, decanol, dodecanol, tetradecanol, hexadecanol, oct.adec~nol, 2,6,8-trimethylno,1al1ol, 2-t-butyl-cyclohexanol, 4-cyclohexyl-5 1-butanol, 2,4,6,-trimethyl benzyl alcohol, branched chain primary alcohols and mixtures thereof (which are available from Henkel under to Standamul trademark) and mixtures of linear primary alcohols (which are available from Shell under the Neodol trademark).
~,ererled ether~ontaining monoalcohols include ethoxy methanol, 10 methoxy ethanol, ethoxy ethanol, the isomeric methoxy or ethoxy propanols, the isomeric propoxy methanols and ethanols, the isomeric methoxy butanols, the isomeric butoxy methanols, furfuralcohol and other monoalcohols which have a molecular weight of up to 2500 and are based on ethylene oxide, propylene oxide and/or butylene oxide.
It is also possible in accorda,1ce with the present invention to use mixtures of the previously described monoalcohols.
When the polyisocyanates co"lai"ing isocyanurate groups and allopha"aLe groups accorcli.,gly to the invention are prepared from monoalcohols containing ethylene oxide units, the polyisocyanates may be dispersed in water as described in U.S. Patent 5,200,489, the disclosure of which is herein incorporated by reference.
The reaction temperature for isocyanurate and allophanate formation in accordance with the present invention is about 40 to 180C, prerera~ly about 80 to 150C and more preferably about 90 to 120C.
The process accordi, lg to the invention may take place either batchwise or continuously, for example, as described below. The starting diisocyanate is introduced with the exclusion of moisture and optionally with an inert gas into a suitable stirred vessel or tube and optionally mixed with a solvent which is inert to isocyanate groups such as toluene, Mo4193 216~91.
butyl acetate, diisopropylether or cyclohexane. The previously described monoalcohol may be introduced into the reaction vessel in accorda"ce with several embodiments. The monoalcohol may be prereacted with the starting diisocyanate to form urethane groups prior to introducing the 5 diisocyanates into the reaction vessel; the monoalcohol may be mixed with the diisocyanates and introduced into the reaction vessel; the monoalcohol may be separately added to the reaction vessel either before or after, preferably after, the diisocyanates are added; or the catalyst may be dissolved in the monoalcohol prior to introducing the 10 solution into the reaction vessel.
In accorda"ce with another embodiment of the present invention the polyisocyanates may be prepared by blending polyisocyanates containing isocyanurate groups with polyisocyanates containing allophanate groups.
At a temperature of about 40C and in the presence of the required catalyst or catalyst solution the trimeri,alion begins and is indicated by an exothermic reaction. As the reaction temperature increases the conversion rate of urell~a~1e groups to allophanate groups increases faster than the formation of isocyanurate groups. Accordingly, 20 at some temperature for a given degree of trime,i dlion, the urethane groups are substantially converted to allopl,anale groups, while at some lower temperature unreacted urethane groups remain. The progress of the reaction is followed by determining the NC0 col,lenl by a suitable method such as lil,dlion, ~er,~cli,/e index or IR analysis. Thus, the 25 reaction may be terminated at the desired degree of trimeri,dlion. The trimerization reaction is generally terminated when 40 to 90%, preferably 45 to 65%, of the isocyanate groups have reacted. When using 1,6-hexamethylene diisocyanate as the sole monomeric starting material, Mo41 93 these perce,1lages correspond to an NC0 cor,le"l for the reaction mixture of 5 to 30%, preferably 18 to 28%.
By terminating the reaction at a lower NC0 content than is conventionally done to prepare low viscosity polyisocyanates, higher 5 viscosity polyisocyanates are obtained due to the formation of polyisocyanurates, polyallophanates and other higher molecular weight polyisocyanates COI ,lai"ing both isocyanurate groups and allophanate groups.
The termination of the trimeli~alion reaction can take place, for 10 example, by the addition of a catalyst poison of the type named by way of example in the above-mentioned literature references. For example, when using basic catalysts the reaction is terminated by the addition of a quantity, which is at least equivalent to the catalyst quantity, of an acid chloride such as benzoyl chloride. When using heat-labile catalysts, for 15 example, the previously described qualer"ary ammonium hydroxides, it is possible, though not pr~ferled, to dispense with the addition of a catalyst poison since these catalysts decompose during the course of the reaction. When using such catalysts, the catalyst quantity and the reaction temperature are preferably selected such that the catalyst, which 20 continuously decomposes, is totally decomposed when the desired degree of trime, i~alion is reached. The quantity of catalyst or reaction temperature which is necessary to achieve this decomposition can be determined by a preliminary experiment. It is also possible initially to use a lesser quantity of a heat sensitive catalyst than is necessary to achieve 25 the desired degree of trimerization and to subsequently catalyze the reaction by a further incremental addition of catalyst, whereby the quantity of catalyst added later is calculated such that when the desired degree of trimeri~dlion is achieved, the total quantity of catalyst is spent.
The use of suspended catalysts is also possible. These catalysts are Mo41 93 g removed after achieving the desired degree of trimeri~aliG" by filtering the reaction mixture.
The working-up of the reaction mixture, optionally after previous separalio" of insoluble catalyst constituents, may take place in various 5 ways depending upon how the reaction was conducted and the area of application for the isocyanates. Any unreacted monomer present in the polyisocyanate product and opliollally any solvent used during the trimeli~alio,l reaction may be removed by distillation in known manner.
The product obtained after distillation generally contains a total of less 10 than 2% by weight, prerer;ably less than 1 % by weight, based on the solids content of the polyisocyanate mixture, of free (unreacted) monomeric diisocyanates. The products accorcli"g to the invention are generally viscous liquids having a minimum viscosity of greater than 10,000, preferably gredler than 12,000 and more preferably greater than 15,000 and a maximum viscosity of 100,000, preferably 90,000 and more preferably 70,000, when determined at 25C on a sample having a solids content of 100% and containing less than 2% by weight of unreacted diisocyanates a) and b).
The polyisocyanate mixtures accordi, lg to the invention are almost 20 colorless, i.e., they have a yellowness index as measured on the APHA
color scale of 10 to 150, preferably 10 to 100 and more prererably 10 to 50. The polyisocyanate mixtures have an average functionality of at least 2, preferably 2 to 7 and more preferably 2.5 to 5; and an equivalent weight which is at least 30% greater, preferably 40% greater and more 25 preferably 50% greater, than the average molecular weight of the monomeric starting material used to prepare the polyisocyanate mixture.
The products accordi, lg to the present invention are polyiso-cyanates containing isocyanurate groups and allophanate groups. The products may also conlai.) residual urethane groups which have not been Mo4193 21fi3591 converted to allopl ,a"ale groups depending upon the temperature maintained during the reaction and the degree of isocyanate group consumption. However, the content of urethane groups (c.~'cl~l~ted as NHCOO, MW 59) should be less than 10% by weight, preferably less 5 than 5% by weight and more prererably less than 2%, based on the solids co"le,ll of the polyisocyanate mixture. The ratio of isocyanurate groups to al'o~.l ,anale groups in the polyisocyanates according to the invention is about 10:1 to 1 :10, preferably about 5:1 to 1:7. These values may be determined spectroscopically or by gel permeation 10 chromatography (GPC) using a standard.
The products according to the invention are valuable starting materials for use in two-component coating compositions for the production of polyisocyanate polyaddition products. Polyisocyanate component A) is used in combination with compounds containing at least 15 two isocyanate-reactive groups, such as hydroxyl groups and/or amino groups, preferably hydroxyl groups. The isocyanate-reactive component preferat.ly has a viscosity (at 25C and a solids cGnle"l of 100%) which is greater, I.rerelal,ly 20% greater and more preferably 50% greater than the viscosity of polyisocyanate component A). The products according to 20 the invention may also be used as moisture-cure resins.
P,eferred reaction partners for the products according to the invention, which may optionally be present in blocked form, are the polyhydroxy polyesters, polyhydroxy polyethers, polyhydroxy poly-acrylates, polyhydroxy polylactones, polyhydroxy polyurethanes, 25 polyhydroxy polyepoxides and optionally low molecular weight, polyhydric alcohols known from polyurethane coatings technology. Polyamines, particularly in blocked form, for example as polyketimines, oxazolidines or polyaldimines are also suitable reaction partners for the products accordi"g to the invention. Also suitable are polyaspartic acid derivatives Mo41 93 11 2J 635~1 (aspa,lales) co"lai"ing secondary amino groups, which also function as reactive diluents.
To prepare the coating compositions the amount of the polyiso-cyanate component and the isocyanate reactive component are selected 5 to provide equivalent ratios of isocyanate groups (whether present in blocked or unblocked form) to isocyanate-reactive groups of about 0.5 to 20, prererably 0.8 to 3 and more preferably about 0.9 to 1.5.
To accelerate hardening, the coating compositions may contain known polyurethane catalysts, e.g., tertiary amines such as triethylamine, 10 pyridine, methyl pyridine, benzyl dimethylamine, N,N-dimethylamino cyclohexane, N-methyl-piperidine, pentamethyl diethylene triamine, 1,4-diazabicyclo[2,2,2]-octane and N,N'-dimethyl piperazine; or metal salts such as iron(lll)-chloride, zinc chloride, zinc-2-ethyl caproate, tin(ll)-ethyl caproale, dibutyltin(lV)-dilaurate and molybdenum glycolate.
The products according to the invention are also valuable starting materials for two-component polyurethane stoving enamels in which the isocyanate groups are used in a form blocked by known blocking agents.
The blocking reaction is carried out in known manner by reacting the isocyanate groups with suitable blocking agents, ~JrereraL,ly at an 20 elevated temperature (e.g. about 40 to 160C), and optionally in the presence of a suitable catalyst, for example, the previously desc,ibed tertiary amines or metal salts.
Suitable blocking agents include monophenols such as phenol, the cresols, the trimethylphenols and the tert. butyl phenols; tertiary alcohols 25 such as tert. butanol, tert. amyl alcohol and dimethylphenyl carbinol;
compounds which easily form enols such as acetoacetic ester, acetyl acetone and malonic acid derivatives, e.g. malonic acid diethylester;
secondary aromatic amines such as N-methyl aniline, the N-methyl toluidine, N-phenyl toluidine and N-phenyl xylidine; imides such as Mo41 93 succinimide; lactams such as ~-caprolactam and ~-valerolactam; oximes such as butanone oxime, methyl amyl ketoxime and cyclohexanone oxime; mercaptans such as methyl mercaptal" ethyl mercaptan, butyl mercapta,l, 2-merca~.tobe"~lhiazole, a-naphthyl mercaptan and dodecyl 5 mercapta"; and triazoles such as 1 H-1 ,2,4-triazole.
The coating compositions may also contain other additives such as pigments, dyes, fillers, levelling agents and solvents. The coating compositions may be applied to the substrate to be coated in solution or from the melt by conventional methods such as painting, rolling, pouring 10 or spraying.
Due to their high equivalent weights, the products according to the invention, when blended with a suitable isocyanate reactive component will need less solvent to obtain a particular processing viscosity than a similar coating composition prepared from a corresponding low viscosity, 15 low equivalent weight polyisocyanate and the same isocyanate reactive component when both coating compositions are prepared at the same equivalent ratio of isocyanate groups to isocyanate reactive groups.
The coating compositions containing the polyisocyanates according to the invention provide coatings which have improved dry 20 times, adhere surprisingly well to a metallic base, and are particularly light-fast, color-stable in the presence of heat and very resistant to abrasion. Furthermore, they are characteli~ed by high hardness, elasticity, very good resistance to chemicals, high gloss, good weather resislal,ce, good environmental etch resistance and good pigmenting 25 qualities. The polyisocyanates according to the invention also possess good compatibility with highly branched polyester resins.
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 otherwise specified.
Mo41 93 -- -13- 21~35 EXAMPLES
Polyisocyanate 1 - According to the invention To a reactor equipped with a gas bubbler, stirrer, thermometer and dropping funnel were added 100 parts of hexamethylene diisocyanate 5 (HDI). The stirred HDI was heated to 90C while dry nitrogen was bubbled through the HDI. To the stirred HDI were added 4.4 parts of n-butanol containing 0.0068 parts of trimethylbenzyl ammonium hydroxide at such a rate that the 90C temperature was maintained. After the addition was complete the reaction mixture was held at 90C for an 10 additional 15 minutes followed by the addition of 0.0068 parts of di-(2-ethylhexyl) phosphate to terminate the reaction. The reaction mixture had an NCO w,lt~"l of 21.9%. The excess monomer was removed by wiped thin film evaporation to provide a clear liquid having an APHA of c50, a viscosity of 53,100 mPa.s (25C), an NC0 cGnLelll of 15.8%, and 15 a free monomer (HDI) c~nlellt of <0.1%.
Using the procedure described in Example 1, additional polyisocyanates were prepared using the reactants and conditions set in in Table 1.
Mo41 93 FlNAL PRODUCT2 DExample #Alcohol Parts Parts Crude % % NCOEquiv. wt. % Visc. @ APHA
Alcohol perCatalyst' NCO Increase in 25C Color 100 parts Equiv. wt.3 mPas HDI
2 1-BuOH 4.4 0.0050 25.1 17.3 243 44.5 18,000 ~ 25 3 1-BuOH 4.4 0.0052 24.1 16.7 251 49.7 24,600 < 25 4 1-BuOH 4.4 0.0064 23.3 16.4 256 52.4 41,200 1-BuOH 6.0 0.0040 23.0 15.8 266 58.2 20,100 ~ 25 6 1-BuOH 6.0 0.0045 20.1 14.9 282 67.8 83,400 c 25 7 1-BuOH 10.0 0.0040 20.6 13.6 309 83.8 51,800 < 25 8 Isocetyl 14.4 0.0075 18.6 13.7 307 82.5 50,600 9 Cyclohexanol 5.9 0.0050 25.7 17.1 246 46.2 20,000 Cyclohexanol 5.9 0.0060 24.2 16.5 255 51.5 49,400 11 Cyclohexanol 5.9 0.0090 21.9 16.0 263 56.3 99,000 12(Comp) 1-BuOH 0.12 0.0060 26.5 18.4 228 35.7 54,800 75 1 - the same amount of di(2-ethylhexyl)phosphd~e was added. C~
2 - the final product contained <0.1% free HDI Monomer.
3 - % increase in equivalent weight coll,par~d to monomeric starting material.
In the preparation of the polyisocyanate of Comparison Example 12, a minor amount of alcohol was used to dissolve the catalyst.
However, this amount was outside the scope of the present invention.
The resulting product, which did not contain the amount of allophanate groups required by the present invention, had an APHA color of 75, while the polyisocyanates accordi~y to the invention, which did contain allophanate groups, had an APHA color of less than 25. It is apparent from the yellowness values that the presence of allophanate groups su".risi"gly improves the color of the high equivalent weight, high viscosity polyisocyanates.
To demonstrate that high solids coating compositions can be pre~ared with the high viscosil~ polyisocyanates accordi"g to the invention, coating compositions were prepared from the-following ingredients. One coating composition contained Polyisocyanate 4 as the polyisocyanate component, while the other contained a commercially available isocyanurate group-contai"ing polyisocyanate prepared from 1,6-hexamethylene diisocyanate (HDI) and having an isocyanate conle"l of 21.6%, a conlenl of monomeric diisocyanate of ~0.2% and a viscosity at 20C of 3000 mPa.s (available from Miles Inc. as Desmodur N 3300).
In both compositions the NCO/OH equivalent ratio was 1.1:1.0, the solids content was 38.4% by weight and the VOC content was 5.0 Ibs/gal. The coating compositions contained the following ingredients:
Mo4193 2163~91 Composition accordi"g Compariso"
to the invention Composition Component 1 Polyol A4 37.19 39.61 Additives 0.24 0.24 Catalyst A6 0.12 0.12 Butyl acetale 21.29 20.03 Total Solvent 39.89 39.84 Component 2 Polyisocyanate from Example 4 6.16 Commercial Polyisocyanate - 5.0 4 - an acrylic polyol having a solids colltellt of 50% (available from Miles as Desmophen A-450).
5 - an acrylate copolymer (available as Byk 358 from Byk Chemie).
6 - a 10% solution in butyl acetate of dibutyltin dilaurate (available as Metacure T-12 from Air Products and Chemicals).
The initial viscosity of the compositions was determined at 25C
using a Brookfield LV Viscometer with a #2 spindle at 60 rpm.
Viscosity for composition according to the invention 125 mPa.s Viscosity for comparisol, composition 130 mPa.s The results demollslrale that even though the compositions accordi"g to the invention were prepared from a polyisocyanate having a viscosity of 41,200 mPa.s, they resulted in a lower viscosil~, than the comparison compositions, which were prepared from a polyisocyanate having a viscosity of 3000 mPa.s.
Mo4193 ~16~
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 varialior,s can be made therein by those skilled in the art without departing from the spirit and scope of 5 the invention except as it may be limited by the claims.
Mo41 93
The initial viscosity of the compositions was determined at 25C
using a Brookfield LV Viscometer with a #2 spindle at 60 rpm.
Viscosity for composition according to the invention 125 mPa.s Viscosity for comparisol, composition 130 mPa.s The results demollslrale that even though the compositions accordi"g to the invention were prepared from a polyisocyanate having a viscosity of 41,200 mPa.s, they resulted in a lower viscosil~, than the comparison compositions, which were prepared from a polyisocyanate having a viscosity of 3000 mPa.s.
Mo4193 ~16~
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 varialior,s can be made therein by those skilled in the art without departing from the spirit and scope of 5 the invention except as it may be limited by the claims.
Mo41 93
Claims (21)
1. A polyisocyanate mixture which i) is prepared from a monomeric starting material comprising a) 30 to 100% by weight, based on the weight of a) and b), of an aliphatic diisocyanate having 4 to 18 carbons in the hydrocarbon chain and b) 0 to 70% by weight, based on the weight of a) and b), of a diisocyanate other than component a), ii) has an equivalent weight that is at least 30% greater than the average molecular weight of said monomeric starting material and a viscosity of greater than 10,000 to 100,000 mPa.s when determined at 25 °C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having a molecular weight of up to 2500.
2. The polyisocyanate mixture of Claim 1 wherein component a) is present in an amount of 90 to 100% by weight, based on the weight of a) and b), and comprises 1,6-hexamethylene diisocyanate.
3. The polyisocyanate mixture of Claim 1 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 20 carbon atoms.
4. The polyisocyanate mixture of Claim 2 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 20 carbon atoms.
5. The polyisocyanate mixture of Claim 1 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
6. The polyisocyanate mixture of Claim 2 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
7. The polyisocyanate mixture of Claim 1 wherein said monoalcohol comprises 1-butanol.
8. The polyisocyanate mixture of Claim 2 wherein said monoalcohol comprises 1-butanol.
9. A polyisocyanate mixture which i) is prepared from a monomeric starting material comprising a) 60 to 100% by weight, based on the weight of a) and b) of aliphatic diisocyanate having 4 to 18 carbon atoms in the hydrocarbon chain and b) 0 to 40% by weight based on the weight of a) and b), of a diisocyanate other than component a), ii) has an equivalent weight that is at least 40% greater than the average molecular weight of said monomeric starting material and a viscosity of greater than 10,000 to 100,000 mPa.s when determined at 25°C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having 1 to 20 carbon atoms.
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having 1 to 20 carbon atoms.
10. The polyisocyanate mixture of Claim 9 wherein component a) is present in an amount of 90 to 100% by weight, based on the weight of a) and b), and comprises 1,6-hexamethylene diisocyanate.
11. The polyisocyanate mixture of Claim 9 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
12. The polyisocyanate mixture of Claim 10 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
13. The polyisocyanate mixture of Claim 9 wherein said monoalcohol comprises 1-butanol.
14. The polyisocyanate mixture of Claim 10 wherein said monoalcohol comprises 1-butanol.
15. A polyisocyanate mixture which i) is prepared from a monomeric starting material comprising a) 60 to 100% by weight, based on the weight of a) and b), of aliphatic diisocyanate having 4 to 18 carbon atoms in the hydrocarbon chain and b) 0 to 40% by weight, based on the weight of a) and b), of a diisocyanate other than component a), ii) has an equivalent weight that is at least 50% greater than the average molecular weight of said monomeric starting material and a viscosity of greater than 15,000 to 100,000 mPa.s when determined at 25 °C on a sample having a solids content of 100%
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having 1 to 20 carbon atoms.
and containing less than 2% by weight of unreacted diisocyanates a) and b), and iii) contains isocyanurate groups and allophanate groups in a molar ratio of 10:1 to 1:10, wherein the allophanate groups are derived from urethane groups that are the reaction product of starting material i) with 0.01 to 0.6 moles, per mole of starting material i), of a monoalcohol having 1 to 20 carbon atoms.
16. The polyisocyanate mixture of Claim 15 wherein component a) is present in an amount of 90 to 100% by weight, based on the weight of a) and b), and comprises 1,6-hexamethylene diisocyanate.
17. The polyisocyanate mixture of Claim 15 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
18. The polyisocyanate mixture of Claim 16 wherein said monoalcohol comprises a hydrocarbon monoalcohol containing 1 to 8 carbon atoms.
19. The polyisocyanate mixture of Claim 15 wherein said monoalcohol comprises 1-butanol.
20. The polyisocyanate mixture of Claim 16 wherein said monoalcohol comprises 1-butanol.
21. A one- or two-component coating composition comprising the polyisocyanate of Claim 1 and a compound containing isocyanate-reactive groups.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35998194A | 1994-12-20 | 1994-12-20 | |
| US08/359,981 | 1994-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2163591A1 true CA2163591A1 (en) | 1996-06-21 |
Family
ID=23416106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2163591 Abandoned CA2163591A1 (en) | 1994-12-20 | 1995-11-23 | High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2163591A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014233A1 (en) | 2001-08-09 | 2003-02-20 | Basf Coatings Ag | Rheological adjuncts, method for production and use thereof |
| US6777090B2 (en) | 1999-12-22 | 2004-08-17 | Basf Coatings Ag | Substance mixture which can be cured thermally and by using actinic radiation, and the use thereof |
| US7915321B2 (en) | 2000-08-24 | 2011-03-29 | Basf Coatings Ag | Aqueous dispersion and the use thereof in the production of coating agents, adhesives and sealing agents that can be cured by heat or by actinic radiation |
| US8013099B2 (en) | 2005-09-22 | 2011-09-06 | Basf Coatings Ag | Use of phosphonic acid diesters and diphosphonic acid diesters and silane group containing, curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters |
| US8138249B2 (en) | 2007-03-23 | 2012-03-20 | Basf Coatings Japan Ltd. | Phosphonate-containing two-component coating system and the production and use thereof |
| US8337649B2 (en) | 2005-11-10 | 2012-12-25 | Basf Coatings Gmbh | Repair film and use thereof |
| US9018330B2 (en) | 2006-05-29 | 2015-04-28 | Basf Coatings Gmbh | Use of curable mixtures comprising silane group-containing compounds and phosphonic acid diester or diphosphonic acid diester as adhesives |
| US10294389B2 (en) | 2005-09-22 | 2019-05-21 | Basf Coatings Gmbh | Use of phosphonic acid diesters and diphosphonic acid diesters and thermally curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters |
-
1995
- 1995-11-23 CA CA 2163591 patent/CA2163591A1/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777090B2 (en) | 1999-12-22 | 2004-08-17 | Basf Coatings Ag | Substance mixture which can be cured thermally and by using actinic radiation, and the use thereof |
| US7915321B2 (en) | 2000-08-24 | 2011-03-29 | Basf Coatings Ag | Aqueous dispersion and the use thereof in the production of coating agents, adhesives and sealing agents that can be cured by heat or by actinic radiation |
| WO2003014233A1 (en) | 2001-08-09 | 2003-02-20 | Basf Coatings Ag | Rheological adjuncts, method for production and use thereof |
| US8013099B2 (en) | 2005-09-22 | 2011-09-06 | Basf Coatings Ag | Use of phosphonic acid diesters and diphosphonic acid diesters and silane group containing, curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters |
| US10294389B2 (en) | 2005-09-22 | 2019-05-21 | Basf Coatings Gmbh | Use of phosphonic acid diesters and diphosphonic acid diesters and thermally curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters |
| US8337649B2 (en) | 2005-11-10 | 2012-12-25 | Basf Coatings Gmbh | Repair film and use thereof |
| US9018330B2 (en) | 2006-05-29 | 2015-04-28 | Basf Coatings Gmbh | Use of curable mixtures comprising silane group-containing compounds and phosphonic acid diester or diphosphonic acid diester as adhesives |
| US8138249B2 (en) | 2007-03-23 | 2012-03-20 | Basf Coatings Japan Ltd. | Phosphonate-containing two-component coating system and the production and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5777061A (en) | Blocked polyisocyanate crosslinkers for providing improved flow properties to coating compositions | |
| US5574122A (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| US5576411A (en) | Low surface energy polyisocyanates and their use in one-or two component coating compositions | |
| US5541281A (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| US5691439A (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| US5747629A (en) | Low surface energy polyisocyanates and their use in one-or two-component coating compositions | |
| US5646227A (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| EP1707583B1 (en) | Low surface energy polyisocyanates and their use in one- or two-component coating compositions | |
| US5789519A (en) | High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositions | |
| CA2162832A1 (en) | Polyisocyanates containing allophanate groups | |
| US5714564A (en) | Low viscosity polyisocyanates prepared from monomeric triisocyanates | |
| US5606001A (en) | Polyisocyanates containing allophanate groups and optionally isocyanurate groups | |
| EP1919974B1 (en) | Low surface energy polyisocyanates and their use in one-or two-component coating compositions | |
| CA2163591A1 (en) | High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositions | |
| MXPA97006250A (en) | Low viscosity polyisocianates prepared from triisocianatos monomeri | |
| US5506327A (en) | Blocked polyisocyanates with improved thermal stability | |
| CA2172680A1 (en) | Blocked polyisocyanates with improved thermal stability | |
| CA2172676A1 (en) | Blocked polyisocyanates with improved thermal stability | |
| MXPA97000787A (en) | Polyisocianatos of low surface energy and its use in compositions of coating of one or two components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |