Alkylphenylbisacylphosphine oxides and photoinitiator mixtures

Details Alkylphenylbisacylphosphine oxides and photoinitiator mixtures Alkylphenylbisacylphosphine oxides and photoinitiator mixtures

1998-01-20

2001-09-04

Ashton, Rosemary E. (Department: 1752)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S012000, C522S018000, C522S064000, C430S916000

Reexamination Certificate

active

06284813

ABSTRACT:

The invention relates to alkylphenylbisacylphosphine oxides and to specific mixtures of bisacylphosphine oxide compounds with other photoinitiators.
Bisacylphosphine oxide compounds are known as photoinitiators from EP-A-184095, for example. Alkylbisacylphosphine oxides and also mixtures of these compounds with &agr;-hydroxy ketones or benzophenone compounds are disclosed in GB-A-2259704. EP-A-446175 describes mixtures of three components, namely mono- or bisacylphosphine oxide, &agr;-hydroxyketone and benzophenone.
In industry there is a need for effective photoinitiators and photoinitiator mixtures which are capable of curing photopolymerizable compositions efficiently and without extreme yellowing phenomena.
It has now been found that compounds of the formula I
in which
R
1
is C
1
-C
4
alkyl,
R
2
is hydrogen, C
1
-C
4
alkyl or C
1
-C
4
alkoxy and
R
3
, R
4
, R
5
, R
6
and R
7
independently of one another are hydrogen, halogen, C
1
-C
20
alkyl, cyclopentyl, cyclohexyl, C
2
-C
12
akenyl, C
2
-C
18
alkyl which is interrupted by one or more oxygen atoms, or are phenyl-substituted C
1
-C
4
alkyl, or are phenyl which is unsubstituted or is mono- or disubstituted by C
1
-C
4
alkyl and/or C
1
-C
4
alkoxy, with the provisos that at least one of the radicals R
3
, R
4
, R
5
, R
6
and R
7
is other than hydrogen and that, if R
1
and R
2
are methyl, R
3
and R
6
are not methyl, are suitable as very good photoinitiators.
It has also been found that the photoinitiators of the formula 1a can be combined with compounds of the formula II, III and/or IV to give initiator mixtures (blends) having good curing properties, especially in respect of the required surface curing and through-curing of polymerizable compositions. The cured compositions, moreover, exhibit highly advantageous properties in the context of yellowing. This application therefore provides a photoinitiator mixture comprising at least one compound of the formula (1a)
in which
R
1
is C
1
-C
4
alkyl;
R
2
is hydrogen, C
1
-C
4
alkyl or C
1
-C
4
alkoxy, and
R
3
, R4, R
5
, R
6
and R
7
independently of one another are hydrogen, halogen, C
1
-C
20
alkyl, cyclopentyl, cyclohexyl, C
2
-C
12
alkenyl, C
2
-C
18
alkyl which is interrupted by one or more oxygen atoms, or are phenyl-substituted C
1
-C
4
allyl, or are phenyl which is unsubstituted or is mono- or disubstituted by C
1
-C
4
alkyl and/or C
1
-C
4
alkoxy; and at least one compound of the formula (II)
in which
R
8
is hydrogen, C
1
-C
18
alkyl, C
1
-C
18
alkoxy, —OCH
2
CH
2
—OR
12
, a group
or a group
in which I is a number from 2 to 10 and A is a radical
R
9
and R
10
independently of one another are hydrogen, C
1
-C
6
alkyl, phenyl, C
1
-C
16
alkoxy, OSiR
13
R
14
R
14a
or —O(CH
2
CH
2
O)
q
—C
1
-C
16
alkyl, in which q is a number from 1 to 20, or R
9
and R
10
, together with the carbon atom to which they are attached, form a cyclohexyl ring;
R
11
is hydroxyl, C
1
-C
16
alkoxy or —O(CH
2
CH
2
O)
q
—C
1
-C
16
alkyl;
where R
9
, R
10
and R
11
, are not all simultaneously C
1
-C
16
alkoxy or —O(CH
2
CH
2
O)
q
—C
1
-C
16
alkyl,
R
12
is hydrogen, C
1
-C
8
alkyl
and
R
13
R
14a
, and R
14
independently of one another are C
1
-C
4
alkyl or phenyl; and/or at least one compound of the formula (III)
in which
R
15
, R
15a
, R
16
and R
17
independently of one another are hydrogen, methyl, phenyl, methoxy, —COOH, unsubstituted or C
1
-C
4
alkyl-substituted phenyl, or a group —OCH
2
CH
2
OR
12
or —SCH
2
CH
2
OR
12
in which R
12
is as defined for formula II; and/or at least one compound of the formula (IV)
in which R
18
is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, halogen or a group N(R
22
)
2
; R
19
is as defined for R
18
or is the group
in which case the radical R
18
from the formula IV and the radical R
18
of this group (IVa) together are a direct bond, and the other radicals are as defined below;
R
20
is C
1
-C
8
alkyl;
R
21
is hydrogen, —CH═CHR
24
, or phenyl which is unsubstituted or is substituted one to three times by C
1
-C
12
alkyl, C
1
-C
4
alkoxy or halogen;
or R
20
and R
21
, together with the carbon atom to which they are attached, form a cyclohexyl ring;
R
22
and R
23
independently of one another are C
1
-C
4
alkyl, or
R
22
and R
23
, together with the nitrogen atom to which they are attached, form a five- or six-membered saturated or unsaturated ring which can be interrupted by —O—, —NH— or —N(CH
3
)—,
R
24
is hydrogen or C
1
-C
4
alkyl; and
R
25
is hydrogen or C
1
-C
12
alkyl.
C
1
-C
20
alkyl can be linear or branched and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl or eicosyl. Preference is given to C
1
-C
18
alkyl, e.g. C
1
-C
12
- or C
1
-C
8
alkyl, especially C
1
-C
4
alkyl.
C
1
-C
18
alkyl, C
1
-C
6
alkyl and C
1
-C
4
alkyl can have the same meanings as given above up to the corresponding number of carbon atoms.
C
2
-C
18
alkyl interrupted by one or more oxygen atoms is, for example, interrupted by 1-5, e.g. 1-3 or 1 or 2 times by —O—. This produces structural units such as —O(CH
2
)
2
OH, —-O(CH
2
)
2
OCH
3
, —O(CH
2
CH
2
O)
2
CH
2
CH
3
, —CH
2
—O—CH
3
, —CH
2
CH
2
—O—CH
2
CH
3
, —[CH
2
CH
2
O]
y
—CH
3
, where y=1-5, —(CH
2
CH
2
O)
5
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
.
The radical —O(CH
2
CH
2
O)
q
—C
1
-C
16
alkyl represents 1 to 20 successive ethylene oxide units whose chain ends in a C
1
-C
16
alkyl. q is preferably q 1 to 10, e.g. 1 to 8, especially 1 to 6. The chain of ethylene oxide units ends in a C
1
-C
12
alkyl, e.g. C
1
-C
8
alkyl, in particular in a C
1
-C
4
alkyl. Here C
1
-C
16
alkyl can have the meanings given above up to the corresponding number of carbon atoms.
C
2
-C
12
alkenyl can be linear or branched and there may be more than one unsaturated bond in the molecule. Examples are vinyl, allyl, methylvinyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl.
C
1
-C
18
alkoxy can be linear or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy or octadecyloxy. Further examples are C
1
-C
12
alkoxy or C
1
-C
8
alkoxy, especially C
1
-C
4
alkoxy. C
1
-C6alkoxy and C
1
-C
4
alkoxy can have the same meanings as given above up to the corresponding number of carbon atoms.
C
1
-C
4
alkylthio can be linear or branched and is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio or tert-butylthio, especially methylthio.
Phenyl-substituted C
1
-C
4
alkyl is, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, &agr;-methylbenzyl or &agr;,&agr;-dimethylbenzyl, especially benzyl.
Substituted phenyl is substituted from one to five times, for example once, twice or three times, especially once or twice, on the phenyl ring. The pattern of substitution on the phenyl ring is, for example, 2-, 3-, 4-, 5-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 2,4,6- or 3,4,5-. C
1
-C
4
alkyl and C
1
-C
4
alkoxy substituents can have the meanings given above. Examples of substituted phenyl are tolyl, xylyl, 4-methoxyphenyl, 2,4- and 2,5-dimethoxyphenyl, ethylphenyl, and 4-alkoxy-2-methylphenyl.
Halogen is, for example, chlorine, bromine or iodine, especially chlorine.
If R
19
is the group
where the radical R
18
from the formula IV and the radical R
18
of this group together are a direct bond, then the result is structures of the formula IVb
If R
22
and R
23
, together with the nitrogen atom to which they are attached, form a ring which can additionally be interrupted by —O—, —NH— or —N(CH
3
)—, then the ring formed is, for example, a morpholino, piperidino or methylpiperidino ring.
The novel compounds of the formula I (and 1a) can be prepared, for example, by double acylation of a primary phosphine (V) with at least 2 equivalents of an acid chloride (VI) in the presence of at least two equivalents of a base and subsequent oxidation of the resulting diacylph

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