Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1997-09-12
2001-10-23
Berman, Susan W. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S135000, C522S136000, C522S137000, C522S138000, C522S139000, C522S140000, C522S141000, C522S142000, C522S143000, C522S144000, C522S145000, C526S262000, C526S263000
Reexamination Certificate
active
06306923
ABSTRACT:
The present invention relates to ultraviolet or visible light polymerizable and/or crosslinkable coating compositions, comprising at least one compound (A) containing electron depleted olefinic double bonds and at least one compound (B) containing electron enriched olefinic double bonds.
Maleimides are monomers which are useful as compounds having electron depleted double bonds in radiation polymerizable coating compositions, which also comprise compounds having electron enriched double bonds. The maleimides are all the more interesting in this kind of composition as they allow, if in other respects the compounds having electron enriched double bonds are selected in a suitable manner, to do without any photoinitiator, as described in U.S. Pat. No. 5,446,073.
However, the synthesis of maleimides remains very difficult, which renders these compounds very expensive, and, consequently, which also renders the compositions containing them very expensive.
The maleimides which are currently available on the market (those of which the synthesis is the least expensive) are the maleimides N-substituted by aromatic groups. Such maleimides are hardly soluble, which prevents their use in certain cases. Moreover, the aromatic groups decrease the electron withdrawing character of the maleimides which include them and absorb a part of the ultraviolet light.
Furthermore, in general, the maleimides introduced as monomers may induce migration problems if they are not completely polymerized in the polymerized compositions.
With the objective of providing new maleimides which do not have all the above-mentioned disadvantages, we have now found a new class of compounds of type (A) which consist in prepolymers functionalized by maleimide groups, and which offer many possibilities to satisfy the requirements of the applications such as the coating of optical fibers, the coating of substrates such as wood, paper, metal, plastics, and glass, which require properties of adherence, hardness, flexibility, elasticity, abrasion strength, solvent strength, and weather resistance, thanks to the great adaptability and to the versatility of the synthesis process, which gives access to a very wide range of compounds and which allows to modulate the nature and the structure of the polymer chains according to the desired properties. Besides, this new class of compounds (A) includes aliphatic maleimides, the preparation of which was hitherto difficult, and which are particularly interesting in radiation polymerizable coating compositions, involving both compounds having electron-depleted double bonds and compounds having electron-enriched double bonds. So, it has been found, in a surprising manner, that the reactivity of a formulation, the compound (A) of which is a prepolymer functionalized by maleimide groups as defined hereinbelow, is up to 10 times more efficient than that of an equivalent formulation, the compound (A) of which is a prepolymer similar to the previous one but not functionalized by maleimide groups, and up to 6 times more efficient than the same prepolymer non maleimide-functionalized in mixture with a maleimide monomer available on the market.
In other words, a coating made with the new formulation leads to a tack-free film within a period up to 10 times shorter than with these reference formulations.
The subject of the present invention is thus polymerizable and/or crosslinkable compositions such as defined above, characterized by the fact that said at least one compound (A) is selected among the prepolymers having maleimide functions (f):
wherein each of R
1
and R
2
represents independently H, a C
1
-C
12
alkyl group or a halogen,
and consisting in the reaction products:
of at least one maleic anhydride represented by formula (I):
wherein R
1
and R
2
are such as defined above;
of at least one compound (II) having at least one —NH
2
function and at least another function F selected from the group consisting of —OH, —NH
2
, —NH—, —COOH, —C—O—R
3
R
3
representing a C
1
-C
5
alkyl group;
of at least one compound (III) capable of forming the chain of the prepolymers by polycondensation and/or polyaddition,
said compound(s) (II) having first reacted with said maleic anhydride(s) (I) in order to open the maleic anhydride rings with formation of maleamic acid functions (f′):
said maleamic acid functions having then been at least partially closed again under the action of heat into maleimides N-substituted by groups functionalized by a function F,
the chain of said prepolymers having been formed by polycondensation and/or polyaddition:
of the N-substituted maleimide formed bearing the function F;
of compound(s) (III)
of uncyclized products bearing or not a function F formed simultaneously with said N-substituted maleimides;
of maleic anhydride(s) (I) which could have remained in excess after their opening by compound(s) (II);
the functionalities of compound(s) (III) being selected in order to allow the constitution of the chain with the grafting of said N-substituted maleimides on the chain directly by their function F when the latter is at least one selected among —OH, —NH
2
, —NH— and —COOH, or after transesterification of the functions F when the latter are —COOR
3
or —OCOR
3
in order to allow the condensation or the addition of said N-substituted maleimide on the chain, the functionalities and proportions of compounds (II) and (III) having been selected in order to exclude any gelation of the reaction medium.
In the prepolymer (A), in general the compound(s) (II) has (have) reacted with anhydride(s) (I) under stoichiometric or substantially stoichiometric conditions or in excess of the anhydride(s) (I) with respect to compound(s) (II).
Preferably, the anhydride of formula (I) is maleic anhydride.
The compounds (II) are especially selected among the compounds represented by the formulae H
2
N—A—OH, H
2
N—A—
represents a straight, branched or cyclic alkylene group, or an arylene group, it being possible for said groups to be interrupted by oxygen or sulfur atoms, or by —NR
4
—groups, wherein R
4
represents hydrogen or alkyl.
As examples of these compounds (II),
aminoalcohols, such as ethanolamine, propanolamine, isopropanolamine, 2-(2-aminoethoxy) ethanol, N-(2-amino-ethyl)ethanolamine;
aminoacids, such as valine, p-amino-benzoic acid, alanine, 2-aminohexanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 2-aminoisobutyric acid;
the methyl or ethyl esters of the abovementioned aminoacids;
the esters of carboxylic acids having 2 to 5 carbon atoms, such as acetic acid, with the abovementioned aminoalcohols;
diamines, such as ethylenediamine, 2-methyl-1,5-pentamethylenediamine, hexamethylenediamine, 2,2,4-and/or 2,4,4-trimethylhexamethylenediamine, dodecamethylenediamine, 5-methylnonamethylenediamine, decamethylenediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, bis(3-methyl-4-amino-5-ethylcyclohexyl)methane, 1,2-bis(4-aminocyclohexyl)-ethane, 2,2′-bis(4-aminocyclohexyl)propane, 2,2′-bis(3-methyl-4-aminocyclohexyl)propane, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxa-tridecane-1,13-diamine; and
polyoxyethylenated and/or polyoxypropylenated di- or triamines sold under the tradename “Jeffamine®”, can be cited.
Trifunctional compounds (II) such as L-serine, 3-hydroxy 4-amino benzoic acid and 3-amino 4-hydroxy benzoic acid and other triamines such as N-(2-aminoethyl)-1,2-ethanediamine and N-(3-aminopropyl)-1,3-propanediamine, can also be cited.
When the N-substituted maleimide has a function F which is —OH, —NH
2
or —NH—, the compounds (III) are especially:
at least one polyacid and/or at least one cyclic anhydride; and
at least one compound selected among a polyol, a mono- or polyfunctional epoxy, a polyamine and a polyisocyanate; or
at least one polyisocyanate; and
possibly at least one compound selected among a polyol, a mono- or polyfunctional epoxy, a polyacid and/or a cyclic anhydride and a polyamine.
When the N-substituted maleimide has a function F which is —COOH, the compound
Strub Henri
Thepot Phillippe
Berman Susan W.
Cozen and O'Connor
Fein Michael B.
Sartomer Company, Inc.
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