AU770966B2 - Isocyanate composition containing a masked and an unmasked isocyanate and their use for coating - Google Patents

Abstract

The invention concerns an isocyanate composition useful for applying powder paints. Said composition is characterised in that it contains a masked isocyanate compound and an unmasked cycloaliphatic isocyanate compound. The invention is applicable in the chemistry of paints.

Description

ISOCYANATE COMPOSITION CONTAINING A MASKED AND AN UNMASKED ISOCYANATE AND THEIR USE FOR COATING A subject matter of the present invention is a novel family of isocyanate compositions comprising both masked isocyanates and nonmasked isocyanates. It relates more particularly to isocyanate compositions for the purpose of their use in the powder form, including in the form of a mixture of powders, more specifically for forming paint powders referred to as single-component powders (sometimes denoted by the name "one shot").

For reasons related to environmental protection and work safety, attempts are increasingly being made to eliminate the use of solvents in coating techniques and in particular in painting techniques. More particularly, the reduction in V.O.C.s (volatile organic compounds) is an increasingly current preoccupation in the paint and varnish industry.

With this aim, the change in products towards higher solid contents makes it possible to reduce the amounts of solvents needed to achieve the applicational viscosity and thus to reduce the solvents evaporated during the drying of the paint film.

An alternative to this technique is the use of aqueousphase products where water has replaced organic solvents as agent for conveying the organic binder. However, an amount of organic solvent, admittedly a low amount, remains necessary for the processing and for the formation of the paint film.

Furthermore, they generate water-soluble residues, the treatment of which can be problematic and expensive.

In this context, techniques for coating by means of powder have been increasingly developed. It is advisable here to briefly describe this technique in order to get a better understanding of the present invention.

The technique employs a very fine pulverulent material for which air will act as carrier.

Generally, an electrostatic charge of several kilovolts applied between a spray gun and the item to be painted will make it possible to attract and to retain the precursor powder of the coating, which powder will be sprayed out by the applicational spray gun.

Once' covered with powder, the item is subjected to baking, generally at a temperature of between 150 and 200 0 C, which baking will make possible the melting, the spreading and then the crosslinking of the paint powder in order to obtain a uniform homogeneous layer of the coating. Here and in the continuation of the description, paint will be regarded as the paradigm of the coatings.

This technique is nonpolluting and exhibits an applicational yield in the vicinity of 100% by virtue of the possibility of recycling the unused powder. For further details on powder paint techniques, reference may be made to the following works: P. Grandou and P. Pastour: Peintures and Vernis [Paints and Varnishes] I. Constituents II. Technique and industries; published by Hermann; R. Lambourne: Paints and Surface Coatings, Theory and practice; published by Halsted Press; Powder Coating, The Complete Finisher Handbook; The Powder Coating Institute; Myers and Long; Treatise on Coatings, 5 volumes; published by Marcel Dekker.

Mention should be made, among the families of products which can be employed in the field of powders, of the following. Most of the market is taken up by epoxy-polyester powder dyes referred to as "hybrid" epoxy-polyester powder dyes, followed by polyesters, polyurethanes and then powders referred to as "epoxy" powders. If high quality exterior behavior (in particular with respect to actinic and atmospheric attacks) is desired, it is then advisable to use coatings based on TGIC-polyesters or else on polyurethanes, which alone make it possible to achieve the performances usually required.

However, the TGIC-polyester system is supposed to be toxic and regulatory restrictions are about to very considerably restrict their use.

As regards polyurethanes, the only powder products currently on the market are products which result from a system in which the crosslinking agent is an isocyanate masked by caprolactam of a very specific type, namely IPDI derivatives.

However, the use as crosslinking or curing agent of IPDI derivatives does not always result in products of good mechanical property. In a prior patent application (EP 680 984), the Applicant Company discloses a system with a blocking agent which makes it possible to significantly widen the family of aliphatic isocyanates which are capable of giving solid products with a sufficient Tg (glass transition temperature) to make possible.use in powder applications.

This technique has led, with the collaboration of the Catalan company Resisa (now Cray Valley Ib6rica), to a matt or satin painting system with a particularly outstanding performance (see the International Patent Application published under No. WO 98/04 608).

However, in order to have a sufficient glass transition temperature, the products disclosed in European Patent Application No. EP A 0 680 984 must meet fairly strict restrictions relating to residual isocyanate functional group content.

In addition, the products disclosed in the abovementioned European Application only represent a small fraction of the masking agents which can be used and which it would be pleasant to be able to employ in the powder paint technique. There is consequently a search for techniques which make it possible to increase the glass transition temperature of the crosslinking agents, sometimes also known as curing agents.

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

According to a first aspect of the present invention there is provided an isocyanate composition for use in powder paint applications, comprising a masked isocyanate compound and a nonmasked cycloaliphatic isocyanate compound and wherein said masked isocyanate compound exhibits an aliphatic backbone which comprises, in its backbone, at least one di- or polymethylene linkage linkage (that is to say (CH 2 )n where 1 represents an integer from 2 to 22/01/04 10:53 BSW SYDNEY 62937999#724 N0.379 P02 According to a second aspect of the present invention there is provided the use of cycloaliphatic compounds with a glass transition temperature (Tg) at least equal to for raising the glass transition temperature (Tg) of masked aliphatic isocyanate.

In a preferred embodiment of the present invention provides isocyanate mixtures with a Tg at least equal to 0 C (advantageously two significant figures), preferably to 25"C and more preferably to 10 In another preferred embodiment of the present invention provides isocyanate compositions capable of exhibiting high free isocyanate contents which can be used in powder paints.

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COMS ID No: SMBI-00582472 Received by IP Australia: Time 10:56 Date 2004-01-22 The invention is particularly advantageous in the case of masked isocyanates with an aliphatic nature. In the present description, any isocyanate functional group in which the nitrogen atom is connected to a carbon atom with sp 3 hybridization is regarded as aliphatic.

According to the present invention, the masked isocyanate, pure or as a mixture, results from a polyisocyanate, that is to say having at least two isocyanate functional groups, advantageously more than two (possibility of a fractional value since it is generally a more or less condensed mixture of oligomers), which itself generally results from a precondensation or from a prepolymerization of unit diisocyanates (sometimes these unit diisocyanates are denoted in the present description by the term "monomers").

These prepolymers and these precondensates are well known to a person skilled in the art and it may be indicated that, generally, the average molecular mass (Mw) of these prepolymers or these precondensates is low and is generally at most equal to 2000 (one significant figure), more commonly to 1 000 (one significant figure, preferably two). Thus, mention may be made, among the polyisocyanates used to synthesize the masked isocyanates according to the invention, of those of the biuret type and those which, by their dior trimerization reaction, have resulted in 5- or 6-membered rings. Mention may be made, among 6 rings, of the isocyanuric rings resulting from a homo- or from a heterotrimerization of various diisocyanates, alone, with other isocyanates or with carbon dioxide gas; in this case, a nitrogen of the isocyanuric ring is replaced by an oxygen. Oligomers with an isocyanuric ring are preferred. The preferred polyisocyanates are those which exhibit at least one aliphatic isocyanate functional group, advantageously two, preferably all.

Among the masked isocyanate functional groups according to the invention, those which are connected to the backbone via an aliphatic carbon (that is to say of sp 3 type) carrying one hydrogen atom, advantageously two, are preferred.

It is also desirable for the said carbon of sp 3 type to be itself carried by a carbon of sp 3 type, itself also carrying one or preferably two hydrogen atoms, in order to avoid the isocyanate functional group under consideration being in the neopentyl position.

In other words, it is advisable to choose, as monomers (which generally carry two isocyanate functional groups), at least one compound which carries at least one aliphatic functional group which is neither secondary nor tertiary nor neopentyl.

The problem of the masked isocyanates exhibiting a particularly low glass transition temperature is particularly acute in the case where use is made of monomers which exhibit a high conformational freedom and high rotational freedoms.

This is the case with the monomers which exhibit polymethylene (CH 2 linkages, were n represents an integer from 2 to 10, advantageously from 4 to 8.

These polymethylene linkages result in excellent mechanical properties. In addition, it is desirable for at least one, preferably all, [lacuna] these linkages to be free to rotate and thus exocyclic.

In the case of a mixture obtained from several (in general two) types of monomers, it is preferable for that or those of the monomers which corresponds to the above conditions and in particular to the condition with regard to the presence of polymethylene (CH2)7 linkages to represent at least one third, advantageously half, preferably two thirds of the masked isocyanate functional groups.

Of course, the results are particularly good when all of the monomer used exhibits this characteristic of having polymethylene linkages.

The above restrictions are applicable both in the case of prepolymers or of precondensates obtained from a mixture of monomers and of prepolymers and of precondensates obtained by simple mixing of prepolymers and of precondensates.

The present invention is particularly advantageous for masked isocyanates with a Tg at most equal to 40 0 C, advantageously at most equal to 300C, preferably at most equal to 200C, more preferably of less than 200C.

Thus, the present invention is particularly advantageous for masked isocyanates which do not exhibit masked isocyanate functional groups which are carried by an endocyclic cycloaliphatic carbon. This is because these masked isocyanates often naturally exhibit glass transition temperatures which are greater than those of masked non-cycloaliphatic isocyanates, in particular resulting from polymethylene diisocyanate.

Thus, the invention exhibits numerous advantages for polymethylene diisocyanate derivatives, among which may be mentioned hexamethylene diisocyanate, tetramethylene diisocyanate and a hexamethylene diisocyanate isomer, namely pentamethylene diisocyanate substituted by a methyl.

The masked isocyanates result from free isocyanates by reaction with various masking agents.

The masking agents which are particularly suitable for the present invention are those which, in the octanol test, exhibit a release temperature at least equal to 100°C, advantageously to 110 0

C,

preferably to 1200C. The release temperature is advantageously at most equal to 2000C, preferably 180 0

C.

The masked isocyanates according to the present invention can be masked by several masking agents. Mention should be made, among masking agents, of triazole, its derivatives and the various compounds mentioned in the patents cited in the present application.

The nonmasked isocyanates according to the present invention exhibit an aliphatic ring. It is also desirable for them to be chosen from compounds with a glass transition temperature at least equal to approximately 400C.

The compounds which are particularly well suited are the oligomers or the oligocondensates of cycloaliphatic monomers, that is to say the backbone of which comprises an aliphatic ring. Among these products, those which are preferred are those which result from the homo- or from the heterotrimerization of a cycloaliphatic monomer.

These monomers are advantageously such that at least one, advantageously both, [lacuna] isocyanate functional groups are distant from the closest ring by at most one carbon and preferably is connected directly to it. In addition, these cycloaliphatic monomers advantageously exhibit at least one, preferably two, isocyanate functional groups chosen from secondary, tertiary or neopentyl isocyanate functional groups.

The best results are obtained when the conformational freedom of the cycloaliphatic monomer is low. Mention may be made, as monomers capable of giving good results, of, by way of example and even of paradigm, the following monomers: the compounds corresponding to the hydrogenation of the aromatic nucleus or nuclei carrying isocyanate functional groups of aromatic isocyanate monomer and in particular of TDI (toluene diisocyanate) and of diisocyanatobiphenyls, the compound known under the abbreviation H 12 MDI and the various BICs [Bis(isocyanatomethylcyclohexane)]; and in particular norbornane diisocyanate, often known by the abbreviation NBDI; isophorone diisocyanate or IPDI or 3isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.

In order to obtain an effect on the increase in glass transition temperature of the composition, it is preferable for the (FI/MI) ratio by mass of the free isocyanate compound(s) to the masked isocyanate compound(s) to be at least equal to 0.1, advantageously to 0.2, preferably to 0.3.

On the other hand, in order to maintain the qualities related to the masked isocyanates (in part at least noncyclic isocyanates), it is preferable for the (FIF/MIF) ratio in equivalents of the free isocyanate functional groups to the masked isocyanate functional groups to be at most equal to approximately 1, advantageously to 1.0, preferably to 0.7.

The compositions according to the present invention can easily be prepared by mixing the free isocyanate in the molten masked isocyanate (see the procedure in the examples), advantageously at a temperature of less than that of the deblocking.

The presence of a catalyst for condensation between the masking agents and the isocyanates is not harmful in any way. This is particularly true for tertiary amines (in a ratio of 0.1 to 5% in molar equivalents with respect to the combined masked and nonmasked isocyanate functional groups), which are often used as catalyst.

The present application is also targeted at the use, according to the techniques specified above, of the cycloaliphatic compound with a glass transition temperature at least equal to 400C for raising the glass transition temperature of masked aliphatic isocyanates.

OCTANOL TEST Definitions "Release" (or "deblocking") This is the lowest temperature: temperature at which the masking agent of the Shelf life: masked isocyanate is 9/10 (mathematically roundedoff) displaced by a primary monoalcohol (the primary alcohol is generally octanol).

In order to ensure a good shelf life, it is preferable to choose masked isocyanate functional groups for which the octanol test shows a "release" at 0 C, advantageously at 900C, at most equal to The reaction is considered to be complete if it is carried out to more than Progress of the reaction:

PROCEDURE

Approximately 5 mmol of protected masked NCO equivalent to be evaluated are charged to a Schott-type tube with magnetic stirring.

to 3 ml of 1,2-dichlorobenzene (solvent) [lacuna] the equivalent of 1-octanol (5 mmol, i.e.

0.61 g, and optionally with the catalyst to be tested with the masking group) are added.

The reaction medium is subsequently brought to the test temperature. Heating is then carried out for 6 h at the test temperature, so as to deblock and thus render reactive the isocyanate functional groups.

On completion of the reaction, the solvent is removed by vacuum distillation and the residue is analyzed by NMR, mass and infrared [lacuna].

The percentage of masked isocyanate functional groups condensed with the 1-octanol is evaluated from these data.

The following nonlimiting examples illustrate the invention.

Examples of powder syntheses with free NCO

IPDT.

Example 1 Synthesis of a powder polyisocyanate composition (triazole-blocked HDT/IPDT (70/30 weight/weight)) 290 g of hexamethylene diisocyanate trimer (Tolonate HDT) (NCO content: 0.521 equivalent/100 g), 107.5 g of 1,2,4-triazole and 3.98 g of triethylamine by mass with respect to all the compounds/2.6 molar% with respect to the free NCO functional groups of the HDT) are successively added to a stirred jacketed reactor. The reaction medium is heated to 0 C. The reaction is exothermic and the temperature of the reaction medium rises to 125 0 C. The temperature gently falls back to 950C. After 1 h 30, infrared analysis of a withdrawn sample shows that all the isocyanate functional groups are blocked by the triazole. 170.5 g of isophorone diisocyanate trimer (IPDT) (NCO content: 0.45 equivalent/100 g) are then added at 110 0 C. After mixing for a quarter of an hour, the product is cast and then milled to give 568 g of a white powder with a Tg of 34 0 C which is stable on storage.

The composition thus comprises an HDT polyisocyanate with isocyanate functional groups which are masked by a single blocking agent and a cycloaliphatic polyisocyanate with free isocyanate functional groups.

Example 2 Synthesis of a powder polyisocyanate composition (HDT blocked with triazole/para-hydroxybenzoic acid (80/20 mol/mol)/IPDT (70/30 weight/weight)) (TOL 6598) 201.84 g of Tolonate HDT, 58.11 g of 1,2,4triazole and 33.41 g of para-hydroxybenzoic acid are successively added to a stirred 500 ml jacketed reactor. The reaction mixture is heated to 90 0 C. After reacting for one hour, 2.93 g of triethylamine are added. After 1 h 30, infrared analysis of a withdrawn sample shows that all the isocyanate functional groups are blocked by the triazole. 125.73 g of isophorone diisocyanate trimer are then added at 110 0 C. After mixing for 1 h, the product is cast and then milled to give 420 g of a white powder with a Tg of 450C (i.e.

200C more than the product to which IPDT has not been added) which is stable on storage.

The composition thus comprises an HDT polyisocyanate with isocyanate functional groups masked by a system of blocking agents, one of which comprises a carboxylic acid functional group, and a cycloaliphatic polyisocyanate with free isocyanate functional groups.

The absorption spectra show NCO, amide and anhydride functional groups.

Everything happens as if the masked isocyanate protected or stabilized the nonmasked isocyanate.

Example 3 (comparative) Triazole-masked HDT The following are successively charged to a 250 ml reactor 107.5 g of hexamethylene diisocyanate isocyanurate trimer known under the trade name HDT, the content of isocyanate (NCO) functional groups of which is 0.526 mol of NCO functional groups per 100 g of product, 22/01/04 10:53 BSW SYDNEY 4 62037999724 N0.379 P03 -18 39.3 g of 1,2,4-triazole (with a purity equal to 99.5%).

The reaction mixture is subsequently heated to a temperature of 1300C and stirred. After reacting for 1 h, infrared analysis of a sample of the reaction mass shows that the reaction for the masking of the isocyanate functional groups is complete. The disappearance of the band signifying the isocyanate functional groups at 2272 &2 cm 1 is observed.

The product is then poured onto a plate and then left to cool. The product is subsequently milled at a 0@@Otemperature of -100C.

At ambient temperature, the milled product behaves like an instant adhesive (sticky like pitch) and does not give a powder which can be handled under conventional industrial conditions, in particular at ambient temperature (approximately 20 0

C).

The measured Tg of the product is unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited too.

COMS ID No: SMBI-00582472 Received by IP Australia: Time 10:56 Date 2004-01-22

Claims (4)

19- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:- 1. An isocyanate composition for use in powder paint applications, comprising a masked isocyanate compound and a nonmasked cycloaliphatic isocyanate compound and wherein said masked isocyanate compound exhibits an aliphatic backbone which comprises, in its backbone, at least one di- or polymethylene linkage linkage (that is to say (CH 2 )n where n represents an integer from 2 to 2. A composition as claimed in claim 1, wherein said masked isocyanate compound is at least partially aliphatic. 3. A composition according to claim 1 or claim 2 wherein said masked isocyanate compound exhibits an aliphatic backbone, which comprises, in its backbone at least one di-or polymethylene linkage which is free to rotate. 4. A composition as claimed in any one of claims 1 to 3, wherein said masked isocyanate compound does not exhibit masked isocyanate functional groups which are carried by an endocyclic cycloaliphatic carbon. A composition as claimed in any one of the preceding claims, wherein said masked isocyanate compound results from a polymethylene diisocyanate monomer, from one of the (co)oligomers of the latter or from one of its (co)oligocondensates having an average molecular mass at most equal to 2000. 6. A composition as claimed in claim 5, wherein said polymethylene diisocyanate monomer is tetra-, penta- or hexamethylene diisocyanate, substituted at the most once. 7. A composition as claimed in any one of the preceding claims, wherein said (co)oligomer or (co)oligocondensate having an average molecular mass at most equal to 2000 comprises one or more uretinedione, imidazolinedione, isocyanuric, biuret, allophanate or polyol carbamate functional groups. 8. A composition as claimed in any one of the preceding claims, wherein said nonmasked cycloaliphatic isocyanate exhibits a Tg at least equal to approximately 40 0 C. 9. A composition as claimed in any one of the preceding claims, wherein said cycloaliphatic isocyanate is an oligomer of a cycloaliphatic monomer having an average molecular mass at most equal to 2000. A composition as claimed in any one of the preceding claims, wherein said cycloaliphatic isocyanate results from the homo- or from the heterotrimerization of a cycloaliphatic monomer. 20/01/04 12:47 BSW SYDNEY 0262837999tt6a5 NO.340 004 11. A composition as claimed in any one of the preceding claims, wherein at least one, advantageously two, isocyanate functional group(s) is/are distant from the closer ring by at most one carbon and is/arc preferably connected directly to it. 12. A composition as claimed in any one of the preceding claims, wherein said Snonmasked isocyanate compound exhibits at least one, advantageously two, isocyanate functional group(s) chosen from secondary, tertiary or neopentyl isocyanate function groups. 13. A composition as claimed in any one of the preceding claims, wherein the (FI/MI) ratio by mass of the free isocyanate compound to the masked isocyanate compound is at least equal to 0.1. 14. A composition as claimed in any one of the preceding claims, wherein the (FI/MI) ratio by mass of the free isocyanate compound to the masked isocyanate .compound is at least equal to 0.2. 15. A composition as claimed in any one of the preceding claims, wherein the I 15 (FI/MI) ratio by mass of the free isocyanate compound to the masked isocyanate compound is at least equal to 0,3. 16. A composition as claimed in any one of the preceding claims, wherein the ratio (in equivalents) of the free isocyanate functional groups to the masked isocyanate functional groups is at most equal to approximately 1. o o 20 17. A composition as claimed in any one of the preceding claims, wherein the ratio *se (in equivalents) of the free isocyanate functional groups to the masked isocyanate 9.9.99 S* functional groups is at most equal to approximately 9*99 18. A composition as claimed in any one of the preceding claims, wherein the ratio 9*e9 (in equivalents) of the free isocyanate functional groups to the masked isocyanate 25 functional groups is at most equal to approximately 0.7. 19. A process for the preparation of a composition as claimed in any one of the preceding claims, wherein the free isocyanate is mixed in the molten masked isocyanate. The use of cycloaliphatic compounds with a glass transition temperature (Tg) at least equal to 40 0 C for raising the glass transition temperature (Tg) of masked aliphatic isocyanate in accordance with any one of claims 1-18.

21. The use of a composition as claimed in any one of the claims 1 to 18 or prepared by the process of claim 19 as ingredient of a coating, advantageously in the powder form. COMS ID No: SMBI-00578516 Received by IP Australia: Time 12:51 Date 2004-01-20 -21

22. An isocyanate composition substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples but excluding the comparative example.

23. The use of cycloaliphatic compounds substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples but excluding the comparative example. DATED this 1 5 th day of January 2004 BALDWIN SHELSTON WATERS Attorneys for: RHODIA SERVICES