CA2184236A1 - Coating compositions containing isocyanurate group-containing polyisocyanates prepared from 1,4-diisocyanato-butane and their use - Google Patents
Coating compositions containing isocyanurate group-containing polyisocyanates prepared from 1,4-diisocyanato-butane and their useInfo
- Publication number
- CA2184236A1 CA2184236A1 CA002184236A CA2184236A CA2184236A1 CA 2184236 A1 CA2184236 A1 CA 2184236A1 CA 002184236 A CA002184236 A CA 002184236A CA 2184236 A CA2184236 A CA 2184236A CA 2184236 A1 CA2184236 A1 CA 2184236A1
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- Prior art keywords
- component
- weight
- coating compositions
- isocyanate
- bdi
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to coating compositions in which the binder contains a) an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30% by weight and a monomeric BDI content of less than 2% by weight and b) a polyol component, in amounts sufficient to provide an equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) of 0.8:1 to 3:1.
The present invention is also directed to coated substrates prepared from these coating compositions.
The present invention is also directed to coated substrates prepared from these coating compositions.
Description
218g236 Mo4405 LeA 31,303-US
COATING COMPOSITIONS CONTAINING ISOCYANURATE
GROUP-CONTAINING POLYISOCYANATES PREPARED
FROM 1.4-DIISOCYANATOBUTANE AND THEIR USE
BACKGROUND OF THE INVENTION
5 Field of the Invention The present invention relates to coating compositions containing as binder an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and a polyol and to their use for the coating substrates.
10 Description of the Prior Art Two-component coating compositions in which the binder is based on a polyisocyanate component and an isocyanate-reactive component, preferably a polyhydroxyl component, are known. They are suitable for the production of high quality coatings which are hard, flexible and 15 resistant to abrasion, solvents and weathering.
- However, these coating compositions have very long dry times, which are detrimental to their use for economic reasons. Hardening can be significantly speeded up, e.g, by increasing the temperature, but this is only possible to a limited extent for plastics components or bulky 20 products. Spray-painting repair work on finished, assembled motor vehicles or coatings in the field of large vehicle and industrial lacquering are only possible to a limited extent with these coating compositions.
The dry times of two-component polyurethane coating compositions at room temperature can be shortened by the addition of 25 polyisocyanates based on cycloaliphatic diisocyanates te.g. EP-A 3,765 and EP-A 17,998) to the binder composition. This shorter dry time has a physical basis, i.e, chemical crosslinking does not occur at a faster rate, which results in a deterioration of the solvent-resistance, particularly in the early phase of drying. This is primarily a disadvantage in automobile ~2184236 Mo4405 -2-refinish coatings. In addition, coatings produced from cycloaliphatic polyisocyanates exhibit a certain brittleness and limited flexibility. These coating compositions are also unsuitable for producing coatings that require flexibility at low temperatures.
For example, EP-A 470,461 describes special two-component compositions suitable for automobile refinish coating, which are based on diamines containing special ester groups and prepared by the reaction of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane with diethyl maleate or fumarate, in admixture with polyacrylate polyols and polyester polyols in a defined ratio as reactants for the polyisocyanate component. However, two-component polyurethane compositions containing polyamines as the isocyanate-reactive component not only exhibit more rapid hardening than compositions containing polyols, but also have a shorter processing time. This further limits their use in these systems, in addition to the fact that the polyamines are limited by the type and mixture ratio of the polyols they can be used in combination with. The ability freely to select the polyol component would be desirable to be able to adjust the requisite properties of the system for the particular application by varying the isocyanate-reactive component.
An object of the present invention is to provide binder compositions which have outstanding application properties, may be used in many different applications of two-component polyurethane lacquers, rapidly dry to form coatings under mild hardening conditions, e.g. at temperatures below 100C, particularly for automobile refinish and industrial lacquering, and result in coatings having good solvent resistance and flexibility.
218423~
Mo4405 -3-SUMMARY OF THE INVENTION
The present invention relates to coating compositions in which the binder contains a) an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30% by weight and a monomeric BDI content of less than 2% by weight and .
b) a polyol component, in amounts sufficient to provide an equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) of 0.8:1 to 3:1.
The present invention is also directed to coated substrates prepared from these coating compositions.
DETAILED DESCRIPTION OF THE INVENTION
The use of trimers based on 1 ,4-diisocyanatobutane as the polyisocyanate component in two-component coating compositions is known and described in EP-A 571,038. This application describes a process for preparing an isocyanurate group-containing polyisocyanate by trimerizing 1,4-diisocyanatobutane (BDI) at temperatures below 90C and 20 subsequently removing excess BDI.
The isocyanurate group-containing polyisocyanate used according to the present invention, which is prepared from 1,4-diisocyanatobutane, is known from EP-A 57,653. It is prepared by the trimerization of 1,4-diisocyanatobutane in the presence of catalysts containing aminosilyl 25 groups. However, the outstanding suitability of isocyanurate group-containing polyisocyanates prepared from 1,4-diisocyanatobutane for coatings is not taught or suggested by these references.
Therefore, it must be considered to be extremely surprising that the binders according to the present invention, which use BDI trimers as 30 the polyisocyanate component, are particularly suitable for coating ~184236 Mo4405 -4-substrates at temperatures below 100C. In this respect, the binders according to the invention may be rapidly dried to obtain coatings having good solvent resistance and flexibility, which is of great importance in the automobile refinish and industrial lacquering fields.
Suitable isocyanurate group-containing polyisocyanates are those prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30%, preferably 22 to 28.5%, and more preferably 23 to 28% by weight, and a content of free monomeric BDI of less than 2%, preferably less than 0.5% by weight. They may be prepared by partially trimerizing 1,4-diisocyanatobutane to form isocyanurate groups.
Unreacted 1,4-diisocyanatobutane can be removed by distillation, for example.
Instead of using BDI as the sole starting material, it may be blended with up to 50, preferably up to 35 and more preferably up to 20 mole% of other (cyclo)aliphatic diisocyanates having a molecular weight of 138 to 300 for the trimerization reaction. However, BDI is preferably used as the diisocyanate starting material.
Examples of these other optional (cyclo)aliphatic diisocyanates include 1,6-diisocyanatohexane, isomeric diisocyanatononanes, 1,12-diisocyanatododecane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate), 1,3-diisocyanato-cyclobutane, 1,3- and 1,4-diisocyanatocyclohexane, 4,4'-bis-(isocyanato-cyclohexyl)-methane, 1,2-bis-(isocyanatomethyl)-cyclobutane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, hexahydro-2,4- and/or 2,6-diisocyanatotoluene, bis-(isocyanatomethyl)-norbornane (mixture of isomers), and 1-isocyanato-4(3)-isocyanatomethyl-1-methylcyclohexane.
When mixtures of (cyclo)aliphatic diisocyanates are used as the starting diisocyanate, polyisocyanates a) have isocyanate contents of 15 to 30% by weight, preferably 15 to 25% by weight.
Mo4405 -5-Preferably, isocyanurate group-containing polyisocyanates are prepared in accordance with EP-A 57,653 (U.S. Patent 4,412,073, herein incorporated by reference) by trimerizing 1,4-diisocyanatobutane in the presence of aminosilyl compounds as catalysts at temperatures of 0 to 300C, preferably 40 to 200C and more preferably 60 to 150C.
Other suitable catalysts include quaternary ammonium hydroxides, ammonium carboxylates, and mixtures of alkali metal fluorides and - - -quaternary ammonium and phosphonium salts, which have been disclosed in EP-A 330,966 and EP-A 355,479.
The trimerization reaction is conducted, optionally in a solvent, until the desired degree of trimerization has been achieved. At the desired isocyanate content of the reaction mixture, which is preferably 35 to 58, more preferably 40 to 55 and most preferably 42 to 54% by weight, the reaction is terminated by the addition of a suitable catalyst poison (e.g.
water) or by cooling. Excess diisocyanate may then be removed from the reaction mixture by known methods, for example by thin-film distillation. Isocyanurate group-containing polyisocyanates based on BDI
and a free monomer content of less than 2%, preferably less than 0.5%
by weight, are obtained.
Mixtures of these isocyanurate group-containing polyisocyanates prepared from BDI with up to 50, preferably up to 35 and most preferably up to 20 equivalent % of known (cyclo)aliphatic lacquer polyisocyanates may also be used. Examples of suitable lacquer polyisocyanates include polyisocyanates containing isocyanurate, biuret, allophanate and/or uretdione groups and prepared from 1,6-diisocyanatohexane and/or isophorone diisocyanate.
Polyol component b) is selected from the known polyhydroxyl compounds of polyurethane chemistry. Examples include (i) polyacrylate polyols, (ii) polyester polyols, (iii) polycarbonate polyols, (iv) polyester ~184236 Mo4405 -6-poiyols, optionally in admixture with low molecular weight, polyhydric alcohols.
Polyacrylate polyols (i) include hydroxyl group-containing copolymers of olefinically unsaturated compounds having a molecular 5 weight (Mn~ determined by vapour pressure or membrane osmosis measurements) of 800 to 50,000, preferably 1000 to 20,000, and more preferably 5000 to 10,000, and a hydroxyl group content of 0.1 to 12%, preferably 1 to 10% and more preferably 2 to 6 % by weight.
The polyacrylate polyols are copolymers of olefinically unsaturated 10 monomers containing hydroxyl groups with other olefinically unsaturated monomers which are free from hydroxyl groups, e.g., vinyl or vinylidene monomers such as styrene, a-methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert.-butylstyrene, acrylic acid, (meth)acrylonitrile, and acrylic and methacrylic acid esters containing 1 to 15 8 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, n- or isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate or 2-ethylhexyl methacrylate);
diesters of fumaric acid, itaconic acid or maleic acid containing 1 to 8 20 carbon atoms in the alcohol component such as dimethyl, diethyl, dibutyl and dioctyl maleate or fumarate; (meth)acrylamide; vinyl esters of alkane monocarboxylic acids containing 2 to 5 carbon atoms such as vinyl acetate or vinyl propionate; and hydroxyalkyl esters of acrylic acid or methacrylic acid containing 2 to 4 carbon atoms in the hydroxyalkyl 25 radical such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl acrylate or methacrylate, 1,1,1-trimethylolpropane monoacrylate or mono-methacrylate, pentaerythritol monoacrylate or monomethacrylate and mixtures thereof.
Examples of polyester polyols (ii), which are suitable as polyol 30 components b), include those having an average molecular weight (M
218923~
Mo4405 -7-caiculated from the functionality and hydroxyl group content) of 200 to 3000, preferably 250 to 2500, and a hydroxyl group content of 1 to 21%
by weight, preferably 2 to 18% by weight. They may be prepared in known manner by the reacting polyhydric alcohols with sub-stoichiometric amounts of polybasic carboxylic acids, carboxylic acid anhydrides and/or polycarboxylic acid esters of C,-C~0 alcohols or lactones.
Suitable polyhydric alcohols which may be used for the preparation of polyester polyols (ii) preferably have a molecular weight range from 62 to 400 and include 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-(1-methylethylidene)-bis-cyclohexanol, 1,2,3-propanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis-(hydroxymethyl)-1,3-propanediol, 1,3,5-tris-(2-hydroxyethyl) isocyanurate and mixtures thereof.
Saturated or unsaturated aliphatic, cycloaliphatic and/or heteroaromatic acids or acid derivatives, which may optionally be substituted (e.g. by halogen atoms such as Cl or Br) may be used for the preparation of polyester polyols (ii) Examples include carboxylic acids having a molecular weight of 118 to 300 or derivatives thereof, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester and mixtures thereof.
Polyester polyols (ii), which are preferred for use in component b), are those prepared by the known ring opening of lactones in the presence of the previously described polyhydric alcohols. Examples of suitable lactones include ~-propiolactone, r- and ~-valerolactone, ~-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone and mixtures of these lactones. They are generally prepared in the presence of Mo4405 -8-catalysts, such as Lewis or Bronsted acids or organic tin or titanium compounds, at a temperature of 20 to 200C, preferably 50 to 160C.
Polycarbonate polyols (iii), which are suitable as polyol component b), are those prepared, for example, by the reaction of dihydric alcohols having a molecular weight of 62 to 400 with phosgene or diaryl carbonates such as diphenyl carbonate. They have an average molecular weight (Mn~ calculated from the functionality and hydroxyl group content) of 250 to 1000.
Polyester carbonate polyols (iv), which are particularly suitable as polyol component b), are selected from the known diols containing ester groups and carbonate groups described, e.g., in DE-A 1,770,245. They may be obtained by the reaction of dihydric alcohols with lactones, particularly ~-caprolactone, and subsequent reaction of the resulting diols with diphenyl carbonate. They generally have an average molecular weight (Mnl calculated from the functionality and hydroxyl group content) of 500 to 3000.
Polyether polyols (v), which are suitable as polyol component b), have an average molecular weight (Mnl calculated from the functionality and hydroxyl group content) of 200 to 6000, preferably 250 to 4000, and have a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. They may be prepared in known manner by the alkoxylation of polyhydric alcohols, preferably those having a molecular weight of 62 to 400. Preferred alkylene oxides are ethylene oxide and propylene oxide, which can be used in any order or in admixture.
Polyol component b) may optionally contain up to 50% by weight, preferably up to 20% by weight, based on the total weight of polyol component b), of polyhydric alcohols~ which may optionally contain ether group and which have a molecular weight of 62 to 400. These polyhydric alcohols may be used to adjust the viscosity of the two-component coating compositions according to the invention.- The alcohols are Mo4405 -9-preferably liquid at room temperature and include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol and mixtures thereof.
0 to 100% of polyol component b) may be replaced by polyamines, 5 particularly in blocked form, such as polyketimines or oxazolidines, as reactants for polyisocyanate a) in the binder compositions according to the invention. - -Also suitable as polyol component b) are "polyaspartic acid esters," preferably those containing secondary amino groups (e.g. EP-A
403,921, EP-A 470,461 and U.S. Patent 5,126,170, herein incorporated by reference), which may be used in combination with polyester polyols and particularly with polyacrylate polyols. If polyamines are used in the binder compositions according to the invention, the amine groups must be taken into consideration when calculating the ratio of isocyanate groups to isocyanate-reactive groups.
Preferably polyols and more preferably polyacrylate, polyester, polycarbonate polyols and mixtures thereof are used as component b) in the coating compositions according to the invention.
In the coating compositions according to the invention, the equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) is 0.8:1 to 3:1, preferably 0.8:1 to 2:1, and more preferably 0.8:1 to 1.5:1.
The binder compositions according to the invention are produced by mixing the individual components. The production of the coating compositions is generally conducted in the presence of known solvents from coating technology, such as xylene, butyl acetate, methyl isobutyl ketone, methoxypropyl acetate, N-methyl pyrrolidone, Solvesso solvent, petrol, chlorobenzene and mixtures thereof.
The weight ratio of the sum of binder components a) and b) to solvent is generally 40:60 to 100:0, preferably 45:55 to 65:35.
~184236 Mo4405 -10-Coating compositions containing the binder compositions according to the invention may also contain other known additives from coating technology, such as pigments, fillers, flow agents, catalysts and UV stabilizers.
The coating compositions may be applied to any desired substrate concerned by known methods, such as brushing, dipping, flooding, with the aid of rollers or doctor blades, and preferably by spraying. The coating compositions according to the invention are primarily distinguished by their rapid drying under mild hardening conditions and by their outstanding solvent resistance and flexibility. They constitute excellent automobile refinish and industrial coatings, and in this regard may be used to produce both intermediate coats and pigmented and non-pigmented top coats.
Lacquers produced using the binder compositions according to the invention are generally hardened at a temperature below 100C, preferably 0 to 80C and more preferably 10 to 60C.
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 indicated.
EXAMPLES
The following starting materials were used in the examples:
Polyisocyanate components a) Polyisocyanate a1) - isocyanurate group-containing polyisocyanate according to EP-A 57,653 (U.S. Patent 4,412,054) 2100 9 (15 mole) of 1,4-diisocyanatobutane (BDI) were placed in a stirred vessel fitted with an internal thermometer and a nitrogen inlet tube. 31.4 9 (0.2 mole ~ 1.5% by weight) of hexamethyldisilazane were slowly added under nitrogen at 120 to 125C until an NCO content of 47.4% was obtained after about 6 hours. The reaction was then stopped 30 by the addition of 1.8 9 (0.1 mole) of water. After work-up and thin-film Mo4405 -11-distillation a clear, almost colorless product was obtained at a yield of 33% and had an NCO content of 24.5% and a viscosity according to DIN
53 019 of 15,000 mPa.s at 23C.
Polyisocyanate a2) A commercially available lacquer polyisocyanate obtained by the trimerization of 1,6-diisocyanatohexane (90% solution in butyl acetate, NCO content of solution = 19.4%).
Polyisocyanate a3) A commercially available lacquer polyisocyanate, obtained by the trimerization of isophorone diisocyanate (70% solution in solvent naphtha 100 solvent, NCO content of solution = 11.7%).
Polyisocyanate a4) A mixture of polyisocyanates a2) and a3) at a 70:30 weight ratio, based on solids (70% solution in butyl acetate/solvent naphtha 100 solvent, NCO content of solution = 13.9%).
Polyol component b) A polyhydroxy polyacrylate (70% solution in butyl acetate) was used as polyol component b). It had an OH number of 140 and was prepared by the copolymerization of styrene, hydroxyethyl methacrylate, butyl acrylate and acrylic acid, in a weight ratio of the monomers of 40:34:25:1. The viscosity of the 70% solution at 23C was 4000 mPa.s.
Example 1 (according to the invention) 146 g of polyisocyanate a1) were blended with 500 g of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl acetate/xylene/butyl acetate (1 :1 :1).
218g236 Mo4405 -12-Example 2 (comparison example) 173 g of polyisocyanate a2) were blended with 469 g of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 5 acetate/xylene/butyl acetate (1: 1: 1).
Example 3 (comparison example) 265 9 of polyisocyanate a3) were blended with 432 9 of polyol b) -- -at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 10 acetate/xylene/butyl acetate (1: 1: 1).
Example 4 (comparison example) 208 9 of polyisocyanate a4) were blended with 404 9 of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 15 acetate/xylene/butyl acetate (1:1:1).
Both glass plates and steel panels were coated with the clear coating compositions from Examples 1 to 4.
Bodywork panels of type UST 1405, which were coated with a customary two-component polyurethane primer surfacer (40 ,u) and a 20 base lacquer (15 ,u) based on a solvent-containing mixture of cellulose acetobutyrate and a high molecular weight polyacrylate, were used as the steel panels.
The test results obtained from the bodywork panels are set forth in the following table.
TABLE
Example 1 2 (comp.) 3 (comp.) 4 (comp.) Solids content % 50 50 50 50 NCO/OH ratio 1.0:1.0 1.0:1.0 1.0:1.0 1.0:1.0 Catalysta) wt. % based on solid binder % 0.3 0.3 0.3 0.3 Run-out time DIN 53 211 0 hr (sec) 19 17 16 17 1 hr (sec) 21 20 17 19 2 hr (sec) 21 20 17 19 3 hr (sec) 27 22 18 21 Drying DIN 53 150 Sand dry (hrs) 0.5 2 0.5 0.5 Touch dry (hrs) 5 6 5 5 Coating thickness ,um (50) (50) (50) (50) Pendulum impact hardness DIN 53 157 after 1 day 23C 80 60 70 63 oe~
after 2 days 23C 114 110 115 119 c.~:~
after 7 days 23C 140 132 180 161 after 30 min. at 60Cb) + 2 hrs 23C 123 87 80 92 +1 day 23C 190 165 135 180 +2 days 23C 195 190 165 197 TABLE (Cont'd) Example 1 2 (comp.) 3 (comp.) 4 (comp.) Erichsen cupping test DIN 53 156 after 7 days 23C 7 7 0.5 Cross-cutting (2 mm) DIN 53 151 after 7 days 23C O 0 5 0 Resistance to premium gasoline after 1 day 23C 0/1 2/2 515 315 after 2 days 23C 0/0 0/0 515 1/1 after 7 days 23C 0/0 0/0 415 1/1 after 30 min. at 60Cb) +2 hrs 23C 214 214 515 515 +1 day 23C 1/1 1/1 515 315 +2 days 23C 0/0 0/0 515 215 +7 days 23C 0/0 0/0 4/5 0/3 a) 1,4-diazabicyclo[2.2.2]octane, DABCO LV 33 catalyst supplied by Air Products co b) standard drying conditions for automotive refinish coating c) assessment O - 5, 0 best value, 5 worst value c~
218423~
Mo4405 -1 5-As can be seen from the Table, the BDI trimer (Example 1, according to the invention) exhibits rapid drying while also retaining its elasticity (Erichsen cupping test, cross cutting), and has excellent resistance to premium gasoline as a measure of its solvent resistance.
In contrast, the coating composition containing the HDI trimer (Example 2, comparison example) dries too slowly. The coating compositions containing the IPDI trimer (Example 3, comparison example) and the blend of IPDI and HDI trimers (Example 4, comparison example) have faster dry times. However, the resistance to premium gasoline is substantially reduced, which indicates that the IPDI trimer dries purely physically with a considerably delayed c:hemical cure. The elasticity is also considerably poorer than that of the BDI or HDI trimer.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
COATING COMPOSITIONS CONTAINING ISOCYANURATE
GROUP-CONTAINING POLYISOCYANATES PREPARED
FROM 1.4-DIISOCYANATOBUTANE AND THEIR USE
BACKGROUND OF THE INVENTION
5 Field of the Invention The present invention relates to coating compositions containing as binder an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and a polyol and to their use for the coating substrates.
10 Description of the Prior Art Two-component coating compositions in which the binder is based on a polyisocyanate component and an isocyanate-reactive component, preferably a polyhydroxyl component, are known. They are suitable for the production of high quality coatings which are hard, flexible and 15 resistant to abrasion, solvents and weathering.
- However, these coating compositions have very long dry times, which are detrimental to their use for economic reasons. Hardening can be significantly speeded up, e.g, by increasing the temperature, but this is only possible to a limited extent for plastics components or bulky 20 products. Spray-painting repair work on finished, assembled motor vehicles or coatings in the field of large vehicle and industrial lacquering are only possible to a limited extent with these coating compositions.
The dry times of two-component polyurethane coating compositions at room temperature can be shortened by the addition of 25 polyisocyanates based on cycloaliphatic diisocyanates te.g. EP-A 3,765 and EP-A 17,998) to the binder composition. This shorter dry time has a physical basis, i.e, chemical crosslinking does not occur at a faster rate, which results in a deterioration of the solvent-resistance, particularly in the early phase of drying. This is primarily a disadvantage in automobile ~2184236 Mo4405 -2-refinish coatings. In addition, coatings produced from cycloaliphatic polyisocyanates exhibit a certain brittleness and limited flexibility. These coating compositions are also unsuitable for producing coatings that require flexibility at low temperatures.
For example, EP-A 470,461 describes special two-component compositions suitable for automobile refinish coating, which are based on diamines containing special ester groups and prepared by the reaction of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane with diethyl maleate or fumarate, in admixture with polyacrylate polyols and polyester polyols in a defined ratio as reactants for the polyisocyanate component. However, two-component polyurethane compositions containing polyamines as the isocyanate-reactive component not only exhibit more rapid hardening than compositions containing polyols, but also have a shorter processing time. This further limits their use in these systems, in addition to the fact that the polyamines are limited by the type and mixture ratio of the polyols they can be used in combination with. The ability freely to select the polyol component would be desirable to be able to adjust the requisite properties of the system for the particular application by varying the isocyanate-reactive component.
An object of the present invention is to provide binder compositions which have outstanding application properties, may be used in many different applications of two-component polyurethane lacquers, rapidly dry to form coatings under mild hardening conditions, e.g. at temperatures below 100C, particularly for automobile refinish and industrial lacquering, and result in coatings having good solvent resistance and flexibility.
218423~
Mo4405 -3-SUMMARY OF THE INVENTION
The present invention relates to coating compositions in which the binder contains a) an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30% by weight and a monomeric BDI content of less than 2% by weight and .
b) a polyol component, in amounts sufficient to provide an equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) of 0.8:1 to 3:1.
The present invention is also directed to coated substrates prepared from these coating compositions.
DETAILED DESCRIPTION OF THE INVENTION
The use of trimers based on 1 ,4-diisocyanatobutane as the polyisocyanate component in two-component coating compositions is known and described in EP-A 571,038. This application describes a process for preparing an isocyanurate group-containing polyisocyanate by trimerizing 1,4-diisocyanatobutane (BDI) at temperatures below 90C and 20 subsequently removing excess BDI.
The isocyanurate group-containing polyisocyanate used according to the present invention, which is prepared from 1,4-diisocyanatobutane, is known from EP-A 57,653. It is prepared by the trimerization of 1,4-diisocyanatobutane in the presence of catalysts containing aminosilyl 25 groups. However, the outstanding suitability of isocyanurate group-containing polyisocyanates prepared from 1,4-diisocyanatobutane for coatings is not taught or suggested by these references.
Therefore, it must be considered to be extremely surprising that the binders according to the present invention, which use BDI trimers as 30 the polyisocyanate component, are particularly suitable for coating ~184236 Mo4405 -4-substrates at temperatures below 100C. In this respect, the binders according to the invention may be rapidly dried to obtain coatings having good solvent resistance and flexibility, which is of great importance in the automobile refinish and industrial lacquering fields.
Suitable isocyanurate group-containing polyisocyanates are those prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30%, preferably 22 to 28.5%, and more preferably 23 to 28% by weight, and a content of free monomeric BDI of less than 2%, preferably less than 0.5% by weight. They may be prepared by partially trimerizing 1,4-diisocyanatobutane to form isocyanurate groups.
Unreacted 1,4-diisocyanatobutane can be removed by distillation, for example.
Instead of using BDI as the sole starting material, it may be blended with up to 50, preferably up to 35 and more preferably up to 20 mole% of other (cyclo)aliphatic diisocyanates having a molecular weight of 138 to 300 for the trimerization reaction. However, BDI is preferably used as the diisocyanate starting material.
Examples of these other optional (cyclo)aliphatic diisocyanates include 1,6-diisocyanatohexane, isomeric diisocyanatononanes, 1,12-diisocyanatododecane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate), 1,3-diisocyanato-cyclobutane, 1,3- and 1,4-diisocyanatocyclohexane, 4,4'-bis-(isocyanato-cyclohexyl)-methane, 1,2-bis-(isocyanatomethyl)-cyclobutane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, hexahydro-2,4- and/or 2,6-diisocyanatotoluene, bis-(isocyanatomethyl)-norbornane (mixture of isomers), and 1-isocyanato-4(3)-isocyanatomethyl-1-methylcyclohexane.
When mixtures of (cyclo)aliphatic diisocyanates are used as the starting diisocyanate, polyisocyanates a) have isocyanate contents of 15 to 30% by weight, preferably 15 to 25% by weight.
Mo4405 -5-Preferably, isocyanurate group-containing polyisocyanates are prepared in accordance with EP-A 57,653 (U.S. Patent 4,412,073, herein incorporated by reference) by trimerizing 1,4-diisocyanatobutane in the presence of aminosilyl compounds as catalysts at temperatures of 0 to 300C, preferably 40 to 200C and more preferably 60 to 150C.
Other suitable catalysts include quaternary ammonium hydroxides, ammonium carboxylates, and mixtures of alkali metal fluorides and - - -quaternary ammonium and phosphonium salts, which have been disclosed in EP-A 330,966 and EP-A 355,479.
The trimerization reaction is conducted, optionally in a solvent, until the desired degree of trimerization has been achieved. At the desired isocyanate content of the reaction mixture, which is preferably 35 to 58, more preferably 40 to 55 and most preferably 42 to 54% by weight, the reaction is terminated by the addition of a suitable catalyst poison (e.g.
water) or by cooling. Excess diisocyanate may then be removed from the reaction mixture by known methods, for example by thin-film distillation. Isocyanurate group-containing polyisocyanates based on BDI
and a free monomer content of less than 2%, preferably less than 0.5%
by weight, are obtained.
Mixtures of these isocyanurate group-containing polyisocyanates prepared from BDI with up to 50, preferably up to 35 and most preferably up to 20 equivalent % of known (cyclo)aliphatic lacquer polyisocyanates may also be used. Examples of suitable lacquer polyisocyanates include polyisocyanates containing isocyanurate, biuret, allophanate and/or uretdione groups and prepared from 1,6-diisocyanatohexane and/or isophorone diisocyanate.
Polyol component b) is selected from the known polyhydroxyl compounds of polyurethane chemistry. Examples include (i) polyacrylate polyols, (ii) polyester polyols, (iii) polycarbonate polyols, (iv) polyester ~184236 Mo4405 -6-poiyols, optionally in admixture with low molecular weight, polyhydric alcohols.
Polyacrylate polyols (i) include hydroxyl group-containing copolymers of olefinically unsaturated compounds having a molecular 5 weight (Mn~ determined by vapour pressure or membrane osmosis measurements) of 800 to 50,000, preferably 1000 to 20,000, and more preferably 5000 to 10,000, and a hydroxyl group content of 0.1 to 12%, preferably 1 to 10% and more preferably 2 to 6 % by weight.
The polyacrylate polyols are copolymers of olefinically unsaturated 10 monomers containing hydroxyl groups with other olefinically unsaturated monomers which are free from hydroxyl groups, e.g., vinyl or vinylidene monomers such as styrene, a-methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert.-butylstyrene, acrylic acid, (meth)acrylonitrile, and acrylic and methacrylic acid esters containing 1 to 15 8 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, n- or isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate or 2-ethylhexyl methacrylate);
diesters of fumaric acid, itaconic acid or maleic acid containing 1 to 8 20 carbon atoms in the alcohol component such as dimethyl, diethyl, dibutyl and dioctyl maleate or fumarate; (meth)acrylamide; vinyl esters of alkane monocarboxylic acids containing 2 to 5 carbon atoms such as vinyl acetate or vinyl propionate; and hydroxyalkyl esters of acrylic acid or methacrylic acid containing 2 to 4 carbon atoms in the hydroxyalkyl 25 radical such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl acrylate or methacrylate, 1,1,1-trimethylolpropane monoacrylate or mono-methacrylate, pentaerythritol monoacrylate or monomethacrylate and mixtures thereof.
Examples of polyester polyols (ii), which are suitable as polyol 30 components b), include those having an average molecular weight (M
218923~
Mo4405 -7-caiculated from the functionality and hydroxyl group content) of 200 to 3000, preferably 250 to 2500, and a hydroxyl group content of 1 to 21%
by weight, preferably 2 to 18% by weight. They may be prepared in known manner by the reacting polyhydric alcohols with sub-stoichiometric amounts of polybasic carboxylic acids, carboxylic acid anhydrides and/or polycarboxylic acid esters of C,-C~0 alcohols or lactones.
Suitable polyhydric alcohols which may be used for the preparation of polyester polyols (ii) preferably have a molecular weight range from 62 to 400 and include 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-(1-methylethylidene)-bis-cyclohexanol, 1,2,3-propanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis-(hydroxymethyl)-1,3-propanediol, 1,3,5-tris-(2-hydroxyethyl) isocyanurate and mixtures thereof.
Saturated or unsaturated aliphatic, cycloaliphatic and/or heteroaromatic acids or acid derivatives, which may optionally be substituted (e.g. by halogen atoms such as Cl or Br) may be used for the preparation of polyester polyols (ii) Examples include carboxylic acids having a molecular weight of 118 to 300 or derivatives thereof, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid, maleic acid, maleic anhydride, dimeric and trimeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester and mixtures thereof.
Polyester polyols (ii), which are preferred for use in component b), are those prepared by the known ring opening of lactones in the presence of the previously described polyhydric alcohols. Examples of suitable lactones include ~-propiolactone, r- and ~-valerolactone, ~-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone and mixtures of these lactones. They are generally prepared in the presence of Mo4405 -8-catalysts, such as Lewis or Bronsted acids or organic tin or titanium compounds, at a temperature of 20 to 200C, preferably 50 to 160C.
Polycarbonate polyols (iii), which are suitable as polyol component b), are those prepared, for example, by the reaction of dihydric alcohols having a molecular weight of 62 to 400 with phosgene or diaryl carbonates such as diphenyl carbonate. They have an average molecular weight (Mn~ calculated from the functionality and hydroxyl group content) of 250 to 1000.
Polyester carbonate polyols (iv), which are particularly suitable as polyol component b), are selected from the known diols containing ester groups and carbonate groups described, e.g., in DE-A 1,770,245. They may be obtained by the reaction of dihydric alcohols with lactones, particularly ~-caprolactone, and subsequent reaction of the resulting diols with diphenyl carbonate. They generally have an average molecular weight (Mnl calculated from the functionality and hydroxyl group content) of 500 to 3000.
Polyether polyols (v), which are suitable as polyol component b), have an average molecular weight (Mnl calculated from the functionality and hydroxyl group content) of 200 to 6000, preferably 250 to 4000, and have a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. They may be prepared in known manner by the alkoxylation of polyhydric alcohols, preferably those having a molecular weight of 62 to 400. Preferred alkylene oxides are ethylene oxide and propylene oxide, which can be used in any order or in admixture.
Polyol component b) may optionally contain up to 50% by weight, preferably up to 20% by weight, based on the total weight of polyol component b), of polyhydric alcohols~ which may optionally contain ether group and which have a molecular weight of 62 to 400. These polyhydric alcohols may be used to adjust the viscosity of the two-component coating compositions according to the invention.- The alcohols are Mo4405 -9-preferably liquid at room temperature and include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol and mixtures thereof.
0 to 100% of polyol component b) may be replaced by polyamines, 5 particularly in blocked form, such as polyketimines or oxazolidines, as reactants for polyisocyanate a) in the binder compositions according to the invention. - -Also suitable as polyol component b) are "polyaspartic acid esters," preferably those containing secondary amino groups (e.g. EP-A
403,921, EP-A 470,461 and U.S. Patent 5,126,170, herein incorporated by reference), which may be used in combination with polyester polyols and particularly with polyacrylate polyols. If polyamines are used in the binder compositions according to the invention, the amine groups must be taken into consideration when calculating the ratio of isocyanate groups to isocyanate-reactive groups.
Preferably polyols and more preferably polyacrylate, polyester, polycarbonate polyols and mixtures thereof are used as component b) in the coating compositions according to the invention.
In the coating compositions according to the invention, the equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) is 0.8:1 to 3:1, preferably 0.8:1 to 2:1, and more preferably 0.8:1 to 1.5:1.
The binder compositions according to the invention are produced by mixing the individual components. The production of the coating compositions is generally conducted in the presence of known solvents from coating technology, such as xylene, butyl acetate, methyl isobutyl ketone, methoxypropyl acetate, N-methyl pyrrolidone, Solvesso solvent, petrol, chlorobenzene and mixtures thereof.
The weight ratio of the sum of binder components a) and b) to solvent is generally 40:60 to 100:0, preferably 45:55 to 65:35.
~184236 Mo4405 -10-Coating compositions containing the binder compositions according to the invention may also contain other known additives from coating technology, such as pigments, fillers, flow agents, catalysts and UV stabilizers.
The coating compositions may be applied to any desired substrate concerned by known methods, such as brushing, dipping, flooding, with the aid of rollers or doctor blades, and preferably by spraying. The coating compositions according to the invention are primarily distinguished by their rapid drying under mild hardening conditions and by their outstanding solvent resistance and flexibility. They constitute excellent automobile refinish and industrial coatings, and in this regard may be used to produce both intermediate coats and pigmented and non-pigmented top coats.
Lacquers produced using the binder compositions according to the invention are generally hardened at a temperature below 100C, preferably 0 to 80C and more preferably 10 to 60C.
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 indicated.
EXAMPLES
The following starting materials were used in the examples:
Polyisocyanate components a) Polyisocyanate a1) - isocyanurate group-containing polyisocyanate according to EP-A 57,653 (U.S. Patent 4,412,054) 2100 9 (15 mole) of 1,4-diisocyanatobutane (BDI) were placed in a stirred vessel fitted with an internal thermometer and a nitrogen inlet tube. 31.4 9 (0.2 mole ~ 1.5% by weight) of hexamethyldisilazane were slowly added under nitrogen at 120 to 125C until an NCO content of 47.4% was obtained after about 6 hours. The reaction was then stopped 30 by the addition of 1.8 9 (0.1 mole) of water. After work-up and thin-film Mo4405 -11-distillation a clear, almost colorless product was obtained at a yield of 33% and had an NCO content of 24.5% and a viscosity according to DIN
53 019 of 15,000 mPa.s at 23C.
Polyisocyanate a2) A commercially available lacquer polyisocyanate obtained by the trimerization of 1,6-diisocyanatohexane (90% solution in butyl acetate, NCO content of solution = 19.4%).
Polyisocyanate a3) A commercially available lacquer polyisocyanate, obtained by the trimerization of isophorone diisocyanate (70% solution in solvent naphtha 100 solvent, NCO content of solution = 11.7%).
Polyisocyanate a4) A mixture of polyisocyanates a2) and a3) at a 70:30 weight ratio, based on solids (70% solution in butyl acetate/solvent naphtha 100 solvent, NCO content of solution = 13.9%).
Polyol component b) A polyhydroxy polyacrylate (70% solution in butyl acetate) was used as polyol component b). It had an OH number of 140 and was prepared by the copolymerization of styrene, hydroxyethyl methacrylate, butyl acrylate and acrylic acid, in a weight ratio of the monomers of 40:34:25:1. The viscosity of the 70% solution at 23C was 4000 mPa.s.
Example 1 (according to the invention) 146 g of polyisocyanate a1) were blended with 500 g of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl acetate/xylene/butyl acetate (1 :1 :1).
218g236 Mo4405 -12-Example 2 (comparison example) 173 g of polyisocyanate a2) were blended with 469 g of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 5 acetate/xylene/butyl acetate (1: 1: 1).
Example 3 (comparison example) 265 9 of polyisocyanate a3) were blended with 432 9 of polyol b) -- -at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 10 acetate/xylene/butyl acetate (1: 1: 1).
Example 4 (comparison example) 208 9 of polyisocyanate a4) were blended with 404 9 of polyol b) at NCO:OH equivalent ratio of 1:1 to form a clear coating composition, and adjusted to a solids content of 50% with methoxypropyl 15 acetate/xylene/butyl acetate (1:1:1).
Both glass plates and steel panels were coated with the clear coating compositions from Examples 1 to 4.
Bodywork panels of type UST 1405, which were coated with a customary two-component polyurethane primer surfacer (40 ,u) and a 20 base lacquer (15 ,u) based on a solvent-containing mixture of cellulose acetobutyrate and a high molecular weight polyacrylate, were used as the steel panels.
The test results obtained from the bodywork panels are set forth in the following table.
TABLE
Example 1 2 (comp.) 3 (comp.) 4 (comp.) Solids content % 50 50 50 50 NCO/OH ratio 1.0:1.0 1.0:1.0 1.0:1.0 1.0:1.0 Catalysta) wt. % based on solid binder % 0.3 0.3 0.3 0.3 Run-out time DIN 53 211 0 hr (sec) 19 17 16 17 1 hr (sec) 21 20 17 19 2 hr (sec) 21 20 17 19 3 hr (sec) 27 22 18 21 Drying DIN 53 150 Sand dry (hrs) 0.5 2 0.5 0.5 Touch dry (hrs) 5 6 5 5 Coating thickness ,um (50) (50) (50) (50) Pendulum impact hardness DIN 53 157 after 1 day 23C 80 60 70 63 oe~
after 2 days 23C 114 110 115 119 c.~:~
after 7 days 23C 140 132 180 161 after 30 min. at 60Cb) + 2 hrs 23C 123 87 80 92 +1 day 23C 190 165 135 180 +2 days 23C 195 190 165 197 TABLE (Cont'd) Example 1 2 (comp.) 3 (comp.) 4 (comp.) Erichsen cupping test DIN 53 156 after 7 days 23C 7 7 0.5 Cross-cutting (2 mm) DIN 53 151 after 7 days 23C O 0 5 0 Resistance to premium gasoline after 1 day 23C 0/1 2/2 515 315 after 2 days 23C 0/0 0/0 515 1/1 after 7 days 23C 0/0 0/0 415 1/1 after 30 min. at 60Cb) +2 hrs 23C 214 214 515 515 +1 day 23C 1/1 1/1 515 315 +2 days 23C 0/0 0/0 515 215 +7 days 23C 0/0 0/0 4/5 0/3 a) 1,4-diazabicyclo[2.2.2]octane, DABCO LV 33 catalyst supplied by Air Products co b) standard drying conditions for automotive refinish coating c) assessment O - 5, 0 best value, 5 worst value c~
218423~
Mo4405 -1 5-As can be seen from the Table, the BDI trimer (Example 1, according to the invention) exhibits rapid drying while also retaining its elasticity (Erichsen cupping test, cross cutting), and has excellent resistance to premium gasoline as a measure of its solvent resistance.
In contrast, the coating composition containing the HDI trimer (Example 2, comparison example) dries too slowly. The coating compositions containing the IPDI trimer (Example 3, comparison example) and the blend of IPDI and HDI trimers (Example 4, comparison example) have faster dry times. However, the resistance to premium gasoline is substantially reduced, which indicates that the IPDI trimer dries purely physically with a considerably delayed c:hemical cure. The elasticity is also considerably poorer than that of the BDI or HDI trimer.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (5)
1. A coating composition in which the binder comprises a) an isocyanurate group-containing polyisocyanate prepared from 1,4-diisocyanatobutane (BDI) and having an isocyanate content of 20 to 30% by weight and a monomeric BDI content of less than
2% by weight and b) a polyol component, in amounts sufficient to provide an equivalent ratio of isocyanate groups of component a) to isocyanate-reactive groups of component b) of 0.8:1 to 3:1.
2. The coating composition of Claim 1 wherein said polyisocyanate has an isocyanate content of 22 to 28.5% by weight and a monomeric BDI content of less than 0.5% by weight.
2. The coating composition of Claim 1 wherein said polyisocyanate has an isocyanate content of 22 to 28.5% by weight and a monomeric BDI content of less than 0.5% by weight.
3. The coating composition of Claim 1 wherein the polyol comprises a member selected from the group consisting of polyacrylate polyols, polyester polyols and polycarbonate polyols.
4. A substrate coated with the coating composition of Claim 1.
5. An automotive substrate coated with the coating composition of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19532063A DE19532063A1 (en) | 1995-08-31 | 1995-08-31 | Binders containing isocyanurate polyisocyanates based on 1,4-diisocyanatobutane and their use for coating substrates |
| DE19532063.8 | 1995-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2184236A1 true CA2184236A1 (en) | 1997-03-01 |
Family
ID=7770857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002184236A Abandoned CA2184236A1 (en) | 1995-08-31 | 1996-08-27 | Coating compositions containing isocyanurate group-containing polyisocyanates prepared from 1,4-diisocyanato-butane and their use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0761707B1 (en) |
| JP (1) | JPH09132751A (en) |
| AT (1) | ATE214718T1 (en) |
| CA (1) | CA2184236A1 (en) |
| DE (2) | DE19532063A1 (en) |
| ES (1) | ES2174003T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210102064A1 (en) | 2019-10-07 | 2021-04-08 | Covestro Llc | Faster cure polyaspartic resins for faster physical property development in coatings |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2023190307A1 (en) | 2022-03-31 | 2023-10-05 | ||
| CN115594852B (en) * | 2022-10-20 | 2023-05-23 | 广州硅碳新材料有限公司 | Trapezoidal organic silicon resin, preparation method thereof and flame retardant material containing trapezoidal organic silicon resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2607499A1 (en) * | 1986-12-02 | 1988-06-03 | Rhone Poulenc Chimie | PURE ISOCYANURIC GROUPING POLYISOCYANATES AND PROCESS FOR OBTAINING THESE POLYISOCYANATES |
| NL9200906A (en) * | 1992-05-22 | 1993-12-16 | Dsm Nv | METHOD FOR PREPARING AN ISOCYANURATE GROUPS CONTAINING POLYISOCYANATE. |
| DE4406157A1 (en) * | 1994-02-25 | 1995-08-31 | Bayer Ag | Powder paint and its use |
-
1995
- 1995-08-31 DE DE19532063A patent/DE19532063A1/en not_active Withdrawn
-
1996
- 1996-08-19 ES ES96113238T patent/ES2174003T3/en not_active Expired - Lifetime
- 1996-08-19 DE DE59608905T patent/DE59608905D1/en not_active Expired - Lifetime
- 1996-08-19 EP EP96113238A patent/EP0761707B1/en not_active Expired - Lifetime
- 1996-08-19 AT AT96113238T patent/ATE214718T1/en not_active IP Right Cessation
- 1996-08-27 CA CA002184236A patent/CA2184236A1/en not_active Abandoned
- 1996-08-29 JP JP8245420A patent/JPH09132751A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210102064A1 (en) | 2019-10-07 | 2021-04-08 | Covestro Llc | Faster cure polyaspartic resins for faster physical property development in coatings |
| US11827788B2 (en) | 2019-10-07 | 2023-11-28 | Covestro Llc | Faster cure polyaspartic resins for faster physical property development in coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2174003T3 (en) | 2002-11-01 |
| EP0761707B1 (en) | 2002-03-20 |
| JPH09132751A (en) | 1997-05-20 |
| EP0761707A1 (en) | 1997-03-12 |
| ATE214718T1 (en) | 2002-04-15 |
| DE19532063A1 (en) | 1997-03-06 |
| DE59608905D1 (en) | 2002-04-25 |
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