# Patent

## Title
Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates

## Abstract

The present invention relates to a new process for preparing polyisocyanates containing isocyanurate groups and being flocculation-stable in solvents from (cyclo)aliphatic diisocyanates.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 61/552,464, filed on Oct. 28, 2011.


The present invention relates to a new process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates.
para-Toluenesulfonyl isocyanate (H3C(C6H4)SO2—NCO) and triethyl orthoformate are literature examples of water scavengers which are used in polyisocyanates for stabilization. This stabilization encompasses among other things the prevention of flocculation of aliphatic polyisocyanates in diluted form in solvents as are used for coatings applications. Here it is assumed that water-scavenging compounds in competition with the polyisocyanate prevent isocyanate groups being hydrolyzed with water to form amines, and these amines from reacting with further polyisocyanate to form high-functionality (poly)urea polyisocyanates. The latter polyisocyanates have a poor solubility in polyisocyanates and their solutions, and flocs and precipitates may form.
Flocculation in the sense of this patent refers comprehensively to formation of solids in such a way as to be visible to the naked eye. It ranges from slight hazing, fine precipitates which eddy only as a result of rotating movement about the longitudinal axis of the storage vessel, to the formation of suspended flocs and severe precipitates.
A disadvantage of water scavengers is that they have to be added (at least) stoichiometrically to the amount of water which is present or is anticipated. In the case of para-toluenesulfonyl isocyanate, this corresponds to 12 times the amount by weight of water, and in the case of triethyl orthoformate to 9 times the amount. In the case of para-toluenesulfonyl isocyanate, manufacturers in fact recommend twice the equivalent amount relative to water, respective amounts of para-toluenesulfonyl isocyanate of 0.5-4.0% and 1-3% of triethyl orthoformate, based on the total weight of the formulation. Where such amounts are used, they have the effect, as a result of the dilution factor alone, of reducing the NCO groups accordingly, and this is deleterious for the coatings properties.
para-Toluenesulfonyl isocyanate is a highly reactive monofunctional isocyanate which reacts preferentially with water in place of the polyisocyanate that is to be protected. This reaction forms inert sulfonamide and, as in the case of the reaction of the polyisocyanate itself, carbon dioxide, possibly with a build-up of pressure in the storage vessel.
DE 124,590 describes the application of sulfonyl isocyanates as water-binding components in polyurethane prepolymers. EP 86871 describes disadvantages of these compounds, since the pronounced crystallization tendency of the tosylamide formed by reaction with water leads to bittiness in the coating material. Moreover, the tosyl isocyanate is so highly reactive that it reacts extremely vigorously with water.
JP 2001/081,400 describes moisture-curing urethane resin coating compositions comprising a urethane prepolymer having two or more isocyanate groups in one molecule, e.g., from the aromatic diphenylmethane diisocyanate (MDI) and polypropylene glycol, blocked amines, two kinds of water scavenger, and a defoamer. Water scavengers are, for example, a combination of para-toluenesulfonyl isocyanate and triethyl orthoformate. Background is a storage stability for avoiding premature hydrolysis of the blocked amine and curing of the latent reaction mixture.
U.S. Pat. No. 6,291,577 discloses a method for scavenging moisture in polyisocyanate formulations by admixing the polyisocyanate formulation with water scavengers comprising a) di-tert-butylhydroxytoluene selected from the group of 2,6-di-tert-butylhydroxytoluene and 2-tert-butylhydroxytoluene and b) alkyl esters of toluenesulfonic acid with an at least 90% fraction of para-alkyl esters, optionally in at least one solvent. Stated by way of example is a package of moisture scavengers consisting of 0.19% bis(tert-butyl)hydroxytoluene (BHT) and 1.0% methyl para-toluenesulfonate, optionally in combination with other moisture scavengers, relative to a polyisocyanate containing isocyanurate groups and based on hexamethylene diisocyanate, as a 40% strength solution in n-butyl acetate. Corresponding mixtures are stable on storage for 11 weeks without hazing or yellowing. A disadvantage of the method is that the amounts of moisture scavengers are very high, meaning that the NCO value of the polyisocyanate is reduced by 1% by dilution by the moisture scavenger package. Moreover, only the methyl and ethyl esters of para-toluenesulfonic acid are readily available commercially. Moreover, the solubility of methyl para-toluenesulfonate is poor. At room temperature, for example, it does dissolve 1% in butyl acetate, but not in 10% strength form.
U.S. Pat. No. 5,328,635 discloses imino alcohols and oxazolidines as water and formaldehyde scavengers with diverse advantages, hence as corrosion inhibitors, reactive diluents, rheology modifiers, and against foaming. Suitability as antiflocculant for the storage of polyisocyanates in solvents is not described. An apparent disadvantage for application in the sense of the invention is that as water scavengers such compounds must be added stoichiometrically, and they have consequences for the properties of the polyisocyanates in coating formulations, leading to differences in behavior of stabilized and unstabilized polyisocyanates in coating formulations and therefore to problems in application. Likewise a disadvantage is that, depending on the storage conditions, amine-containing compounds such as imino alcohols and oxazolidines tend toward yellowing and have an effect on the reactivity of the coating system, by shortening the working life, for example. Oxazolidines react with water in ring-opening reactions to form difunctional isocyanate-reactive amino alcohols. These alcohols oligomerize with polyisocyanate. This may result in an increase in viscosity during storage.
EP 86,971 describes the use of isocyanatosilanes for improving the shelf life of polyisocyanates in relation to viscosity. There is no reference to stabilization of polyisocyanate (solutions) with respect to flocculation. Isocyanatosilanes are available commercially only on a very limited basis.
US 2008/0257214 describes the use of certain trimethylsilyl-containing compounds such as bistrimethylsilylacetamide or hexamethyldisilazane as water scavengers for preventing instances of hazing and formation of carbon dioxide by polyisocyanates in solvents. As with the majority of drying agents, these compounds have to be added at least stoichiometrically. The cleavage products formed consume NCO groups.
EP 203,874 discloses trialkyl-chloro-tin compounds for stabilizing polyisocyanates in organic solvents against floc. Triorgano-tin compounds are highly toxic.
WO 08/116,607 describes two-component coating systems comprising as components

    a) one or more polyisocyanates,
    b) one or more oligomeric and/or polymeric compounds which are reactive with component (a), and
    c) one or more phosphonates selected from the group of the phosphonic diesters and diphosphonic diesters,


where

    i) component (b) comprises all of the oligomeric and/or polymeric compounds which are reactive with component (a) in the two-component coating system, and
    ii) component (b) comprises not more than 15% by weight, based on the total weight of component (b), of oligomeric and/or polymeric compounds comprising isocyanate-reactive amino groups.


The system has the advantage that it ensures a good potlife and at the same time a good appearance and sufficient hardness.
In the examples of the patent application, components (b), (c), solvents, and additives are mixed directly prior to application. There is no reference to any antiflocculation effect of the components (c).
DE 19,908,793 describes a process for preparing an active isocyanate in the presence of a dialkylphosphonic acid (equally dialkylphosphonic esters) where particularly during the preparation there is no solidification or hazing, and a storage-stable active isocyanate is obtained. According to the inventive examples and page 2, line 57, the active isocyanate comprises aromatic carbodiimides and uretonimines. These are stored without solvent following their preparation.
There is no reference to any stabilizing effect on polyisocyanates other than carbodiimides and uretonimines, and especially not to any antiflocculation effect.
WO 2008/116895 claims polyisocyanate compositions comprising (a) polyisocyanate, (b) urethanization catalyst, (c) phosphonate, and optionally (d) sterically hindered phenol, (e) solvents, (f) acidic stabilizers, (g) further, typical coatings additives. In the presence of a urethanization catalyst, these polyisocyanate compositions are color-stable on storage. The patent application contains no reference to flocculation stability of polyisocyanates in high dilution in solvents, particularly not in the absence of Lewis acids.
EP 341,516 discloses polyisocyanates comprising (optionally methyl-substituted) 2- and 3-chloropropionic acid. Polyisocyanates described are polyester urethanes formed from hydroxypolyesters and the aromatic tolylene diisocyanate. The acids have a stabilizing effect in relation to discoloration during storage (in ethyl acetate solvent) and also in relation to the reactivity of the polyester urethanes toward ketimines after storage. Use in aliphatic polyisocyanates is not described. Storage stability in relation to flocculation in moisture-comprising solvents is not described.
WO 2008/68197 discloses polyisocyanates comprising, in particular, methoxyacetic acid as stabilizer. Storage stability in relation to flocculation in moisture-comprising solvents is not described.
EP 643,042 B1 discloses the stabilization of monomeric isocyanates (diisocyanates), prepared by a phosgene-free process, through use of primary antioxidants, secondary antioxidants or acids, or of combinations of primary antioxidants with acids, optionally in the presence of secondary antioxidants, in relation to reactivity and color in the trimerization of monomeric HDI. Acidic stabilizers specified are monocarboxylic acids, organic polycarboxylic acids, inorganic acids, diesters of phosphoric acid or phosphorous acid, carbonyl chlorides, and inorganic acid chlorides. This stabilization relates to monomeric isocyanates prior to their oligomerization. The oligomerization takes place at high temperature and concludes with a distillation at around 150-160° C. It is known (from EP 1238992, for example) that monocarboxylic acids, for example, react with isocyanates at a relatively high temperature, and are therefore no longer present in active form in the polyisocyanates after distillation at 150° C.
Storage stability in relation to flocculation of polyisocyanates in moisture-comprising solvents is not described.
U.S. Pat. No. 5,256,333 describes a triple combination of diarylamine, sterically hindered phenol and a pentaerythritol diphosphite, especially for stabilizing polyether polyols against discoloration, especially at relatively high temperatures, in the production of polyurethane foams. Column 1 refers to an increased stability toward hydrolysis particularly in the case of the polyethers as compared with use of simple phosphites instead of diphosphites.
A disadvantage of the above-described antiflocculants for polyisocyanates in solvents is that they are almost all water scavengers and, accordingly, must be used at least stoichiometrically, since they are in competition with a massive excess of isocyanate groups. This not only is uneconomic but also gives rise to side effects such as the reduction in the NCO values of the mixtures. Furthermore, on hydrolysis of the water scavengers, cleavage products are formed, which often consume isocyanate groups and lead to derivative products which may adversely affect the coatings properties.
In the amounts that need to be used, para-toluenesulfonyl isocyanate and amine-containing compounds lead to the discoloration of the aliphatic isocyanates. This is especially undesirable when the polyisocyanate component is stored for refinish applications in small containers and is to be used for application in clearcoats.
Triethyl orthoformate is the less reactive water scavenger relative to para-toluenesulfonyl isocyanate.
It was an object of the present invention to provide a method with which polyisocyanates during storage in solvents on exposure to (atmospheric) moisture exhibit a higher flocculation stability in storage.
One specific problem arises, for example, for refinish applications (automotive refinish), where long storage times of the products in small containers are a given. Manufacturers of the polyisocyanate component in solvent provide their customers with guarantees of the retention of the product properties for six months. Storage at the premises of the manufacturer, storage in the course of global transport, or storage of excess by the customer prolong these periods. As a result of low-volume containers and/or repeated opening of these containers, ambient moisture comes into contact with the polyisocyanate component. The solvents used likewise comprise traces of moisture. Storage effects are exacerbated, particularly in countries in Southeast Asia, by high atmospheric humidity and high storage temperatures. The same problems can be assumed generally in all applications involving prolonged storage times, particularly in relatively small containers, as for example in many industrial applications.
The object has been achieved through the use of additives selected from the group consisting of

    a1) organic acids having a pKa of below 4.2, selected from the group consisting of a1a) aromatic sulfonic acids and a1b) singularly or doubly alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acids having two carbon atoms, singularly or doubly halogen-, alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acids, alkenedicarboxylic acids or alkanedicarboxylic acids having at least three carbon atoms,
    a2) phosphites of the formula






    
    
        where R is preferably an aryl group which is substituted in positions 2, 4 and 6 as follows:
        Position 2: tert-butyl, tert-amyl,
        Position 4: hydrogen, alkyl, tert-butyl or tert-amyl, and
        Position 6: hydrogen, alkyl, tert-butyl or tert-amyl,
        with the proviso that at least one of the substituents in positions 4 and 6 is not hydrogen,
    
    
    a3) phosphonites of the formula (RO)2P—X—P(RO)2 
    
        where R is preferably an aryl group which is substituted in positions 2, 4 and 6 as follows:
        Position 2: tert-butyl, tert-amyl,
        Position 4: hydrogen, alkyl, tert-butyl or tert-amyl, and
        Position 6: hydrogen, alkyl, tert-butyl or tert-amyl,
        with the proviso that at least one of the substituents in positions 4 and 6 is not hydrogen, and
    
    


X in this case is an arylene group,

    a4) acidic phosphorus derivatives selected from the group consisting of a4a) mono- and di-C1 to C12 alkyl phosphates, a4b) mono- and di-C1 to C12 alkyl phosphonates, a4c) mono-C1 to C12 alkyl phosphinates, and a4d) alkyl derivatives of phosphorus-containing diacids,
    a5) blocked aromatic sulfonic acids


for reducing flocculation and/or precipitation in polyisocyanate mixtures which comprise at least one solvent.
Polyisocyanates for the purposes of the invention are polyisocyanates in their as-synthesized form, and mixtures of these polyisocyanates.
They include the compounds described in more detail below.
The monomeric isocyanates used for preparing the polyisocyanates may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, as referred to in abbreviated form in this specification as (cyclo)aliphatic; aliphatic isocyanates are particularly preferred.
Aromatic isocyanates are those which comprise at least one aromatic ring system, thus including both purely aromatic and also araliphatic compounds.
Cycloaliphatic isocyanates are those which comprise at least one cycloaliphatic ring system.
Aliphatic isocyanates are those which comprise exclusively linear or branched chains, i.e., acyclic compounds.
The monomeric isocyanates are preferably diisocyanates, which carry precisely two isocyanate groups. They can, however, in principle also be monoisocyanates, having one isocyanate group.
In principle, higher isocyanates having on average more than 2 isocyanate groups are also contemplated. Suitability therefor is possessed for example by triisocyanates such as triisocyanatononane, 2′-isocyanatoethyl (2,6-diisocyanatohexanoate), 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4′-triisocyanatodiphenyl ether, or the mixtures of diisocyanates, triisocyanates, and higher polyisocyanates that are obtained, for example, by phosgenation of corresponding aniline/formaldehyde condensates and represent methylene-bridged polyphenyl polyisocyanates, more particularly triisocyanatononane and 2′-isocyanatoethyl-(2,6-diisocyanatohexanoate).
The monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of typical diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, (e.g., methyl 2,6-diisocyanatohexanoate or ethyl 2,6-diisocyanatohexanoate)trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4′- or 2,4′-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis-(isocyanatomethyl)cyclohexane or 2,4-, or 2,6-diisocyanato-1-methylcyclohexane, and also 3 (or 4), 8 (or 9)-bis(isocyanatomethyl)tricyclo[5.2.1.02,6]decane isomer mixtures, and also aromatic diisocyanates such as tolylene 2,4- or 2,6-diisocyanate and the isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4′- or 4,4′-diisocyanatodiphenylmethane and the isomer mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, diphenylene 4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 3-methyldiphenylmethane 4,4′-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether 4,4′-diisocyanate.
Particular preference is given to hexamethylene 1,6-diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, isophorone diisocyanate, and 4,4′- or 2,4′-di(isocyanatocyclohexyl)methane, very particular preference to isophorone diisocyanate and hexamethylene 1,6-diisocyanate, and special preference to hexamethylene 1,6-diisocyanate.
Mixtures of said isocyanates may also be present.
Isophorone diisocyanate is usually in the form of a mixture, specifically a mixture of the cis and trans isomers, generally in a proportion of about 60:40 to 90:10 (w/w), preferably in a proportion of 70:30 to 90:10.
Dicyclohexylmethane 4,4′-diisocyanate may likewise be in the form of a mixture of the different cis and trans isomers.
For the present invention it is possible to use not only those diisocyanates obtained by phosgenating the corresponding amines but also those prepared without the use of phosgene, i.e., by phosgene-free processes. According to EP-A-0 126 299 (U.S. Pat. No. 4,596,678), EP-A-126 300 (U.S. Pat. No. 4,596,679), and EP-A-355 443 (U.S. Pat. No. 5,087,739), for example, (cyclo)aliphatic diisocyanates, such as hexamethylene 1,6-diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4′- or 2,4′-di(isocyanatocyclohexyl)methane, and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI) can be prepared by reacting the (cyclo)aliphatic diamines with, for example, urea and alcohols to give (cyclo)aliphatic biscarbamic esters and subjecting said esters to thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis takes place usually continuously in a circulation process and in the presence, optionally, of N-unsubstituted carbamic esters, dialkyl carbonates, and other by-products recycled from the reaction process. Diisocyanates obtained in this way generally contain a very low or even unmeasurable fraction of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
In one embodiment of the present invention the isocyanates used have a hydrolyzable chlorine content of less than 100 ppm, preferably of less than 50 ppm, more preferably less than 30 ppm, especially less than 20 ppm. This can be measured by means, for example, of ASTM specification D4663-98. The amounts of total chlorine are for example below 1000 ppm, preferably below 800 ppm, and more preferably below 500 ppm (determined by argentometric titration after hydrolysis).
It will be appreciated that it is also possible to employ mixtures of those monomeric isocyanates which have been obtained by reacting the (cyclo)aliphatic diamines with, for example, urea and alcohols and cleaving the resulting (cyclo)aliphatic biscarbamic esters, with those diisocyanates which have been obtained by phosgenating the corresponding amines.
The polyisocyanates which can be formed by oligomerizing the monomeric isocyanates are generally characterized as follows:
The average NCO functionality of such compounds is in general at least 1.8 and can be up to 8, preferably 2 to 5, and more preferably 2.4 to 4.
The isocyanate group content after oligomerization, calculated as NCO=42 g/mol, is generally from 5% to 25% by weight unless otherwise specified.
The polyisocyanates are preferably compounds as follows:

    1) Polyisocyanates containing isocyanurate groups and derived from aromatic, aliphatic and/or cycloaliphatic diisocyanates. Particular preference is given in this context to the corresponding aliphatic and/or cycloaliphatic isocyanatoisocyanurates and in particular to those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl and/or trisisocyanatocycloalkyl isocyanurates, which constitute cyclic trimers of the diisocyanates, or are mixtures with their higher homologs containing more than one isocyanurate ring. The isocyanatoisocyanurates generally have an NCO content of 10% to 30% by weight, in particular 15% to 25% by weight, and an average NCO functionality of 2.6 to 8. The polyisocyanates containing isocyanurate groups may to a more minor extent also comprise urethane groups and/or allophanate groups, preferably with a bound alcohol content of less than 2% based on the polyisocyanate.
    2) Polyisocyanates containing uretdione groups and having aromatically, aliphatically and/or cycloaliphatically attached isocyanate groups, preferably aliphatically and/or cycloaliphatically attached, and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
    
        The polyisocyanates containing uretdione groups are frequently obtained as a mixture with other polyisocyanates, more particularly those specified under 1). Polyisocyanates containing uretdione groups typically have functionalities of 2 to 3. This also includes uretdione/isocyanurate mixtures of any desired composition, more particularly having a monomeric uretdione (dimer) content of 1-40%, in particular 3-15, more particularly 5-10%.
        For this purpose the diisocyanates can be reacted under reaction conditions under which not only uretdione groups but also the other polyisocyanates are formed, or the uretdione groups are formed first of all and are subsequently reacted to give the other polyisocyanates, or the diisocyanates are first reacted to give the other polyisocyanates, which are subsequently reacted to give products containing uretdione groups.
    
    
    3) Polyisocyanates containing biuret groups and having aromatically, cycloaliphatically or aliphatically attached, preferably cycloaliphatically or aliphatically attached, isocyanate groups, especially tris(6-isocyanatohexyl)biuret or its mixtures with its higher homologs. These polyisocyanates containing biuret groups generally have an NCO content of 18% to 24% by weight and an average NCO functionality of 2.8 to 6.
    4) Polyisocyanates containing urethane and/or allophanate groups and having aromatically, aliphatically or cycloaliphatically attached, preferably aliphatically or cycloaliphatically attached, isocyanate groups, such as may be obtained, for example, by reacting excess amounts of diisocyanate, such as of hexamethylene diisocyanate or of isophorone diisocyanate, with mono- or polyhydric alcohols. These polyisocyanates containing urethane and/or allophanate groups generally have an NCO content of 12% to 24% by weight and an average NCO functionality of 2.0 to 4.5. Polyisocyanates of this kind containing urethane and/or allophanate groups may be prepared without catalyst or, preferably, in the presence of catalysts, such as ammonium carboxylates or ammonium hydroxides, for example, or allophanatization catalysts, such as bismuth, cobalt, cesium, Zn(II) or Zr(IV) compounds, for example, in each case in the presence of monohydric, dihydric or polyhydric, preferably monohydric, alcohols.
    
        These polyisocyanates containing urethane groups and/or allophanate groups frequently occur in mixed forms with the polyisocyanates identified under 1).
    
    
    5) Polyisocyanates comprising oxadiazinetrione groups, derived preferably from hexamethylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this kind comprising oxadiazinetrione groups are accessible from diisocyanate and carbon dioxide.
    6) Polyisocyanates comprising iminooxadiazinedione groups, derived preferably from hexamethylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this kind comprising iminooxadiazinedione groups are preparable from diisocyanates by means of specific catalysts.
    7) Hyperbranched polyisocyanates, of the kind known for example from DE-A110013186 or DE-A110013187.
    8) Polyurethane-polyisocyanate prepolymers, from di- and/or polyisocyanates with alcohols.
    9) Polyurea-polyisocyanate prepolymers.
    10) The polyisocyanates 1)-9), preferably 1), 3), 4), and 6), can be converted, following their preparation, into polyisocyanates containing biuret groups or urethane/allophanate groups and having aromatically, cycloaliphatically or aliphatically attached, preferably (cyclo)aliphatically attached, isocyanate groups. The formation of biuret groups, for example, is accomplished by addition of water or by reaction with amines. The formation of urethane and/or allophanate groups is accomplished by reaction with monohydric, dihydric or polyhydric, preferably monohydric, alcohols, in the presence if desired of suitable catalysts. These polyisocyanates containing biuret or urethane/allophanate groups generally have an NCO content of 10% to 25% by weight and an average NCO functionality of 3 to 8.
    11) Hydrophilically modified polyisocyanates, i.e., polyisocyanates which as well as the groups described under 1-10 also comprise groups which result formally from addition of molecules containing NCO-reactive groups and hydrophilizing groups to the isocyanate groups of the above molecules. The latter groups are nonionic groups such as alkylpolyethylene oxide and/or ionic groups derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, and/or their salts.
    12) Modified polyisocyanates for dual cure applications, i.e., polyisocyanates which as well as the groups described under 1-11 also comprise groups resulting formally from addition of molecules containing NCO-reactive groups and UV-crosslinkable or actinic-radiation-crosslinkable groups to the isocyanate groups of the above molecules. These molecules are, for example, hydroxyalkyl(meth)acrylates and other hydroxyvinyl compounds.


The diisocyanates or polyisocyanates recited above may also be present at least partly in blocked form.
Classes of compounds used for blocking are described in D. A. Wicks, Z. W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and also 43, 131-140 (2001).
Examples of classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.
In one preferred embodiment of the present invention the polyisocyanate is selected from the group consisting of isocyanurates, biurets, urethanes, and allophanates, preferably from the group consisting of isocyanurates, urethanes, and allophanates; more preferably it is a polyisocyanate containing isocyanurate groups.
In one particularly preferred embodiment the polyisocyanate encompasses polyisocyanates comprising isocyanurate groups and obtained from 1,6-hexamethylene diisocyanate.
In one further preferred embodiment the polyisocyanate encompasses a mixture of polyisocyanates comprising isocyanurate groups and obtained very preferably from 1,6-hexamethylene diisocyanate and from isophorone diisocyanate.
In one particularly preferred embodiment the polyisocyanate is a mixture comprising low-viscosity polyisocyanates, preferably polyisocyanates comprising isocyanurate groups, having a viscosity of 600-1500 mPa*s, more particularly below 1200 mPa*s, low-viscosity urethanes and/or allophanates having a viscosity of 200-1600 mPa*s, more particularly 600-1500 mPa*s, and/or polyisocyanates comprising iminooxadiazinedione groups.
In this specification, unless noted otherwise, the viscosity is reported at 23° C. in accordance with DIN EN ISO 3219/A.3 in a cone/plate system with a shear rate of 1000 s−1.
The process for preparing the polyisocyanates may take place as described in WO 2008/68198, particularly from page 20, line 21 to page 27, line 15 therein, as is hereby made part of the present specification by reference.
The reaction may be terminated, for example, as described therein from page 31, page 19 to page 31, line 31, and the product may be worked up as described therein from page 31, line 33 to page 32, line 40, as is hereby made part of the present specification in each case by reference.
The reaction may alternatively take place as described in WO 2005/087828 for ammonium alpha-hydroxycarboxylate catalysts. The ammonium α-hydroxycarboxylates described in WO 2005/87828 at page 3 line 29 to page 6 line 7 are hereby expressly part of the present disclosure content. The reaction may be terminated, for example, as described therein from page 11, line 12 to page 12, line 5, as is hereby made part of the present specification by reference.
The reaction may alternatively take place as described in CN 10178994A or CN 101805304.
In the case of thermally unstable catalysts it is also possible, moreover, to terminate the reaction by heating the reaction mixture to a temperature above at least 80° C., preferably at least 100° C., more preferably at least 120° C. In general the heating of the reaction mixture as required to remove the unreacted isocyanate by distillation in the work-up procedure is sufficient for this purpose.
Both for thermally stable and thermally unstable catalysts, the possibility exists of terminating the reaction at relatively low temperatures by adding deactivators. Deactivators may also be added in a stoichiometric deficit to the catalyst, if the catalyst is at least partially destroyed thermally or the product is stable in terms of its viscosity on subsequent storage (e.g., when stored in the 100% form over 10 weeks at 80° C. under nitrogen, undergoing not more than a three fold increase in its viscosity). Examples of suitable deactivators include hydrogen chloride, phosphoric acid, organic phosphates, such as dibutyl phosphate or diethylhexyl phosphate, and carbamates such as hydroxyalkyl carbamate.
These compounds are added neat or diluted in suitable concentration needed for termination of reaction.
Additives with Inventive Antiflocculating Effect:
a1) organic acids with pKa values of less than 4.2
a1a) preferred examples in the sense of the invention are aromatic sulfonic acids having pKa values of less than 4.2, more preferably benzene or naphthalene derivatives, more particularly alkylated benzene or naphthalene derivatives.
Examples of preferred sulfonic acids include 4-alkylbenzenesulfonic acids with alkyl radicals of 6 to 12 C atoms, preferably in ortho- or para-position, preferably para-position, to the sulfonic acid group such as, for example, 4-hexylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, 4-decylbenzenesulfonic acid or 4-dodecylbenzenesulfonic acid. In this context it is also possible, in a way which is known in principle, for the compounds in question to be technical products exhibiting a distribution of different alkyl radicals of different lengths.
Particularly preferred acids include the following:

    
    
        benzenesulfonic acid
        para-toluenesulfonic acid
        para-ethylbenzenesulfonic acid
        dodecylbenzenesulfonic acid
        bisnonylnaphthalenesulfonic acid
        bisnonylnaphthalenebissulfonic acid
        bisdodecylnaphthalenesulfonic acid
        Nacure® XC-C210 (hydrophobic acid catalyst of undisclosed structure from King Industries)
    
    


a1b)
Other preferred acids for the purposes of the invention are singularly or doubly alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acids having two carbon atoms, and singularly or doubly halogen-, alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acids, alkenedicarboxylic acids or alkanedicarboxylic acids having at least three carbon atoms, preferably the stated substituted alkanecarboxylic acids having a pKa of below 4.2.
Examples of alkanecarboxylic acids having two or at least three carbon atoms are those having 2 to 8, preferably 2 to 6, more preferably 2 to 4, and very preferably 2 or 3 carbon atoms. These alkanecarboxylic acids may be linear or branched.
Particularly noteworthy such alkanecarboxylic acids as parent structures are acetic acid, propionic acid, butyric acid, isobutyric acid, and caproic acid.
The parent structures of these alkanecarboxylic acids are substituted singularly or doubly, preferably singularly, by halogen, alkoxy, mercapto or alkylmercapto, it being possible for the substituents to be alike or different.
Halogen here is chlorine or bromine, preferably chlorine. Haloacetic acid derivatives are not inventive.
Alkoxy here means C1 to C12 alkyloxy, preferably C1 to C8 alkyloxy, more preferably C1 to C4 alkyloxy and very preferably C1 to C2 alkyloxy.
Examples are methoxy, ethoxy, isopropyloxy, n-propyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, 2-ethylhexyloxy, and 2-propylheptyloxy.
Mercapto here means a thiol group (—SH).
Alkylmercapto here means C1 to C12 alkylmercapto, preferably C1 to C8 alkylmercapto, more preferably C1 to C4 alkylmercapto, and very preferably C1 to C2 alkylmercapto. Examples thereof are the sulfur-analog compounds of the above-recited alkoxy groups. Arylthio groups, more particularly phenylthio groups, are possible as well.
Aryl in this specification refers to monovalent aromatic radicals having 6 to 12 carbon atoms and being able optionally, although less preferably, to be substituted. Examples thereof are phenyl, α-naphthyl, and β-naphthyl.
Among the substituents, halogen, alkoxy, and mercapto are preferred, particular preference being given to halogen and alkoxy and more preference to halogen.
Particularly preferred substituted alkanecarboxylic acids are those which carry at least one substituent in α- or β-position to the carboxyl group, the β-position being relevant, of course, only in the case of alkanecarboxylic acids having at least three carbon atoms.
Examples of particularly preferred acids for the purposes of the invention are 2- or 3-chloroalkanecarboxylic acids having at least three, preferably three to six, more preferably three to four, and very preferably three carbon atoms.
Examples of an alkenedicarboxylic acid are maleic acid and fumaric acid.
One example of an alkanedicarboxylic acid is the formal adduct of hydrochloric acid with maleic acid, i.e., chlorine-substituted succinic acid.
Particularly preferred examples of acids a1b) of the invention are

    
    
        3-chloropropionic acid and
        2-chloropropionic acid.
    
    


These are very good antiflocculants, even in comparison to acids of comparable pKa such as methoxyacetic acid. It cannot be ruled out, without wishing to be confined to one mechanism of action, that chloropropionic acids react in a basic environment with elimination of hydrochloric acid, hence constituting latently blocked hydrochloric acid with a relatively low pKa.
pKa values: the table below shows the pKa values of some acids:














Acid
pKa value



















Not inventive




Ethylhexanoic acid
4.8



Acetic acid
4.76



Pivalic acid



Acrylic acid
4.3



Phenylacetic acid
4.31



Benzoic acid
4.2



Formic acid
3.8



Chloroacetic acid
2.86



Dichloroacetic acid
1.29



Trichloroacetic acid
0.65



Trifluoroacetic acid
0.2



Methanesulfonic acid
−1.9



Trifluoromethanesulfonic acid
−5.5



Inventive



3-Chloropropionic acid
4.1



Mercaptoacetic acid
3.55



Methoxyacetic acid
3.48



Diethylhexyl phosphate
3.2



Fumaric acid
3.0



2-Chloropropionic acid
2.8



Nacure ® 5076 from King Industries
−3



(aromatic sulfonic acid)










Surprisingly, even some acids with a pKa of below 4.2 have no significant antiflocculant effect, examples being trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.
Not inventive are unsubstituted or relatively short alkylcarboxylic acids such as formic acid, acetic acid, ethylhexanoic acid, pivalic acid, acrylic acid, and also arylcarboxylic acids such as benzoic acid.
Acids are used in part in the trimerization and allophanatization (isocyanuratization) as stoppers or in biuretization as catalysts, and may therefore be inherently present in the products. Explicitly cited in the prior art as isocyanatization stoppers are, for example, hydrochloric acid, acid chlorides, phosphoric acid, and phosphorous acid, and derivatives thereof, such as dibutyl phosphate, di(2-ethylhexyl)phosphate, and dibutyl phosphite, and also sulfonic acids such as para-toluenesulfonic acid and its methyl and ethyl esters (EP 330966).
Explicitly cited as biuretization catalysts are dialkyl phosphates (EP 918809).
However, there is no indication therein that products stocked in this way have particular antiflocculant advantages in the context of the use of the polyisocyanates in solutions.
As specifically added antiflocculants, the acids preferred in accordance with the invention may be used universally and independently of the preparation process, as for example also in the case of a silicon-based isocyanuratization catalyst, such as silazanes, with stopping by alcohols such as n-butanol, as described in specifications EP 57653 B1 and EP 89297 B1, for example, or in the case of thermal stopping in the isocyanuratization and allophanatization with ammonium carboxylates, or in the case of uretdiones with phosphine catalysis and chemical stopping with sulfur. In the case in particular of isocyanuratization with thermal stopping, i.e., thermal deactivation of the catalyst used, the stabilizing method of the invention exhibits a particular advantage. Catalysts of this kind are more particularly quaternary 2-hydroxyalkyl-ammonium salts.
2-Chloropropionic acid as a chemical stopper in the isocyanuratization with a trimethylbenzylammonium hydroxide or tetralkylammonium hydroxycarboxylate catalyst at 65° C. in stoichiometric amount is not sufficiently strong, and so the product, although preparable, then turns into a gelatinous state, presumably as a result of undimished polymerization of isocyanate groups through further catalysis by the incompletely deactivated catalyst.
On addition to a stable isocyanurate, in contrast, 2-chloropropionic acid is a very good antiflocculant.
a2) Polycyclic Phosphites
Phosphites are known to be secondary antioxidants, combating oxidation of the products they are used to stabilize, particularly in synergy with primary antioxidants such as sterically hindered phenol derivatives, and hence reducing, for example, a color drift. Surprisingly it has been found that certain phosphites also have antiflocculant effect for polyisocyanates in solvents. The antiflocculant effect takes place alone and optionally in combination with sterically hindered phenols, but not in the case of monophosphites (cf. experimental series 2, comparative example 5 etc). As a common structural feature of the phosphites with antiflocculant effect, it has been found that they are oligophosphites, more particularly diphosphites, more particularly pentaerythritol diphosphites (see the figure below). For the purposes of the invention, therefore, reference is to pentaerythritol diphosphites and comparable structures, respectively, of corresponding effect. In one form in accordance with the invention they are bisaryl pentaerythritol diphosphites. More particularly the latter are compounds in which the aryl groups are substituted phenol groups having at least two branched, preferably tertiary aliphatic substituents.
Triphenyl phosphite, as the most widely used phosphate in polyisocyanates or mixtures thereof and solutions thereof, has no effect in this context (cf. experimental series 2, comparative example 5 etc). On the contrary, the flocculation effect is even increased.
In some cases these sterically tensioned diphosphites are known to be sensitive to hydrolysis, such as Irgafos® 126. Surprisingly, however, even in markedly substoichiometric amounts, they have a very strong antiflocculating effect. 600 ppm of Irgafos® 126 relative to 30% of polyisocyanate in solvent correspond, in the case of equimolar hydrolysis, to 8 ppm of water on solvent, which is negligible in relation to the 800 ppm of water in the solvent of examples below. Accordingly, the antiflocculant effect cannot be authoritatively attributed to capacity as a water scavenger.
Diphosphites are, for example, compounds of the following structure based on pentaerythritol:




where R is an aryl group which may be substituted in positions 2, 4, and 6 as follows:
position 2: tert-butyl, tert-amyl,
position 4: hydrogen, alkyl, tert-butyl or tert-amyl, and
position 6: hydrogen, alkyl, tert-butyl or tert-amyl,
with the proviso that at least one of the substituents in positions 4 and 6 of the aryl group is not hydrogen.
Preferred examples are as follows:

    
    
        “9228=Doverphos® S-9228=3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CAS=154862-43-8)
        3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CAS 80693-00-1)=ADK Stab PEP-3
        Irgafos® 126=bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (CAS 26741-53-7)
        Weston® 618=Doverphos® S 680=dioctadecylpentaerythritol diphosphite (CAS 3806-34-6)
        ADK Stab PEP 36 (CAS 80693-00-1)
        bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; 3,9-bis(2,4-bis-(1,1-dimethylethyl)phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane=ADK Stab PEP 24=Doverphos® S 9432=Weston® 626
    
    


a3) Phosphonites
Phosphonites are known to be secondary antioxidants which particularly in synergy with primary antioxidants such as sterically hindered phenol derivatives act to counter oxidation of the products they are used to stabilize, and hence, for example, reduce a color drift. Surprisingly it has been found that phosphonites also have an antiflocculating effect in aliphatic solvents. Phosphonites as stabilizers against yellowing are described in WO 2008/116894, for example. These compounds, and compounds described in U.S. Pat. No. 4,075,163, are hereby incorporated as part of this invention. The phosphonites which can be used in accordance with the invention have the following structure:

(RO)2P—X—P(OR)2 

where R is an aryl group which may be substituted in positions 2, 4 and 6 as follows:
position 2: tert-butyl, tert-amyl
position 4: hydrogen, alkyl, tert-butyl or tert-amyl, and
position 6: hydrogen, alkyl, tert-butyl or tert-amyl,
with the proviso that at least one of the substituents in positions 4 and 6 of the aryl group is not hydrogen.
X here is an arylene group, i.e., a divalent organic radical having 6 to 12 carbon atoms, such as phenylene, naphthylene or biphenylene, for example.
Particular preference is given to

    
    
        Irgafos® P-EPQ=formal reaction product of phosphorus trichloride with 1,1′-biphenyl- and 2,4-bis(1,1-dimethylethyl)phenol (see figure below with R═H. R=methyl is likewise preferred.)
    
    






Irgafos® P-EPQ may undergo hydrolysis in the presence of moisture and preferably under acidic conditions, and hence may act formally as a water scavenger. This reaction occurs autocatalytically, since the hydrolysis generates further acid. Surprisingly, Irgafos® P-EPQ has an antiflocculant effect even in a significantly substoichiometric amount. 600 ppm of Irgafos® P-EPQ relative to 30% of polyisocyanate in solvent correspond, in the case of equimolar hydrolysis, to 5 ppm of water, which is negligible in relation to the 800 ppm of water in the solvent of numerous experiments. Accordingly, the antiflocculant effect cannot be authoritatively attributed to the capacity as a water scavenger, and is therefore surprising.
a4) Other Examples are Acidic Phosphorus Derivatives Independently of the Oxidation State and pKa:
a4a) Compounds a4a) are mono- and di-C1 to C12-alkyl phosphates and mixtures thereof, preferably the dialkyl phosphates, more preferably those with C1 to C8 alkyl groups, very preferably with C2 to C8 alkyl groups, and more particularly those with C4 to C8 alkyl groups.
The alkyl groups in dialkyl phosphates here may be alike or different, and are preferably alike.
Examples of C1 to C12 alkyl groups are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, 2-ethylhexyl, and 2-propylheptyl.
These are more particularly monoalkyl and dialkyl phosphates and mixtures thereof such as

    
    
        di(ethylhexyl) phosphate
        di-n-butyl phosphate
        diethyl phosphate
        Nacure® 4000 (formerly Nacure® C 207), an unspecified alkyl phosphoric ester, from King Industries
        Nacure® 4054, an unspecified alkyl phosphoric ester, from King Industries
        Cycat® 296-9, an unspecified alkyl phosphoric ester, from Cytec
    
    


For use in polyisocyanates it is preferred to employ these compounds a4a) in the form of the 100% product or in a solvent which does not react with isocyanate groups.
a4b) Examples of low-valence phosphorus-containing compounds with acidic character are compounds a4b) dialkyl phosphonates and dialkyl diphosphonates.




Examples thereof are mono- and di-C1 to C12 alkyl phosphonates and mixtures thereof, preferably the dialkyl phosphonates, more preferably those with C1 to C8 alkyl groups, very preferably with C1 to C12 alkyl groups, and more particularly those with C1, C2, C4 or C8 alkyl groups.
The alkyl groups in dialkyl phosphonates here may be alike or different, and are preferably alike.
Examples of C1 to C12 alkyl groups are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, 2-ethylhexyl, and 2-propylheptyl.
The examples described in WO 2008/116895 are hereby an inherent part of this patent. Specific examples that may be mentioned explicitly include the following:

    
    
        dioctyl phosphonate, di-n-octyl phosphonate Irgafos® OPH (see figure above)
        di-(2-ethylhexyl)phosphonate
        dibutyl phosphonate
        diethyl phosphonate
        dimethyl phosphonate, preferably the dioctyl phosphonates.
    
    


The aromatic diphenyl phosphonate, in contrast, exhibits no significant antiflocculant effect (experimental series 6 and 7).
a4c) Further examples of phosphorus-containing compounds with acidic character are phosphinic esters.
Examples thereof are mono-C1 to C12 alkyl phosphinates, more preferably those with C1 to C8 alkyl groups, very preferably with C2 to C8 alkyl groups, and more particularly those with C4 to C8 alkyl groups.
Further examples thereof are mono-C6 to C12 aryl phosphinates, more preferably those with C6 aryl groups.
The alkyl groups in dialkyl phosphinates here may be alike or different, and are preferably alike.
Examples of C1 to C12 alkyl groups are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, 2-ethylhexyl, and 2-propylheptyl.
On their central phosphorus atom, the phosphinates may carry a substituent, which may be an alkyl or aryl radical and which may optionally be joined to the oxygen atom, thus forming an ester group.
Examples thereof are phosphaphenanthrene derivatives such as

    
    
        Sanko HCA=“DOPO”=9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (CAS 35948-25-5; see figure below), and derivatives of this structure
    
    






and its derivatives.
a4d) Likewise included are alkyl derivatives of the type H4P2On, of hypodisphosphonic acid, diphosphonic acid, hypodiphosphoric acid, and diphosphoric acid, with at least one OH— or PH— acidic group.
a5) Blocked, Preferably Covalently Blocked, Aromatic Sulfonic Acids
Blocked sulfonic acid derivatives such as sulfonic esters are being developed to cure hydroxyl-functional polymers with aminoformalde crosslinkers. For unblocking they require an activation temperature which is said for example to be 130 or 150° C. In the context of this invention, surprisingly, they exhibit an antiflocculant effect on additivation of polyisocyanates in solvents.
“Blocking” here means that the free acid is released only as a result of energy supply, from a salt, for example, preferably a salt with an amine, or by cleavage, for example, of an ester (covalent blocking):
In the case of the covalently blocked aromatic sulfonic acids, the compounds in question may be, for example, esters of sulfonic acids and (cyclo-)aliphatic (or aromatic) alcohols and adducts of the sulfonic acids with epoxides, of the kind described in US 2009/104363, WO 2009/045466, and CA 1339319. They may be monomeric, oligomeric or polymeric. These compounds are inherently hereby part of this patent specification as well.
Examples thereof are the following King Industries brands:

    
    
        Nacure® 5414 (polymer-blocked dodecylbenzenesulfonic acid, 25% in xylene; deblocking temperature 130° C.)
        Nacure® 1419 (blocked dinonylnaphthalenesulfonic acid, 30% in xylene/methyl isobutyl ketone; deblocking temperature 150° C.)
        Nacure® XC-194 (latently blocked alkylarylsulfonic acid, 20% in solvent mixture of hydrocarbons; deblocking temperature 150° C.).
    
    


Residual acid contents are not specified. Moreover, the blocked sulfonic acids act in very small, substoichiometric amounts.
The blocked aromatic sulfonic acids are, for example, benzene or naphthalene derivatives, more particularly alkylated benzene or naphthalene derivatives.
Examples of preferred sulfonic acids include 4-alkylbenzenesulfonic acids with alkyl radicals of 6 to 12 C atoms such as, for example, 4-hexylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, 4-decylbenzenesulfonic acid or 4-dodecylbenzenesulfonic acid. These compounds may, in a way which is known in principle, also be technical products which exhibit a distribution of different alkyl radicals of different lengths.
Particularly preferred acids, in each case in blocked form, include the following:

    
    
        benzenesulfonic acid
        para-toluenesulfonic acid
        para-ethylbenzenesulfonic acid
        dodecylbenzenesulfonic acid
        bisnonylnaphthalenesulfonic acid
        bisnonylnaphthalenebissulfonic acid
        bisdodecylnaphthalenesulfonic acid.
    
    


Solvents which can be used for the polyisocyanate component, and also for the binder components and any further components, are those which do not have any groups reactive toward isocyanate groups or toward blocked isocyanate groups, and in which the polyisocyanates are soluble to an extent of at least 10%, preferably at least 25%, more preferably at least 50%, very preferably at least 75%, more particularly at least 90%, and especially at least 95% by weight.
Examples of solvents of this kind are aromatic hydrocarbons (including alkylated benzenes and naphthalenes) and/or (cyclo)aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated alkyl alkanoates, ethers, and mixtures of the solvents.
Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C7 to C14 hydrocarbons and may encompass a boiling range from 110 to 300° C.; particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, ethylbenzene, cumene, tetrahydronaphthalene; and mixtures comprising them.
Examples thereof are the Solvesso® products from ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C9 and C10 aromatics, boiling range about 154-178° C.), 150 (boiling range about 182-207° C.), and 200 (CAS No. 64742-94-5), and also the Shellsol® products from Shell, Caromax® (e.g., Caromax® 18) from Petrochem Carless and Hydrosol from DHC (e.g., as Hydrosol® A 170). Hydrocarbon mixtures comprising paraffins, cycloparaffins, and aromatics are also available commercially under the names Kristalloel (for example, Kristalloel 30, boiling range about 158-198° C. or Kristalloel 60: CAS No. 64742-82-1), white spirit (for example likewise CAS No. 64742-82-1) or solvent naphtha (light: boiling range about 155-180° C., heavy: boiling range about 225-300° C.). The aromatics content of such hydrocarbon mixtures is generally more than 90%, preferably more than 95%, more preferably more than 98%, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures having a particularly reduced naphthalene content.
Examples of (cyclo)aliphatic hydrocarbons include decalin, alkylated decalin, and isomer mixtures of linear or branched alkanes and/or cycloalkanes.
The amount of aliphatic hydrocarbons is generally less than 5%, preferably less than 2.5%, and more preferably less than 1% by weight.
Esters are, for example, n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, and 2-methoxyethyl acetate.
Ethers are, for example, THF, dioxane, and also the dimethyl, diethyl or di-n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
Ketones are, for example, acetone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, methyl amyl ketone, and tert-butyl methyl ketone.
Preferred solvents are n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, 2-methoxyethyl acetate, and mixtures thereof, especially with the aromatic hydrocarbon mixtures recited above, more particularly xylene and Solvesso® 100.
Mixtures of this kind can be made in a volume ratio of 5:1 to 1:5, preferably in a volume ratio of 4:1 to 1:4, more preferably in a volume ratio of 3:1 to 1:3, and very preferably in a volume ratio of 2:1 to 1:2.
Preferred examples are butyl acetate/xylene, methoxypropyl acetate/xylene 1:1, butyl acetate/solvent naphtha 100 1:1, butyl acetate/Solvesso® 100 1:2, and Kristalloel 30/Shellsol® A 3:1.
Preference is given to butyl acetate, 1-methoxyprop-2-yl acetate, methyl amyl ketone, xylene, and Solvesso® 100.
The additives with antiflocculant effect are preferably dispersed homogeneously, preferably using mixing devices.
The additives with antiflocculant defect can be added in a variety of ways—for example, as they are, in solvents and/or other additives, including, in particular, in other solvents, in which there should preferably be good solubility, such as, for example, dialkyldicarboxylic esters such as dioctyladipic ester and dinonyladipic ester, phosphoric acid trialkyl esters, phthalic esters and ring-hydrogenated phthalic esters, such as diisononyl cyclohexane-1,2-dicarboxylate, for example.
The additives with antiflocculant effect may be introduced, for example,

    
    
        into the pure polyisocyanate,
        into a saleable polyisocyanate in solvent,
        in a polyisocyanate component, consisting, for example, of polyisocyanate, solvent(s), and additives. A saleable polyisocyanate component of this kind may be used with a corresponding polyol component without further additions, optionally after separate storage, by blending the two components for coating.
    
    


Preference is given to additives which are present in liquid form or which can be incorporated by stirring with low and short-term shearing forces.
The additives with antiflocculant effect can be added to the polyisocyanate at elevated temperature directly after the distillation at from about 170° C. to the ambient temperature, in the case of solid additives preferably at a temperature above their melting point, or else in solid form, in which case the homogenization effort becomes higher.
In one specific form they are mixed batchwise, optionally in solvent, with the polyisocyanate in less than an hour at between room temperature and 70° C. in a stirred tank.
In another specific form they are added, optionally in solvent, continuously in a static mixer at between room temperature and 70° C.
Preliminary dissolution in solvent may be useful in particular in the case of solid additives with antiflocculant effect, such as the polycyclic phosphites a2) or phosphonites a3) which in some cases have high melting points and poor solubilities in polyisocyanate and solvent.
Another form of use is the preparation of a stock solution, for example, in solvent, additive mixtures and/or polyisocyanate.
In the examples given below, the amounts in which the antiflocculants are added are typically significantly substoichiometric in relation to the total amount of water in the mixture. This, however, is not intended to confine the amounts of additives added, within the ambit of the claims, to a stoichiometric deficit.
In one preferred form it is advantageous, for the reasons given above and further reasons, to add to the polyisocyanate the minimum amount of additive necessary to adequately prevent flocculation for, for example, six months. Further reasons for specifying a minimally necessary amount is that many of the additives may have further functional effect in polyurethane systems. Aromatic sulfonic acids, for example, may act as a urethanization catalyst. Dialkylphosphoric acids may lead to precipitates in interaction with dibutyltin dilaurate, depending on the amount. Acids may interact with basic additives such as UV stabilizers or amine catalysts. It is therefore advantageous to minimize the amount of additive, and to make a selective choice optionally in dependence on other additives.
The antiflocculant defect does not always increase with the amount of additive. The optimum amount must therefore be determined optionally in dependence on the polyisocyanate used and other components.
Generally speaking, the compounds of the invention are added to the polyisocyanate, for the purpose of reducing flocculation, in the following amounts:
Compounds a1a) are added generally in amounts, based on the polyisocyanate, of 1 to 600 ppm by weight, preferably 2 to 100, more preferably 5 to 50 ppm by weight.
Compounds a1b), a2), and a3) are generally added in amounts, based on the polyisocyanate, of 20 to 3000 ppm by weight, preferably 50-800 ppm by weight, more preferably 100-600 ppm by weight.
Compounds a4a) are added generally in amounts, based on the polyisocyanate, of 5 to 1000 ppm by weight, preferably 10 to 600, more preferably 20 to 200, very preferably 20 to 100 ppm by weight.
Compounds a4b), a4c), a4d), and a5) are added generally in amounts, based on the polyisocyanate, of 5 to 1000 ppm by weight, preferably 10 to 600, more preferably 20 to 300, very preferably 30 to 200 ppm by weight.
The choice of the additives may be dependent on the solvent or solvent mixture that is used.
Frequently it is the case that the flocculation tendency goes up with increasing dilution by the solvent, particularly at solvent contents of more than 50%, more particularly at more than 60%.
The polyisocyanate component comprising an additive with antiflocculant effect may, optionally after storage, be reacted with at least one binder component and, optionally, with further components to form, for example, paints or adhesives.
The binders may be, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea polyols; polyester-polyacrylate polyols; polyester-polyurethane polyols; polyurethane-polyacrylate polyols, polyurethane-modified alkyd resins; fatty acid-modified polyester-polyurethane polyols, copolymers with allyl ethers, graft polymers of the stated groups of compound having, for example, different glass transition temperatures, and also mixtures of the stated binders. Preference is given to polyacrylate polyols, polyester polyols, and polyurethane polyols.
Preferred OH numbers, measured in accordance with DIN 53240-2 (potentiometrically), are 40-350 mg KOH/g resin solids for polyesters, preferably 80-180 mg KOH/g resin solids, and 15-250 mg KOH/g resin solids for polyacrylateols, preferably 80-160 mg KOH/g.
Additionally the binders may have an acid number in accordance with DIN EN ISO 3682 (potentiometrically) of up to 200 mg KOH/g, preferably up to 150 and more preferably up to 100 mg KOH/g.
Particularly preferred binders are polyacrylate polyols and polyesterols.
Polyacrylate polyols preferably have a molecular weight Mn of at least 500, more preferably at least 1200 g/mol. The molecular weight Mn may in principle have no upper limit, and may preferably be up to 50 000, more preferably up to 20 000 g/mol, and very preferably up to 10 000 g/mol, and more particularly up to 5000 g/mol.
The hydroxyl-functional monomers (see below) are used in the copolymerization in amounts such as to result in the aforementioned hydroxyl numbers for the polymers, which generally correspond to a hydroxyl group content in the polymers of 0.5% to 8%, preferably 1% to 5% by weight.
These are hydroxyl-containing copolymers of at least one hydroxyl-containing (meth)acrylate with at least one further polymerizable comonomer selected from the group consisting of (meth)acrylic acid alkyl esters, vinylaromatics, α,β-unsaturated carboxylic acids, and other monomers.
(Meth)acrylic acid alkyl esters include, for example, C1-C20 alkyl(meth)acrylates; vinylaromatics are those having up to 20 C atoms; α,β-unsaturated carboxylic acids also include their anhydrides; and other monomers are, for example, vinyl esters of carboxylic acids comprising up to 20 C atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols comprising 1 to 10 C atoms, and, less preferably, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds.
Preferred (meth)acrylic acid alkyl esters are those with a C1-C10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate.
In particular, mixtures of the (meth)acrylic acid alkyl esters are suitable as well.
Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
Examples of possible α,β-unsaturated carboxylic acids and their anhydrides include acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid or maleic anhydride, preferably acrylic acid.
Hydroxy-functional monomers include monoesters of α,β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (identified for short in this specification as “(meth)acrylic acid”), with diols or polyols which have preferably 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyloctane-1,3-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3- and 1,4-bis(hydroxymethyl)cyclohexane, 1,2-, 1,3- or 1,4-cyclohexanediol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, polyTHF with a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol or polypropylene glycol with a molecular weight between 134 and 2000, or polyethylene glycol with a molecular weight between 238 and 2000.
Preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate or 3-(acryloyloxy)-2-hydroxypropyl acrylate, and particular preference to 2-hydroxyethyl acrylate and/or 2-hydroxyethyl methacrylate.
Vinylaromatic compounds contemplated include, for example, vinyltoluene, α-butylstyrene, α-methylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, and, preferably, styrene.
Examples of nitriles are acrylonitrile and methacrylonitrile.
Suitable vinyl ethers are, for example, vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether, and vinyl octyl ether.
Nonaromatic hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds include butadiene, isoprene, also ethylene, propylene, and isobutylene.
Additionally it is possible to use N-vinylformamide, N-vinylpyrrolidone, and N-vinylcaprolactam, and, additionally, ethylenically unsaturated acids, more particularly carboxylic acids, acid anhydrides or acid amides, and also vinylimidazole. Comonomers containing epoxide groups, such as glycidyl acrylate or glycidyl methacrylate, or monomers such as N-methoxymethyl-acrylamide or -methacrylamide, can also be used as well in small amounts.
Preference is given to esters of acrylic acid and/or of methacrylic acid with 1 to 18, preferably 1 to 8, carbon atoms in the alcohol residue, such as, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-stearyl acrylate, the methacrylates corresponding to these acrylates, styrene, alkyl-substituted styrenes, acrylonitrile, methacrylonitrile, vinyl acetate or vinyl stearate, and any desired mixtures of such monomers.
The hydroxyl-bearing monomers are used in the copolymerization of the hydroxyl-bearing (meth)acrylates in a mixture with other polymerizable monomers, preferably free-radically polymerizable monomers, preferably those composed to an extent of more than 50% by weight of C1-C20, preferably C1 to C4 alkyl(meth)acrylate, (meth)acrylic acid, vinylaromatics having up to 20 C atoms, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinyl halides, nonaromatic hydrocarbons having 4 to 8 C atoms and 1 or 2 double bonds, unsaturated nitriles, and mixtures thereof. Particular preference is given to the polymers composed, further to the hydroxyl-bearing monomers, to an extent of more than 60% by weight of C1-C10 alkyl(meth)acrylates, styrene and its derivatives, or mixtures thereof.
The polymers can be prepared by polymerization in accordance with customary processes. Preferably the polymers are prepared in an emulsion polymerization or in organic solution. Continuous or discontinuous polymerization processes are possible. The discontinuous processes include the batch process and the feed process, the latter being preferred. In the feed process, the solvent, alone or with part of the monomer mixture, is introduced as an initial charge and heated to the polymerization temperature, the polymerization, in the case of the inclusion of monomer in the initial charge, is initiated free-radically, and the remainder of the monomer mixture is metered in together with an initiator mixture in the course of 1 to 10 hours, preferably 3 to 6 hours. A subsequent option is to carry out reactivation, in order to take the polymerization to a conversion of at least 99%.
Solvents contemplated include, for example, aromatics, such as solvent naphtha, benzene, toluene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methylglycol acetate, ethylglycol acetate, methoxypropyl acetate, ethers such as butylglycol, tetrahydrofuran, dioxane, ethylglycol ether, ketones such as acetone, methyl ethyl ketone, halogenated solvents such as methylene chloride or trichloromonofluoroethane.
Further binders are, for example, polyester polyols, as are obtainable by condensing polycarboxylic acids, especially dicarboxylic acids, with polyols, especially diols. In order to ensure a polyester polyol functionality that is appropriate for the polymerization, use is also made in part of triols, tetrols, etc, and also triacids etc.
Polyester polyols are known for example from Ullmanns Enzyklopädie der technischen Chemie, 4th edition, volume 19, pp. 62 to 65. It is preferred to use polyester polyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. In lieu of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof to prepare the polyester polyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, by halogen atoms for example, and/or unsaturated. Examples thereof that may be mentioned include the following:
Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimeric fatty acids, their isomers and hydrogenation products, and also esterifiable derivatives, such as anhydrides or dialkyl esters, C1-C4 alkyl esters for example, preferably methyl, ethyl or n-butyl esters, of the stated acids are employed. Preference is given to dicarboxylic acids of the general formula HOOC—(CH2)y—COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, and more preferably succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid.
Suitable polyhydric alcohols for preparing the polyesterols include 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, Poly-THF having a molar mass of between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molar mass between 134 and 1178, poly-1,2-propanediol having a molar mass between 134 and 898, polyethylene glycol having a molar mass between 106 and 458, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexane-dimethanol, 1,2-, 1,3- or 1,4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol or isomalt, which optionally may have been alkoxylated as described above.
Preferred alcohols are those of the general formula HO—(CH2)x—OH, where x is a number from 1 to 20, preferably an even number from 2 to 20. Preferred are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Additionally preferred is neopentyl glycol.
Also suitable, furthermore, are polycarbonate diols of the kind obtainable, for example, by reacting phosgene with an excess of the low molecular mass alcohols specified as synthesis components for the polyester polyols.
Also suitable are lactone-based polyester diols, which are homopolymers or copolymers of lactones, preferably hydroxy-terminated adducts of lactones with suitable difunctional starter molecules. Suitable lactones are preferably those which derive from compounds of the general formula HO—(CH2)z—COOH, where z is a number from 1 to 20 and where one H atom of a methylene unit may also have been substituted by a C1 to C4 alkyl radical. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and/or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone, and mixtures thereof. Examples of suitable starter components include the low molecular mass dihydric alcohols specified above as a synthesis component for the polyester polyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols as well can be used as starters for preparing the lactone polymers. In lieu of the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
In polyurethane coatings, molar masses Mn of the polyesters of 800-4000 g/mol are customary, although the polyesters used here are not restricted to this range.
Additionally suitable as binders are polyetherols, which are prepared by addition reaction of ethylene oxide, propylene oxide and/or butylene oxide, preferably ethylene oxide and/or propylene oxide, and more preferably ethylene oxide, with H-active components. Polycondensates of butanediol are also suitable. In polyurethane coatings, polyether molar masses of 500-2000 g/mol are customary, although the polyethers used here are not restricted to this range.
The polymers may be replaced at least in part by what are called reactive diluents. These may be blocked secondary or primary amines (aldimines and ketimines) or compounds having sterically hindered and/or electron-deficient secondary amino groups, examples being aspartic esters as per EP 403921 or WO 2007/39133.
Additionally there may optionally be a urethanization catalyst present in the coating composition. This catalyst may be, for example, an amine or an organometallic compound.
Amines are, for example, tertiary aliphatic, cycloaliphatic or aromatic amines. Examples thereof are triethylamine, tri-n-butylamine, N-methylmorpholine, N-methylpiperidine, pyrrolidine, quinuclidine or 1,4-diazabicyclo[2.2.2]octane.
Examples of organometallic compounds include tin(IV) and tin(II) salts of organic carboxylic acids, e.g., tin(II) diacetate, tin(II) dioctoate, tin(II) bis(ethylhexanoate), and tin(II) dilaurate. It is also possible to use zinc(II) salts, such as zinc(II) dioctoate, dineooctanoate, diacetate, or oxalate, for example. Metal complexes are also possible, such as acetylacetonates of iron, of titanium, of aluminum, of zirconium, of manganese, of nickel, of zinc, and of cobalt. Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, vol. 35, pages 19-29.
Dialkyltin(IV) salts of organic carboxylic acids are, for example, dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate, and dioctyltin diacetate. Preference is given to dibutyltin diacetate and dibutyltin dilaurate. For toxicological reasons, tin salts are less preferred, but are still frequently used in practice.
Other preferred Lewis-acidic organometallic compounds are zinc(II) dioctoate, zirconium acetylacetonate, and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate.
Bismuth and cobalt catalysts, cerium salts such as cerium octoates, and cesium salts can also be used as catalysts.
Bismuth catalysts are more particularly bismuth carboxylates, especially bismuth octoates, ethylhexanoates, neodecanoates or pivalates; examples are K-KAT 348 and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from Shepherd Lausanne, and also catalyst mixtures of, for example, bismuth organyls and zinc organyls.
Cesium salts contemplated include those compounds in which the following anions are used: F−, Cl−, ClO−, ClO3−, ClO4−, Br−, I−, IO3−, CN−, OCN−, NO2−, NO3−, HCO3−, CO32−, S2−, SH−, HSO3−, SO32−, HSO4−, SO42−, S2O22−, S2O42−, S2O52−, S2O62, S2O72−, S2O82−, H2PO2−, H2PO4−, HPO42−, PO43−, P2O74−, (OCnH2n+1)−, (CnH2n−1O2)−, (CnH2n−3O2)−, and (Cn+1H2n−2O4)2−, where n stands for the numbers 1 to 20. Preference here is given to cesium carboxylates in which the anion conforms to the formulae (CnH2n−1O2)− and also (Cn+1H2n-2O4)2− with n as 1 to 20. Particularly preferred cesium salts have monocarboxylate anions of the general formula (CnH2-1O2)−, where n stands for the numbers 1 to 20. Particularly noteworthy in this context are formate, acetate, propionate, hexanoate, and 2-ethylhexanoate.
As further, typical coatings components and/or additives it is possible for example to make use of the following: stabilizers, UV stabilizers such as UV absorbers and suitable free-radical scavengers (more particularly HALS compounds—hindered amine light stabilizers), activators (accelerants), driers, extenders, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents. Preference is given to UV stabilizers.
Stabilizers are at least one compound with stabilizing effect, “stabilizing” denoting the capacity to reduce the development of a color number and/or of the viscosity of the polyisocyanate in the course of storage over a certain time period relative to those corresponding mixtures which comprise no compounds with stabilizing effect.
Stabilization may relate either to the polyisocyanate alone or else to premixes of the polyisocyanates with further, typical coatings components and/or additives, optionally with addition of other components. This includes, in one particular embodiment, the storage of one of these compounds prior to actual application of the coating material.
These compounds with stabilizing effect are preferably selected from the group consisting of primary antioxidants (free-radical scavengers), secondary antioxidants (compounds which prevent radicals being formed, more particularly by scavenging and/or decomposing peroxides), and acidic stabilizers (Brønsted acids).
The primary antioxidants are preferably sterically hindered phenols. Such sterically hindered phenols are described for example in WO 2008/116894, preferably the compounds described therein from page 14, line 10 to page 16, line 10, hereby incorporated by reference as part of the present disclosure content.
The phenols in question are preferably those which have exactly one phenolic hydroxyl group on the aromatic ring, and more preferably those which have any desired substituent, preferably an alkyl group, in the ortho-positions, very preferably in ortho- and para-position to the phenolic hydroxyl group, more particularly alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionates, or substituted alkyl derivatives of such compounds.
In conjunction with additives of the invention they are part of the invention, preferably 2,6-di-tert-butyl-4-methylphenol (BHT); isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox® 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g. Irganox® 1076).
Such phenols may also be constituents of a polyphenolic system with a plurality of phenol groups: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (e.g., Irganox® 1010); ethylene bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate) (e.g., Irganox 245); 3,3′,3′′,5,5′,5′′-hexa-tert-butyl-a,a′,a′′-(mesitylene-2,4,6-triyl)tri-p-cresol (e.g., Irganox® 1330); 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g., Irganox® 3114), in each case products of Ciba Spezialitätenchemie, now BASF SE.
The secondary antioxidants are preferably selected from the group consisting of phosphonites, phosphonates, and thioethers, preferably from phosphonites or phosphonates.
Preferred phosphonites are described in WO 2008/116894, particularly from page 11, line 8 to page 14, line 8, therein, hereby made part of the present disclosure content by reference.
Preferred phosphonates are described in WO 2008/116895, particularly from page 10, line 38 to page 12, line 41, therein, hereby made part of the present disclosure content by reference.
These latter phosphonites and phosphonates differ from the compounds a3) and a4), respectively, used in accordance with the invention not least in that they fulfill a different purpose in the coating composition, namely an antioxidative effect, compared with the antiflocculant effect in accordance with the present invention.
Preferred thioethers are described in WO 2008/116893, particularly from page 11, line 1 to page 15, line 37, therein, hereby made part of the present disclosure content by reference.
The acidic stabilizers are Brønsted acids, as described in WO 2008/116894, particularly from page 17, line 34 to page 18, line 23, therein, hereby made part of the present disclosure content by reference.
Suitable UV absorbers comprise oxanilides, triazines and benzotriazoles (the latter available, for example, as Tinuvin® products from BASF SE) and benzophenones (e.g., Chimassorb® 81 from BASF SE). Preference is given, for example, to 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7-9-branched and linear alkyl esters; 5% 1-methoxy-2-propyl acetate (e.g., Tinuvin® 384) and α-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl) (e.g., Tinuvin® 1130), in each case products, for example, of BASF SE. DL-alpha-Tocopherol, tocopherol, cinnamic acid derivatives, and cyanoacrylates can likewise be used for this purpose.
These can be employed alone or together with suitable free-radical scavengers, examples being sterically hindered amines (often also identified as HALS or HAS compounds; hindered amine (light) stabilizers) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, e.g., bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate. They are obtainable, for example, as Tinuvin® products and Chimassorb® products from BASF SE. Preference in joint use with Lewis acids, however, is given to those hindered amines which are N-alkylated, examples being bis(1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate (e.g., Tinuvin® 144 from BASF SE); a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (e.g., Tinuvin® 292 from BASF SE); or which are N—(O-alkylated), such as, for example, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products with 1,1-dimethylethyl hydroperoxide and octane (e.g., Tinuvin® 123 from BASF SE) and especially with the HALS triazine 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethyl-amine)-1,3,5-triazine (e.g., Tinuvin® 152 from BASF SE). Additives insensitive to acid, such as Tinuvin® 152, are advantageous here.
UV stabilizers are used typically in amounts of 0.1% to 5.0% by weight, based on the solid components present in the preparation.
Suitable thickeners include, in addition to free-radically (co)polymerized (co)polymers, typical organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
Chelating agents which can be used include, for example, ethylenediamineacetic acid and salts thereof and also β-diketones.
Pigments in the true sense are, according to CD Römpp Chemie Lexikon—Version 1.0, Stuttgart/New York: Georg Thieme Verlag 1995, with reference to DIN 55943, particulate “colorants that are organic or inorganic, chromatic or achromatic and are virtually insoluble in the application medium”.
Virtually insoluble here means a solubility at 25° C. below 1 g/1000 g application medium, preferably below 0.5, more preferably below 0.25, very particularly preferably below 0.1, and in particular below 0.05 g/1000 g application medium.
Examples of pigments in the true sense comprise any desired systems of absorption pigments and/or effect pigments, preferably absorption pigments. There are no restrictions whatsoever on the number and selection of the pigment components. They may be adapted as desired to the particular requirements, such as the desired perceived color, for example, as described in step a), for example. It is possible for example for the basis to be all the pigment components of a standardized mixer system.
Effect pigments are all pigments which exhibit a platelet-shaped construction and give a surface coating specific decorative color effects. The effect pigments are, for example, all of the pigments which impart effect and can be used typically in vehicle finishing and industrial coatings. Examples of such effect pigments are pure metallic pigments, such as aluminum, iron or copper pigments; interference pigments, such as titanium dioxide-coated mica, iron oxide-coated mica, mixed oxide-coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and Cr2O3), metal oxide-coated aluminum; or liquid-crystal pigments, for example.
The coloring absorption pigments are, for example, typical organic or inorganic absorption pigments that can be used in the coatings industry. Examples of organic absorption pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments, titanium dioxide, and carbon black.
Dyes are likewise colorants, and differ from the pigments in their solubility in the application medium; i.e., they have a solubility at 25° C. of more than 1 g/1000 g in the application medium.
Examples of dyes are azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, and triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant dyes, direct dyes, disperse dyes, development dyes, vat dyes, metal complex dyes, reactive dyes, acid dyes, sulfur dyes, coupling dyes or substantive dyes.
Coloristically inert fillers are all substances/compounds which on the one hand are coloristically inactive, i.e., exhibit a low intrinsic absorption and have a refractive index similar to that of the coating medium, and which on the other hand are capable of influencing the orientation (parallel alignment) of the effect pigments in the surface coating, i.e., in the applied coating film, and also properties of the coating or of the coating compositions, such as hardness or rheology, for example. Inert substances/compounds which can be used are given by way of example below, but without restricting the concept of coloristically inert, topology-influencing fillers to these examples. Suitable inert fillers meeting the definition may be, for example, transparent or semitransparent fillers or pigments, such as silica gels, blanc fixe, kieselguhr, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silicon dioxide, amorphous silica, aluminum oxide, microspheres or hollow microspheres made, for example, of glass, ceramic or polymers, with sizes of 0.1-50 μm, for example. Additionally as inert fillers it is possible to employ any desired solid inert organic particles, such as urea-formaldehyde condensates, micronized polyolefin wax and micronized amide wax, for example. The inert fillers can in each case also be used in a mixture. It is preferred, however, to use only one filler in each case.
Preferred fillers comprise silicates, examples being silicates obtainable by hydrolysis of silicon tetrachloride, such as Aerosil® from Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
After mixing of the polyisocyanate component with a binder component and optionally further components, the coating mixture is cured at from ambient temperature to 150° C.
In one preferred variant, the coating mixture is cured at from ambient temperature to 80° C., more preferably to 60° C. (e.g., for refinish applications or large articles difficult to place in an oven).
In another preferred application, the coating mixture is cured at 110-150° C., preferably at 120-140° C. (e.g., for OEM applications).
“Curing” in the context of the present invention means the generation of a tack-free coating on a substrate by the heating of the coating composition applied to the substrate at the temperature indicated above for at least long enough for the desired tack-free state to be established.
In one preferred form, in the context of the present specification, a coating composition means a mixture of at least two components (binder and crosslinker) which is intended for the coating of at least one substrate for the purpose of forming a film and, after curing, a tack-free coating.
The substrates are coated by typical methods known to the skilled person, with at least one coating composition being applied in the desired thickness to the substrate to be coated, and any volatile constituents of the coating composition being removed, optionally with heating. This operation may if desired be repeated one or more times. Application to the substrate may take place in a known way, as for example by spraying, troweling, knifecoating, brushing, rolling, rollercoating, flowcoating, laminating, injection backmolding or coextruding.
The thickness of a film of this kind for curing may be from 0.1 μm up to several mm, preferably from 1 to 2000 μm, more preferably 5 to 200 μm, very preferably from 5 to 60 μm (based on the coating material in the state in which the solvent has been removed from the coating material).
Additionally provided by the present invention are substrates coated with a multicoat paint system of the invention.
Polyurethane coating materials of this kind are especially suitable for applications requiring particularly high application reliability, exterior weathering resistance, optical qualities, solvent resistance, chemical resistance, and water resistance.
The two-component coating compositions and coating formulations obtained are suitable for coating substrates such as wood, wood veneer, paper, cardboard, paperboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as molded cement blocks and fiber-cement slabs, or metals, which in each case may optionally have been precoated or pretreated.
Coating compositions of this kind are suitable as or in interior or exterior coatings, i.e., in those applications where there is exposure to daylight, preferably of parts of buildings, coatings on (large) vehicles and aircraft, and industrial applications, utility vehicles in agriculture and construction, decorative coatings, bridges, buildings, power masts, tanks, containers, pipelines, power stations, chemical plants, ships, cranes, posts, sheet piling, valves, pipes, fittings, flanges, couplings, halls, roofs, and structural steel, furniture, windows, doors, woodblock flooring, can coating and coil coating, for floor coverings, such as in parking levels or in hospitals, in automotive finishes, as OEM and refinish.
Coating compositions of this kind are used preferably at temperatures between ambient temperature to 80° C., preferably to 60° C., more preferably to 40° C. The articles in question are preferably those which cannot be cured at high temperatures, such as large machines, aircraft, large-capacity vehicles, and refinish applications.
In particular the coating compositions of the invention are used as clearcoat, basecoat, and topcoat material(s), primers, and surfacers.
Long storage of the polyisocyanate component is customary especially with refinish applications and in some cases with industrial applications as well. The polyisocyanate admixed with additives with antiflocculant effect, or the polyisocyanate component, can of course also be used for any other application.


EXAMPLES
Ingredients
Polyisocyanates
PI-1-PI-3, PI-5: Various batches of isocyanurate Basonat® HI 100 with a viscosity of about 2800 mPa*s (BASF SE)
PI-4: Biuret Basonat® HB 100 (BASF SE)
PI-6: Isocyanurate of isophorone diisocyanate, 70% in Solvesso® 100, Basonat® IT 270 S (BASF SE)
PI-7: Allophanate of hexamethylene diisocyanate, Basonat® HA 100, viscosity about 1200 mPa*s (BASF SE)
PI-8: Allophanate of hexamethylene diisocyanate, Basonat® HA 300, viscosity about 300 mPa*s (BASF SE)
Additives. The compounds used in the tables below are abbreviated as follows:
Sterically Hindered Phenols (Comparative):

    
    
        “BHT”=2,6-Di-tert-butyl-4-methylphenol
        “1135”=Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C8 branched alkyl ester, Irganox® 1135 (BASF SE)
    
    


Standard Water Scavengers (Comparative):

    
    
        “TI”=para-Toluenesulfonyl isocyanate, additive TI (Borchers)
        “OF”=Triethyl orthoformate, additive OF (Borchers)
    
    


Monocyclic Phosphites (Comparative):

    
    
        “Tppt”=Triphenyl phosphite
        “168”=Tris(2,4-di-tert-butylphenyl)phosphate, Irgafos® 168 (BASF)
    
    


Acids (Comparative):

    
    
        “Ac”=Acetic acid
        “MS”=Methanesulfonic acid
        “TFAc”=Trifluoroacetic acid
    
    


Other Compounds (Comparative):

    
    
        “DPP”=Diphenyl phosphonate
    
    


Polycyclic Phosphites (Inventive):

    
    
        “126”=Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite=Irgafos® 126 (BASF SE)
        “9228”=3,9-Bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane=pentaerythritol diphosphite=Doverphos S-9228 (Dover Chemical Corporation)
        “618”=Weston 618=Doverphos S 680 (CAS 3806-34-6)
        3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CAS 80693-00-1)=ADK Stab PEP-3
    
    


Phosphonite (Inventive):

    
    
        “EPQ”=Phosphorus trichloride, reaction products with 1,1′-biphenyl- and 2,4-bis(1,1-dimethylethyl)-phenol=Irgafos® P-EPQ (BASF SE)
    
    


Acids

    
    
        “2-CPS”=2-Chloropropionic acid
        “3-CPS”=3-Chloropropionic acid
        “DEHP”=Diethylhexyl phosphate
        “OPH”=Irgafos® OPH=dioctyl phosphonate (BASF SE)
        “DOPO”=Sanko HCA (CAS 35948-25-5)=9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxides (Sanko Co., Osaka, Japan)
        “5076”=Dodecylbenzenesulfonic acid, Nacure® 5076 (King Industries)
        “T-Ac”=Mercaptoacetic acid
        “M-Ac”=Methoxyacetic acid
    
    


“blocked” sulfonic acid derivatives

    
    
        “5414”=Nacure® 5414: polymer-blocked dodecylbenzenesulfonic acid (King Industries, Inc.); ppm amounts based on solids fraction
        “1419”=Nacure® 1419=blocked dinonylnaphthalenesulfonic acid, 30% in xylene/methyl isobutyl ketone) (King Industries, Inc.); ppm amounts based on solids fraction
        “194”=Nacure® XC-194=latently blocked alkylarylsulfonic acid, 20% in solvent mixture of hydrocarbons (King Industries, Inc.); ppm amounts based on solids fraction
    
    


Water was added to the solvents in order to produce more rapid flocculation than with the amounts of water present in commercial solvents. The total amounts were 400-800 ppm of total water based on solvents. The higher the water concentration, the quicker, normally, the flocculation. With relatively small amounts of water that are customary in practice, flocculation takes place after longer time periods. The water content in the experiments below is based on the solvents. It was determined by Karl-Fischer titration.
Flocculation measurement: for determining the flocculation, typically 30% or 40% strength solutions of polyisocyanate in solvents or solvent mixtures were prepared. Additives were introduced via the solvents. 50 g of the mixture in 50 ml screw-top lid vessels without writing on the side were blanketed with nitrogen and stored firmly sealed at 23° C. (50% atmospheric humidity). The vessels were inspected typically daily in the first two weeks, excluding the weekends, and thereafter weekly, and at two-week intervals from 10 weeks onwards, against a dark background.
Flocculation Scoring:

    0 last day of measurement before flocculation, or no flocculation throughout the experiment;
    1a the first day of measurement with very slight hazing or fine sediment barely visible to the naked eye
    1b the last day of measurement with very slight hazing or fine sediment barely visible to the naked eye
    2 the first day of measurement with clearly perceptible sediment or flocking
    3 initial gelling
    X no further measurement


The examples which follow are intended to illustrate the invention, but not to confine it to these examples.
The experimental series show that in the inventive examples, longer storage times without flocculation or with lower flocculation are obtained than with the reference examples without additives and with noninventive additives.
It is shown by way of example, moreover, that this effect is obtained in different typical coatings solvents such as n-butyl acetate (BuAc), xylene/butyl acetate=3:1, xylene, methoxypropyl acetate MPA, Solvesso® 100, albeit to different extents.
Moreover, the effect has been shown by way of example in concentrations of 30% and 40% polyisocyanate in solvents, which is typical for coatings, but already corresponds to relatively severe dilution.
Experimental Series 1
Storage of PI-1 Isocyanurate 40% in N-Butyl Acetate with a Water Content of about 800 ppm and Different Additives with Flocculation/Precipitation in Days Over 126 Days













Flocculation


















Comp.
Comp.
Comp.
Comp.
Comp.
Inv.
Inv.
Inv.
Inv.
Inv.






















Additive
none
Tppt
1135
TI
TI
126
9228
EPQ
OPH
1135
EPQ


Amount
0
600
600
600
2000
600
600
200
600
200
600


(ppm)


















0
(d)
13
2
13
13
14
14
126
 98
42
42


1a
(d)
14
7
14
14
21
21
X
112
56
56


1b
(d)
14
7
14
21
21
21
X
126
70
126


2
(d)
21
7
21
21
28
28
X
X
84
X









Experimental Series 2
Storage of PI-1 Isocyanurate 40% Strength in Xylene/N-Butyl Acetate=3:1 with a Water Content of  ̃800 ppm and Different Additives Over 126 Days













Flocculation














Comp.
Comp.
Inv.
Inv.
Inv.
Inv.



















Additive
none
Tppt
9228
EPQ
1135
EPQ
1135
OPH


Amount
0
600
600
600
 200
600
200
600


(ppm)














0
(d)
9
3
11
28
126
98


1a
(d)
10
8
14
42
X
112


1b
(d)
14
8
126
126
X
126


2
(d)
21
8
X
X
X
X









Experimental Series 3
Storage of PI-1 Isocyanurate 40% in Xylene with a Water Content of  ̃400 ppm (Saturated Solution) and Different Additives Over 210 Days



















Comp.
Comp.
Inv.
Inv.
Inv.
Inv.
Inv.

























Additive
None
Tppt
9228
EPQ
126
1135
EPQ
1135
OPH


Amount
0
600
600
600
600
 200
600
 200
600


(ppm)















0
(d)
42
0
98
 98
210
210
210


1a
(d)
56
5
112
112
X
X
X


1b
(d)
98
5
112
140
X
X
X


2
(d)
112
5
112
X
X
X
X









Experimental Series 4
Storage of PI-1 Isocyanurate 40% in Solvesso® 100 with a Water Content of  ̃400 ppm (Saturated Solution) and Different Additives Over 126 Days























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Inv.
Inv.
Inv.
Inv.



























Additive
None
Tppt
168
TI
TI
OF
OF
618
EPQ
126
OPH


Amount
0
600
600
600
2000
600
2000
600
200
600
600


(ppm)



















0
(d)
14
0
14
84
84
84
84
126
126
126
126


1a
(d)
21
5
21
98
98
98
98
X
X
X
X


1b
(d)
126
5
28
98
98
98
98
X
X
X
X


2
(d)
X
5
42
98
98
98
98
X
X
X
X









Experimental Series 5
Storage of PI-2 Isocyanurate 40% In Butyl Acetate with a Water Content of  ̃800 ppm and Different Additives Over 210 Days

















Comp.
Inv.
Inv.
Inv.
Inv.





















Additive
None
DOPO
126
OPH
5414


Amount
0
200
200
200
200


(ppm)


0 (d)
5
 6
 7
 5
210


1a (d)
6
  7*
 12*
  6*
X


1b (d)
12
 210*
 210*
 210*
X


2 (d)
13
X
X
X
X





*The sample showed a very slight hazing, which was no longer apparent after a storage time of around 12 weeks. It is assumed that these values lie in the marginal region of visual perception. No technical aids were employed.






Experimental Series 6
Storage of PI-3 Isocyanurate 30% in Butyl Acetate/Xylene=1:3 with a Water Content of 800 ppm and Different Additives Over 210 Days






















Comp.
Comp.
Comp.
Comp.
Comp.
Inv.
Inv.
Inv.
Inv.





Additive
None
DPP
Ac
MS
TFAc
2-CPS
3-CPS
3-CPS
DEHP


Amount
0
300
300
300
300
300
50
300
300


(ppm)


0 (d)
14
0
7
1
14
42
210
210
210


1a (d)
21
1
8
2
21
56
X
X
X


1b (d)
21
2
8
8
21
98
X
X
X


2 (d)
21
3
9
9
21
112
X
X
X






Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.





Additive
OPH
T-Ac
5076
5414
5414
1419
1419
194
194


Amount
300
300
300
50
300
50
300
50
300


(ppm)


0 (d)
210
210
210
210
210
28
98
210
210


1a (d)
X
X
X
X
X
42
112
X
X


1b (d)
X
X
X
X
X
182
210
X
X


2 (d)
X
X
X
X
X
196
X
X
X









Experimental Series 7
Storage of PI-3 Isocyanurate 30% in Butyl Acetate with a Water Content of 800 ppm and Different Additives Over 210 Days























Comp.
Comp.
Comp.
Comp.
Inv.
Inv.
Inv.
Inv.
Inv.




















Additive
none
DPP
Ac
MS
2-CPS
2-CPS
3-CPS
3-CPS
DEHP


Amount
0
300 
300 
300 
50
300
50
300 
300 


(ppm)

















0
(d)
8
1
11
1
28
42
28
28
14


1a
(d)
X
4
12
4
X
56
X
X
X


1b
(d)
X
4
12
4
X
70
X
X
X


2
(d)
X
4
13
4
X
182
X
X
X


3
(d)
11 
X
X
X
42
X
42
42
21




















Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.




















Additive
OPH
T-Ac
5076
5414 
5414
194
194
1419
1419 


Amount
300
300 
300
50
300
50
300
50
300


(ppm)

















0
(d)
210
21
98
28
210
210
112
21
126


1a
(d)
X
28
X
X
X
X
126
28
X


1b
(d)
X
28
X
X
X
X
210
28
X


2
(d)
X
28
X
X
X
X
X
28
X


3
(d)
X
X
112
42
X
X
X
X
140









Experimental Series 8
Storage of PI-4 Biuret 30% in Butyl Acetate with a Water Content of 800 ppm and Different Additives Over 210 Days

















Comp.
Inv.
Inv.





















Additive
None
OPH
126



Amount
0
300
300



(ppm)



0 (d)
8
112
98



1a (d)
11
126
X



1b (d)
12
182
X



2 (d)
13
196
X



3 (d)
X
X
182










Experimental Series 9
Storage of PI-5 Isocyanurate, 30% in Xylene/Butyl Acetate=3:1 with a Water Content of 600 ppm and Different Additives Over 210 Days






















Comp.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.
Inv.



















Additive
none
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
5076


Amount
 0
 20
 40
100
40
 40
 40
10


(ppm)


Additive




BHT
BHT


Amount




100
100


(ppm)


Additive





OPH
OPH


Amount





300
300


(ppm)
















0
(d)
13
154
210
154
210
 28
154
210


1a
(d)
14
168
X
168
X
 42
168
X


1b
(d)
14
210
X
210
X
210
210
X


2
(d)
21
X
X
X
X
X
X
X


3
(d)
X
X
X
X
X
X
X
X














Inv.
Inv.
Inv.
















Additive
5076
5076
5076 



Amount
20
50
20



(ppm)



Additive


BHT



Amount


100



(ppm)











0
(d)
112
210
210


1a
(d)
126
X
X


1b
(d)
210
X
X


2
(d)
X
X
X


3
(d)
X
X
X









Experimental Series 10
Storage of
a) PI-5 Basonat® HI 100/PI-6 Basonat® IT 270 S=70:30 solids/solids
b) PI-7 Basonat® HA 100
c) PI-8 Basonat® HA 300
30% (total solids) in Solvesso® 100 with a water content of 100 ppm and additive
















Comp.
Inv.
Comp.
Inv.






















Polyisocyanate
PI-7
PI-7
PI-8
PI-8



Additive
none
DEHP
none
DEHP



Amount
0
50
0
50



(ppm)



0 (d)
56
210
140
210



1a (d)
70
X
154
X



1b (d)
140
X
210
X



2 (d)
154
X
X
X



3 (d)
X
X
X
X










Experimental Series 11
Like Experimental Series 10, but in Butyl Acetate with a Water Content of 400 ppm and Additive
















Comp.
Inv.
Comp.
Inv.






















Polyisocyanate
PI-5/PI-6
PI-5/PI-6
PI-8
PI-8



Additive
none
DEHP
none
DEHP



Amount
0
50
0
50



(ppm)



0 (d)
56
182
126
168



1a (d)
70
196
140
182



1b (d)
70
210
210
210



2 (d)
84
X
X
X



3 (d)
X
X
X
X










Experimental Series 12
Like Experimental Series 10, but Xylene/Butyl Acetate Equals 3:1 with a Water Content of about 200 ppm and Additive













Polyisocyanate














Comp.
Inv.
Comp.
Inv.
Comp.
Inv.



PI-5/PI-6
PI-5/PI-6
PI-7
PI-7
PI-8
PI-8

















Additive
none
DEHP
none
DEHP
none
DEHP


Amount
 0
 50
 0
 50
 0
 50


(ppm)














0
(d)
56
182
42
182
70
210


1a
(d)
70
196
56
196
84
X


1b
(d)
70
210
70
210
210 
X


2
(d)
70
X
84
X
X
X


3
(d)
X
X
X
X
X
X

## Claims

1. A method for reducing flocculation and/or precipitation in a polyisocyanate mixture, the method comprising mixing the polyisocyanate mixture with an additive, wherein said mixing is carried out in the presence of water and a solvent, thereby reducing flocculation, precipitation, or both, of the polyisocyanate mixture, and
wherein the additive is selected from the group consisting of
a1) an organic acid having a pKa of below 4.2, selected from the group consisting of
a1a) an aromatic sulfonic acid, and
a1b) a singularly or doubly alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid having two carbon atoms, a singularly or doubly halogen-, alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid, an alkenedicarboxylic acid or an alkanedicarboxylic acid having at least three carbon atoms;

a2) a phosphite:





and
a4) an acidic phosphorus derivative selected from the group consisting of
a4a) a mono- and di-C1 to C12 alkyl phosphate,
a4c) a mono-C1 to C12 alkyl phosphinate, and
a4d) an alkyl derivative of a phosphorus-containing diacid, and

wherein:
a polyisocyanate of the polyisocyanate mixture comprises an isocyanurate, biuret, allophanate, or allophanate with urethane group,
the additive does not include a 2-chloroalkanecarboxylic acid or a 3-chloro alkanecarboxylic acid; and
R is optionally an aryl group which is substituted in positions 2, 4 and 6 as follows:
position 2: tert-butyl, or tert-amyl,
position 4: hydrogen, alkyl, tert-butyl, or tert-amyl, and
position 6: hydrogen, alkyl, tert-butyl, or tert-amyl,


with the proviso that at least one of substituents in positions 4 and 6 is not hydrogen.

2. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture is (cyclo)aliphatic.

3. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture is based on hexamethylene diisocyanate, isophorone diisocyanate, or both, as a monomer.

4. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture comprises an isocyanurate, biuret, or an allophanate group.

5. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture comprises an isocyanurate group, a urethane group, an allophanate group, or a mixture thereof, obtained in the presence of an ammonium carboxylate or an ammonium a-hydroxycarboxylate catalyst.

6. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture comprises an isocyanurate group obtained by thermal deactivation of a catalyst.

7. The method according to claim 1, wherein a polyisocyanate of the polyisocyanate mixture comprises an isocyanurate group obtained by thermal deactivation of a catalyst through addition of a deactivator.

8. The method according to claim 1, wherein a substoichiometric amount of the additive is added in relation to an amount of the water present in the polyisocyanate mixture.

9. The method according to claim 1, wherein the additive is selected from the group consisting of di(2-ethylhexyl) phosphate, dibutyl phosphate, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, a dioctylphosphonic ester, a di(2-ethylhexyl)phosphonic ester, a di-n-butylphosphonic ester, a diethylphosphonic ester, a dimethylphosphonic ester, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, and dodecylbenzenesulfonic acid.

10. The method according to claim 1, wherein a total amount of the water ranges from 100 to 800 ppm relative to an amount of the solvent.

11. The method according to claim 1, wherein a total amount of the water ranges from 400 to 800 ppm relative to an amount of the solvent.

12. The method according to claim 1, wherein the solvent is at least one selected from the group consisting of an aromatic hydrocarbon, a (cyclo)aliphatic hydrocarbon, a chlorinated hydrocarbon, a ketone, an ester, an alkoxylated alkyl alkanoate, and an ether.

13. The method according to claim 1, wherein the solvent is at least one selected from the group consisting of n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, 2-methoxyethyl acetate, and an aromatic hydrocarbon.

14. The method according to claim 1, wherein the polyisocyanate mixture further comprises at least one phenyl or bridged bisphenol which has one phenolic hydroxyl group on an aromatic ring of the at least one phenyl or bridged bisphenol and has alkyl groups in positions ortho to the phenolic hydroxyl group.

15. The method according to claim 14, wherein the polyisocyanate mixture further comprises a dialkyl phosphate, a dialkyl phosphonate, an aromatic sulfonic acid, or a mixture thereof.

16. The method according to claim 14, wherein the polyisocyanate mixture further comprises a Lewis acid.

17. A method for stabilizing a polyisocyanate or a polyisocyanate mixture in a solvent against flocculation during storage, the method comprising mixing, in the presence of water and a solvent, the polyisocyanate or the polyisocyanate mixture with at least one additive selected from the group consisting of
a1) an organic acid having a pKa of below 4.2, selected from the group consisting of
a1a) an aromatic sulfonic acid, and
a1b) a singularly or doubly alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid having two carbon atoms, a singularly or doubly halogen-, alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid, an alkenedicarboxylic acid or an alkanedicarboxylic acid having at least three carbon atoms;

a2) a phosphite:





and
a4) an acidic phosphorus derivative selected from the group consisting of
a4a) a mono- and di-C1 to C12 alkyl phosphate,
a4c) a mono-C1 to C12 alkyl phosphinate, and
a4d) an alkyl derivative of a phosphorus-containing diacid,

wherein:
the polyisocyanate mixture comprises at least one selected from the group consisting of a Lewis acid as a catalyst, an antioxidant, and a coating additive;
the additive does not include a 2-chloroalkanecarboxylic acid or a 3-chloro alkanecarboxylic acid; and
R is optionally an aryl group which is substituted in positions 2, 4 and 6 as follows:
position 2: tert-butyl, or tert-amyl,
position 4: hydrogen, alkyl, tert-butyl, or tert-amyl, and
position 6: hydrogen, alkyl, tert-butyl, or tert-amyl,


with the proviso that at least one of substituents in positions 4 and 6 is not hydrogen.

18. The method according to claim 17, wherein the polyisocyanate mixture comprises at least one selected from the group consisting of a Lewis acid as a catalyst and an antioxidant.

19. A method for coating a substrate with a polyisocyanate or a polyisocyanate mixture stabilized against flocculation during storage in a solvent in the presence of water, the method comprising:
mixing the polyisocyanate or the polyisocyanate mixture with at least one additive, thereby forming a first mixture,
mixing the first mixture with a solvent and optionally with at least one other additive, thereby forming a second mixture,
optionally storing the second mixture in the presence of the water,
mixing the second mixture with at least one binder-comprising component, thereby forming a third mixture, and
applying the third mixture to a substrate,
wherein the at least one additive is selected from the group consisting of
a1) an organic acid having a pKa of below 4.2, selected from the group consisting of
a1a) an aromatic sulfonic acid, and
a1b) a singularly or doubly alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid having two carbon atoms, a singularly or doubly halogen-, alkoxy-, mercapto- or alkylmercapto-substituted alkanecarboxylic acid, an alkenedicarboxylic acid or an alkanedicarboxylic acid having at least three carbon atoms;

a2) a phosphite:





and
a4) an acidic phosphorus derivative selected from the group consisting of
a4a) a mono- and di-C1 to C12 alkyl phosphate,
a4c) a mono-C1 to C12 alkyl phosphinate, and
a4d) an alkyl derivative of a phosphorus-containing diacid,

wherein:
the additive does not include a 2-chloroalkanecarboxylic acid or a 3-chloro alkanecarboxylic acid; and
R is optionally an aryl group which is substituted in positions 2, 4 and 6 as follows:
position 2: tert-butyl, or tert-amyl,
position 4: hydrogen, alkyl, tert-butyl, or tert-amyl, and
position 6: hydrogen, alkyl, tert-butyl, or tert-amyl,


with the proviso that at least one of substituents in positions 4 and 6 is not hydrogen.

20. The method according to claim 19, wherein the binder-comprising component comprises a compound selected from the group consisting of a polyacrylate polyol, a polyester polyol, a polyurethane polyol, a polycarbonate polyol, and a polyether polyol.

21. The method according to claim 19, wherein the substrate is a compound in a primer, a filler, a pigmented topcoat, a basecoat and a clearcoat in an automotive refinishing or large-vehicle finishing sector and for a utility vehicle in an agricultural or construction sector.