Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2000-07-28
2002-07-09
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...
C522S032000, C522S066000, C522S142000, C522S162000, C522S164000, C522S166000, C522S170000, C522S172000, C522S173000, C522S179000, C528S025000, C528S026000, C528S065000, C528S297000, C528S307000, C528S421000
Reexamination Certificate
active
06417243
ABSTRACT:
The present invention relates to novel monomers, oligomers and polymers carrying cycloaliphatic epoxy functional groups capable of being polymerized under irradiation and to coatings exhibiting, by comparison with cationically polymerizable systems known to date, an improved resistance to solvents which are obtained by cationic polymerization of compositions comprising the said monomers, oligomers and polymers carrying cycloaliphatic epoxy functional groups.
The coatings industry is continually on the lookout for materials exhibiting an improved resistance to chemical attacks and in particular to solvents, detergents, cleaners, pickling agents and other substances capable of attacking the surfaces and of modifying the essential qualities thereof of colour, of durability, of porosity, and the like. Furthermore, this same industry is also on the lookout for materials which, while possessing the improved resistance expressed above, are polymerizable in the form of a coating, as a thin or thick layer, while having recourse either to thermal curing or to one of the irradiation techniques, such as ultraviolet radiation or ionizing radiation, such as gamma rays, X-rays or an electron beam. This is because these techniques have acquired, in the industry, a well-established reputation for reliability and productivity by virtue of the high rates of polymerization which they make it possible to achieve and of the consistency of the coating characteristics thus obtained.
Coatings have already been obtained by polymerization of compositions comprising oligomers and polymers, in particular polyesters and polyethers, carrying cycloaliphatic epoxy functional groups. Thus, U.S. Pat. No. 3,968,135 discloses the catalytic promotion of the reaction of compounds comprising oxirane groups with organic carboxylic compounds by means of a chromium(III) tricarboxylate compound possessing available coordination sites in the presence of a solvent system comprising a neutral solvent and a coordinating solvent. This process is applied to the reaction either of a monoepoxy compound with a di- or polycarboxylic acid or of a diepoxide with a monoacid. In particular, this document discloses that the epoxide can be epoxidized dicyclohexenecarboxylate and that the polyfunctional acid can be a polyester or polyether comprising carboxyl endings. However, the molar ratio between the compounds to be reacted is such that all the acidic functional groups available lead to the immediate and complete crosslinking of the material obtained. Thus, the examples in this document more specifically describe triepoxide/diacid and triacid/diepoxide systems capable of crosslinking at 75° C. in only 15 minutes. These systems can be used, in the form of solutions or of emulsions, as coating compositions. No mention is made in this document of a cationic photoinitiator.
However, for a number of applicational niches, these polymers do not offer the complete compromise of desired properties. For these applications, moreover, it would be desired to have available compositions based on polyacrylates, on polyurethanes or on one or other of the monomers forming part of these polymers. Finally, for all these compositions starting from different base polymers, a satisfactory ability to polymerize under irradiation, in particular by the effect of ultraviolet radiation or of ionizing radiation, under current industrial conditions would be desired.
In order to solve the problems set out above, the present invention provides a novel category of monomers, oligomers and polymers chosen from those of general formula (I):
in which:
A
1
is chosen from polyester blocks having a molecular weight of between 250 and 10,000 approximately, polyurethane blocks having a molecular weight of between 500 and 5000 approximately, hydrocarbon-comprising backbones of a mono- or polycarboxylic acid and addition products of a polycarboxylic acid and of a cycloaliphatic diepoxide, the said addition products preferably being obtained by reaction of x mol of cycloaliphatic diepoxide with x+2 mol of dicarboxylic acid,
m is a number from 1 to 6,
R
1
is a cycloaliphatic group carrying a hydroxyl group situated in the &agr; position with respect to the oxygen atom to which R
1
is bonded which, if appropriate, carries substituent(s),
R
2
is a second cycloaliphatic group carrying an oxirane group situated at the chain end which, if appropriate, carries substituent(s), and
B is chosen from one or more covalent bonds, an oxygen atom and linear, branched or cyclic hydrocarbon-comprising radicals carrying, if appropriate, oxygen and/or silicon atoms,
and those of general formula (II):
in which:
A
2
is a block chosen from homopolymers and copolymers of at least one vinyl monomer,
n is an integer from 0 to 15 approximately, with the condition that n is at least equal to 1 when Y is sulphur, and
Y is chosen from a sulphur atom, —CR′R″ radicals, in which R′ and R″ are each an aliphatic group having from 1 to 4 carbon atoms, and their mixtures,
q is an integer or non-integer ranging from 1 to 2,
R
1
, B and R
2
are defined as in the above formula (I).
In order for the invention to be fully understood, each of the terms R
1
, R
2
, A
1
, A
2
and B will now be defined in more detail.
R
1
and R
2
are cycloaliphatic groups with a ring preferably having 5 to 6 members which can carry one or more substituents, preferably hydrocarbon-comprising substituents, which are preferably not very sterically hindered. Examples of such substituents comprise alkyl radicals having from 1 to 9 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl and n-nonyl. These cycloaliphatic groups R
1
and R
2
necessarily carry, in addition, one (R
1
) a hydroxyl group at the a position with respect to the oxygen atom to which R
1
is bonded and the other (R
2
) an oxirane group situated at the end of the cyclic chain.
The cycloaliphatic groups R
1
and R
2
are connected to one another by a component B which can be an oxygen atom or else one or more, preferably one or two, covalent bonds, for example as in the following formulae:
The component B can also consist of a linear, branched or cyclic hydrocarbon-comprising radical which can comprise one or more oxygen and/or silicon atoms in the carbon-comprising chain. Mention may be made, as examples of such B radicals, of:
—(CH
2
)
n
— alkylene groups in which n is an integer from 1 to 12 approximately,
a —CH═CH— group
a group of formula
a group of formula
a group of formula (X)
a group of formula (XI)
in which m is an integer from 0 to 20 approximately, preferably from 1 to 6,
a group of formula (XII)
in which R
3
is a cycloaliphatic radical, such as 1,4-cyclohexane, 1,3-cyclohexane, 1,2-cyclohexane and the like, it being possible for the said cyclic radical, if appropriate, to carry an oxirane group
a group of formula (XIII)
in which m
1
and m
2
are each an integer from 1 to 6 approximately and n
1
and n
2
are each an integer from 0 to 2
a group of formula (XIV)
in which p is an integer from 1 to 10 approximately, preferably from 1 to 3, and R
4
, R
5
, R
6
and R
7
are each chosen independently from alkyl radicals having from 1 to 4 carbon atoms, preferably the methyl radical,
a group of formula (XV)
in which p is an integer from 1 to 10 approximately, preferably from 1 to 3, R
4
, R
5
, R
7
, R
8
, R
9
and R
10
are each chosen independently from alkyl radicals having from 1 to 4 carbon atoms, preferably the methyl radical, R
6
is chosen from alkyl radicals having from 1 to 4 carbon atoms, preferably the methyl radical, and aryl radicals having from 6 to 9 carbon atoms, preferably the phenyl radical, and R
2
has the same meaning as in the above formula (I)
a group of formula (XVI)
in which R
4
, R
5
, R
6
and R
7
are each chosen independently from alkyl radicals having from 1 to 4 carbon atoms, preferably the methyl radical, p is an integer from 1 to 20 approximately, preferably from 1 to 6, and R
2
has the same meaning as in the above formula (I).
As indicated ab
Loutz Jean-Marie
Peeters Stephan
Verschueren Kris
Berman Susan W.
Finnegan Henderson Farabow Garrett & Dunner L.L.P.
UCB S.A.
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