Photoinitiator combinations

Details Photoinitiator combinations Photoinitiator combinations

1999-12-01

2001-06-26

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...

C522S018000, C522S081000, C522S083000, C522S084000, C522S086000, C522S107000

Reexamination Certificate

active

06251963

ABSTRACT:

The invention relates to photoinitiator combinations of mono- and bis-acylphosphine oxides, to compositions comprising those combinations and to their use.
Mono- and bis-acylphosphine oxides are known compounds. For example, monoacylphosphine oxides are described as photoinitiators in U.S. Pat. Nos. 4,298,738, 4,324,744, 4,292,152, 4,385,109 and 4,710,523. Bisacylphosphine oxide compounds are disclosed as photo-initiators in, for example, U.S. Pat. Nos 4,737,593 and 4,792,632. Alkyl-bisacylphosphine oxides and mixtures of those compounds with &agr;-hydroxyketones or benzophenone compounds are disclosed in U.S. Pat. No. 5,399,770 and U.S. Pat. No. 5,472,992. Further bisacylphosphine oxides are known from GB 2 292 740. EP 446 175 describes mixtures of three components, namely a mono- or bis-acylphosphine oxide, an &agr;-hydroxyketone and a benzophenone.
There is a need in the art for effective photoinitiators that can be incorporated readily and that are capable of curing photopolymerisable compositions effectively, that is to say with good through cure and without extreme yellowing phenomena.
It has now been found that combinations of mono- and bis-acylphosphine oxides meet those requirements in a surprising manner.
The invention therefore relates to photoinitiator combinations comprising
(a) at least one compound of formula (I)
R
1
is C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen;
R
2
is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen and
R
3
is C
1
-C
20
alkyl, cyclopentyl, cyclohexyl, phenyl-C
1
-C
4
alkyl or a group of formula (III)
or R
3
is naphthyl, biphenylyl or an O—, S— or N-containing 5- or 6-membered heterocyclic ring, the naphthyl, biphenylyl and O—, S— or N-containing 5- or 6-membered heterocyclic ring radicals being unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, halogen, C
1
-C
4
alkylthio;
R
4
, R
5
, R
6
, R
7
and R
8
are each independently of the others hydrogen, halogen, C
1
-C
20
-alkyl, cyclopentyl, cyclohexyl, C
2
-C
12
alkenyl, C
2
-C
20
alkyl interrupted by one or more non-consecutive O atoms, phenyl-C
1
-C
4
alkyl, C
1
-C
20
alkoxy, or phenyl that is unsubstituted or substituted by one or two C
1
-C
4
alkyl or/and C
1
-C
4
alkoxy substituents; and
(b) at least one compound of formula (II)
R
1
and R
2
are as defined above;
R
9
is C
1
-C
20
alkyl, cyclopentyl, cyclohexyl, phenyl-C
1
-C
4
alkyl, a group of formula (III), naphthyl, biphenylyl or an O—, S— or N-containing 5- or 6-membered heterocyclic ring, the naphthyl, biphenylyl and O—, S— or N-containing 5- or 6-membered heterocyclic ring radicals being unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, halogen, C
1
-C
4
-alkylthio; and
R
10
is C
1
-C
20
alkyl, C
2
-C
20
alkyl interrupted by one or more non-consecutive O atoms, C
1
-C
20
oalkoxy, cyclopentyl, cyclohexyl, phenyl-C
1
-C
4
alkyl, a group of formula (III), naphthyl, biphenylyl or an O—, S— or N-containing 5- or 6-membered heterocyclic ring, the naphthyl, biphenylyl and O—, S— or N-containing 5- or 6-membered heterocyclic ring radicals being unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, halogen, C
1
-C
4
alkylthio.
C
1
-C
20
Alkyl is linear or branched and is, for example, C
1
-C
18
-, C
1
-C
12
-, C
1
-C
8
-, C
1
-C
6
- or C
1
-C
4
-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
For example, R
3
is C
1
-C
18
alkyl, especially C
1
-C
8
alkyl, preferably 2,4,4-trimethylpent-1-yl. C
1
-C
4
Alkyl is as defined above up to the corresponding number of carbon atoms. R
1
and R
2
are preferably methyl.
C
2
-C
20
Alkyl interrupted one or more times by non-consecutive O atoms is interrupted, for example, from 1 to 9 times, e.g. from 1 to 7 times or once or twice, by O atoms. If the alkyl radical is interrupted by more than one O atom, then the O atoms are each separated from the other(s) by at least one methylene group, yielding, for example, structural units such as —CH
2
—O—CH
3
, —CH
2
CH
2
—O—CH
2
CH
3
, —[CH
2
CH
2
O]
y
—CH
3
, wherein y=1-9, —(CH
2
CH
2
O)
7
CH
2
CH
3
, —CH
2
—CH(CH
3
)—O—CH
2
—CH
2
CH
3
or —CH
2
—CH(CH
3
)—O—CH
2
—CH
3
. R
10
may, for example, also be —[OCH
2
CH
2
]
y
—OCH
3
, wherein y=1-5, especially wherein y=1, 2 or 3.
R
10
as C
2
-C
20
alkyl interrupted one or more times by non-consecutive O atoms may also be, for example, a radical,
wherein n is a number from 1 to 4 and m is a number from 1 to 10. The group C
n
H
2n
is accordingly linear or branched C
1
-C
4
alkyl.
R
1
, is a C
1
-C
20
alkyl radical. Examples thereof and of C
1
-C
4
alkyl are given above. Examples of a radical
are —OCH
2
CH
2
OCH
3
, —(OCH
2
CH
2
)
2
—OCH
3
, —(OCH
2
CH
2
)
3
—OCH
3
, —(OCH
2
CH
2
)
4
—OCH
3
, —OCH
2
CH
2
OC
2
H
5
, —(OCH
2
CH
2
)
2
—OC
2
H
5
, —(OCH
2
CH
2
)
3
—OC
2
H
5
, —(OCH
2
CH
2
)
4
—OC
2
H
5
, —OCH
2
CH
2
OC
3
H
7
, —(OCH
2
CH
2
)
2
—OC
3
H
7
, —(OCH
2
CH
2
)
3
—OC
3
H
7
, —(OCH
2
CH
2
)
2
—OC
3
H
7
, —OCH
2
CH
2
OC
4
H
9
, —(OCH
2
CH
2
)
2
—OC
4
H
9
, —(OCH
2
CH
2
)
3
—OC
4
H
9
, —(OCH
2
CH
2
)
4
—OC
4
H
9
, etc.
C
1
-C
20
Alkoxy is a linear or branched radical and is, for example, C
1
-C
18
-, C
1
-C
12
-, C
1
-C
8
-, C
1
-C
6
- or C
1
-C
4
-alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethyl-pentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy and eicosyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, preferably methoxy.
C
1
-C
12
Alkoxy, C
1
-C
8
alkoxy, C
1
-C
6
alkoxy and C
1
-C
4
alkoxy are likewise linear or branched and are, for example, as defined above up to the corresponding number of carbon atoms. R
1
and R
2
are preferably methoxy.
C
1
-C
4
Alkylthio is a linear or branched radical and is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio or tert-butylthio, preferably methylthio.
C
2
-C
12
Alkenyl radicals may be mono- or poly-unsaturated and linear or branched and are, for example, C
2
-C
8
-, C
2
-C
6
- or C
2
-C
4
-alkenyl. Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl and dodecenyl, especially allyl. R
4
, R
5
, R
6
, R
7
and R
8
as C
2
-C
8
alkenyl are, for example, C
2
-C
6
alkenyl, especially C
2
-C
4
-alkenyl.
Phenyl-C
1
-C
4
alkyl is, for example, phenyl-C
1
-C
2
alkyl, such as benzyl, phenylethyl, &agr;-methylbenzyl or &agr;,&agr;-dimethylbenzyl, especially benzyl.
Substituted phenyl, naphthyl or biphenylyl or the O—, S— or N-containing 5- or 6-membered heterocyclic radical is mono- to penta-substituted, e.g. mono-, di- or tri-substituted, especially mono- or di-substituted. C
1
-C
4
Alkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio and halogen substituents of those radicals are as defined hereinabove or hereinbelow. Preferred substituents are C
1
-C
4
-alkyl, especially methyl and ethyl, and C
1
-C
4
alkoxy, especially methoxy.
Halogen is fluorine, chlorine, bromine and iodine, especially chlorine and bromine, preferably chlorine.
R
3
as an O—, S— or N-containing 5- or 6-membered heterocyclic ring is, for example, furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. The mentioned heterocyclic radicals may be mono- or poly-substituted. Examples thereof are dimethylpyridyl, dimethylpyrrolyl and methylfuryl.
The term “and/or” is intended to indicate that not only one of the defined alternatives (substituents) but several different defined alternatives (substituents) may be present together, that is to say mixtures of different alternatives (substituents) may be present.
The term “at least one” is intended to indicate “one or more than one”, e.g. one or two or three, preferably one or two.
The preparation of the compounds of formulae I a

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