Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2000-08-11
2001-07-31
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...
C522S146000, C522S170000, C528S087000, C528S418000, C528S419000, C528S421000
Reexamination Certificate
active
06268403
ABSTRACT:
TECHNICAL FIELD
The present invention relates to photopolymerizible compositions containing epoxyalcohol monomers.
BACKGROUND OF THE INVENTION
UV- and radiation-curable systems have become commercially important in traditional applications such as coatings, inks, adhesives and composites due to public concern about the effect of organic vapor emissions on the environment. Such systems typically produce very low emissions, because solvents are not required in formulations and because polymerizations proceed to high conversions. Epoxy monomers are the materials of choice in many UV- and radiation- curable applications because of their excellent chemical resistance and excellent mechanical properties. Cycloaliphatic epoxy monomers undergo the most rapid curing of any type of epoxy monomer. However, the cure speed of even these monomers is insufficient for many high speed production processes. There is, therefore, a need to develop new epoxy monomers which can cure at higher rates.
SUMMARY OF THE INVENTION
It has been found surprisingly that cycloaliphatic epoxyalcohol monomers that bear both hydroxy and epoxy groups have UV and radiation cure rates which exceed those of analogous non-hydroxy-containing epoxy monomers. In addition, when these are combined with conventional multifunctional epoxy monomers, a marked increase in the polymerization rate of the conventional monomers can be obtained.
In one aspect, the invention relates to a photopolymerizible composition comprising:
(a) a cationic photoinitiator; and
(b) at least one cycloaliphatic epoxyalcohol monomer of formula 1
wherein:
A is a direct bond or C
1
-C
4
alkyl
R
1
is hydrogen, or C
1
-C
12
alkyl;
R
2
is a direct bond or C
1
-C
4
alkyl;
R
3
is C
1
-C
12
hydrocarbon;
R
4
is hydrogen, or C
1
-C
4
alkyl; or
R
1
and R
3
, taken together, or A and R
3
, taken together, form a cyclic 5- or 6- membered aliphatic ring, a cyclic 5- or 6- membered aliphatic ring substituted with 1-3 C
1
-C
4
alkyl groups, a bicyclic 9- or 10-membered aliphatic ring, or a bicyclic 9- or 10-membered aliphatic ring substituted with 1-3 C
1
-C
4
alkyl groups. Preferably, the cycloaliphatic epoxyalcohol monomer is chosen from:
More preferably, the cycloaliphatic epoxyalcohol monomer is chosen from:
In another embodiment, curing compositions further comprise a non-hydroxyl-containing epoxy monomer. Preferred non-hydroxyl-containing epoxy monomers are 3,4-epoxycyclohexyl-3′,4′-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 1,2-epoxytetradecane, 1,2-epoxydecane, 1,2-epoxydodecane, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, epoxidized soybean oil, epoxidized linseed oil and diglycidyl phthalate. More preferred non-hydroxyl-containing epoxy monomers are 3,4-epoxycyclohexyl-3′,4′-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, limonene dioxide, and dicyclopentadiene dioxide.
In another aspect, the invention relates to a method of accelerating the cure rate of an epoxy curing composition comprising:
(a) combining to form an epoxy curing composition:
(1) an amount of at least one cycloaliphatic epoxyalcohol monomer of formula 1 sufficient to cause at least 50% increase in cure speed of the epoxy curing composition,
(2) at least one non-hydroxyl-containing epoxy monomer chosen from the group consisting of:
3,4-epoxycyclohexyl-3′,4′-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 1,2-epoxytetradecane, 1,2-epoxydecane, 1,2-epoxydodecane, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, epoxidized soybean oil, epoxidized linseed oil and diglycidyl phthalate; and
(3) a cationic photoinitiator; and
(b) exposing the epoxy curing composition to a source of radiation.
Preferred cycloaliphatic epoxyalcohol monomers and non-hydroxyl-containing epoxy monomers are those listed above under curing compositions.
In yet another aspect, the present invention relates to a polymer comprising repeating units of formula 2:
wherein the definitions of the variable residues are as before. It is preferred that the repeating units be derived from the cycloaliphatic epoxyalcohol monomer and non-hydroxyl-containing epoxy monomers listed above under curing compositions.
REFERENCES:
patent: 3280152 (1966-10-01), Tinsley et al.
patent: 3867323 (1975-02-01), Rifi
patent: 4123445 (1978-10-01), Lyons
patent: 4175972 (1979-11-01), Crivello
patent: 4318766 (1982-03-01), Smith
patent: 4487945 (1984-12-01), Payne
patent: 4554365 (1985-11-01), Mulder
patent: 4707232 (1987-11-01), Batzill et al.
patent: 4814361 (1989-03-01), Koleske et al.
patent: 5198532 (1993-03-01), Blytas et al.
patent: 3233251 A1 (1982-09-01), None
Berman Susan W.
Heslin & Rothenberg, P.C.
Rensselaer Polytechnic Institute
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