Photoinitiator mixtures containing acylphosphinoxides and...

Details Photoinitiator mixtures containing acylphosphinoxides and... Photoinitiator mixtures containing acylphosphinoxides and...

1998-12-30

2001-03-27

Seidleck, James J. (Department: 1711)

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

Synthetic resins

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

C522S007000, C522S028000, C522S030000, C526S328000, C526S208000, C526S100000, C526S138000

Reexamination Certificate

active

06207727

ABSTRACT:

The invention relates to a photoinitiator mixture comprising
a) at least one acyl- or diacylphosphine oxide of the formula I
 where
R
1
is C
1
-C
18
-alkyl, halogen- or C
1
-C
6
-alkoxy-substituted C
1
-C
4
-alkyl, C
5
-C
8
-cycloalkyl, C
7
-C
9
-phenylalkyl, phenyl, naphthyl, biphenylyl, mono- or poly-halogen-, —C
1
-C
12
-alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl, naphthyl or biphenylyl, or a monovalent, N-, O- or S-containing, 5- or 6-membered heterocyclic radical,
R
2
is phenyl, naphthyl, biphenylyl, mono- or poly-halogen-, —C
1
-C
12
-alkyl and/or —C
1
-C
12
-alkoxy-substituted phenyl, naphthyl or biphenylyl, a monovalent, N-, O- or S-containing, 5- or 6-membered heterocyclic radical, C
1
-C
18
-alkoxy, phenoxy, halogen-, C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy-substituted phenoxy, benzyloxy, cyclohexyloxy or a group —CO—R
4
, or R
2
and R
1
together with the phosphorus form a ring,
R
3
is C
1
-C
18
-alkyl, halogen- or C
1
-C
6
-alkoxy-substituted C
1
-C
4
-alkyl, C
5
-C
8
-cycloalkyl, C
7
-C
9
-phenylalkyl, phenyl, naphthyl, biphenylyl, mono- or poly-halogen-, —C
1
-C
12
-alkyl and/or —C
1
-C
12
-alkoxy-substituted phenyl, naphthyl or biphenylyl, a monovalent N-, O- or S-containing, 5- or 6-membered heterocyclic radical or a group
where X is C
2
-C
8
-alkylene, cyclohexylene or unsubstituted or halogen-, C
1
-C
4
-alkyl- or C
1
-C
4
-alkoxy-substituted phenylene or biphenylene, and
R
4
is C
1
-C
18
-alkyl, halogen- or C
1
-C
4
-alkoxy-substituted C
1
-C
4
-alkyl, C
5
-C
8
-cycloalkyl, C
7
-C
9
-phenylalkyl, phenyl, naphthyl, biphenylyl, mono- or poly-halogen-, —C
1
-C
12
-alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl, naphthyl or biphenylyl or a monovalent, N-, O- or S-containing, 5- or 6-membered heterocyclic radical, or R
4
and R
3
together are C
2
-C
12
-alkylene, vinylene or o-phenylene,
and
b) at least one benzophenone derivative of the formula
where R
5
, R
6
and R
7
independently are C
1
-C
12
-alkyl, C
1
-C
4
-alkylthio, C
1
-C
4
-alkoxy, halogen or C
2
-C
6
-alkoxycarbonyl and R
8
, R
9
and R
10
are hydrogen, C
1
-C
12
-alkyl, C
1
-C
4
-alkoxy, halogen or C
2
-C
6
-alkoxycarbonyl or C
1
-C
4
-alkylthio
or a mixture of benzophenone derivatives of the formula II with other benzophenone derivatives.
The invention additionally relates to radiation-curable compositions comprising the photoinitiator mixtures.
Acylphosphine oxides and their use as photoinitiators are known, for example, from EP-A-7508 or EP-A-7086.
Photoinitiator mixtures comprising acylphosphine oxides and benzophenones have already been described in EP-A-446 175.
A large number of requirements are placed on photoinitiators used in radiation-curable compositions. Of particular importance is a high level of reactivity of the photoinitiators, by which is meant, firstly, rapid curing and, secondly, curing which even in thick coats extends down to the lower layers.
A disadvantage of prior art radiation-curable compositions is in many cases the inhibition of curing as caused by atmospheric oxygen.
There are in principle performance advantages with liquid photoinitiators, which are easier to mix with the—generally liquid—radiation-curable compounds. Another requirement is to avoid the odor nuisance often associated with prior art photoinitiators.
It is an object of the present invention, therefore, to provide photoinitiators which go a particularly long way toward meeting the above requirements.
We have found that this object is achieved by the photoinitiator mixtures defined at the outset and by their use in radiation-curable compositions.
The novel photoinitiator mixture comprises at least one acyl- or diacylphosphine oxide of the formula I (constituent a) of the mixture).
The preferred definitions of R
1
to R
4
are as follows.
R
1
: C
1
-C
18
-alkyl; phenyl; C
7
-C
9
-phenylalkyl; mono- or poly-halogen-, —C
1
-C
l2
-alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl
R
2
: C
1
-C
18
-alkoxy; phenoxy; halogen-, C
1
-C
4
-alkyl- or C
1
-C
4
-alkoxy-substituted phenoxy; benzyloxy; phenyl; mono- or poly-halogen-, —C
1
-C
12-
alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl;
R
3
: C
1
-C
18
-alkyl; C
7
-C
9
-phenylalkyl; phenyl; mono- or poly-halogen-, —C
1
-C
12
-alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl
R
4
: C
1
-C
18
-alkyl; phenyl; C
7
-C
9
-phenylalkyl; mono- or poly-halogen-, —C
1
-C
12
-alkyl- and/or —C
1
-C
12
-alkoxy-substituted phenyl
Particularly preferred definitions of R
1
to R
4
are:
R
1
: phenyl, C
2
-C
12
-alkyl, for example isoamyl
R
2
: Phenyl, phenoxy, C
2
-C
12
-alkoxy, especially ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, cyclohexyloxy or —CO—R
4
R
3
: di- or tri-halogen-, —C
1
-C
12
-alkyl- or —C
1
-C
12
-alkoxy-substituted phenyl, substituted preferably in positions 2 and 4 or positions 2, 4 and 6 respectively.
Examples of particularly suitable radicals R
3
are
R
4
: as for R
3
Halogen substituents mentioned above or below in this application are preferably Cl or Br, particularly preferably Cl.
Very particularly preferred compounds are:
and especially
and
Constituent b) of the novel mixture is a benzophenone derivative of the formula II or a mixture of a benzophenone derivative of the formula II with other benzophenone derivatives.
The preferred definitions of R
5
to R
10
are:
R
5
,R
6
,R
7
: independently C
1
-C
12
-alkyl, especially C
1
-C
4
-alkyl, particularly preferably methyl. Substitution is preferably in positions 2, 4 and 6 (carbonyl substitution in position 1)
R
8
,R
9
,R
10
: independently hydrogen or C
1
-C
12
-alkyl, especially C
1
-C
4
-alkyl. With particular preference at least one, preferably at least two, of R
8
, R
9
and R
10
is or are hydrogen and the other(s) is(are) hydrogen or C
1
-C
4
-alkyl, especially methyl.
In a preferred embodiment the benzophenone derivatives b) comprise a mixture of the benzophenone derivatives of the formula II with other benzophenone derivatives, especially those of the formula III,
where R
11
, R
12
, R
13
and R
14
independently are hydrogen, C
1
-C
12
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-alkylthio, halogen or C
2
-C
6
-alkoxycarbonyl.
With preference, R
11
, R
12
, R
13
and R
14
independently are hydrogen or C
1
-C
12
-alkyl, especially C
1
-C
4
-alkyl, or methyl. With preference, at least 2 of the radicals R
11
, R
12
, R
13
and R
14
are hydrogen and the others are hydrogen or the above alkyl.
A particularly preferred mixture of benzophenone derivatives b) is a mixture of
which is sold as TZT® by Fratelli Lamberti.
The mixture of benzophenone derivatives b) consists preferably of
from 10 to 90
% by weight, particularly preferably
from 50 to 85
% by weight, of benzophenone derivatives of
the formula II and preferably of
from 90 to 10
% by weight, particularly preferably
from 15 to 50
% by weight, of other benzophenone
derivatives, especially benzophenone
derivatives of the formula III, based on the
overall amount of benzophenone derivatives
b)
The content of the acyl- or diacylphosphine oxides a) and of the benzophenone derivatives b) is preferably
from 0.5 to 99.5
% by weight, particularly preferably
from 0.5 to 40
% by weight and, with very particular
preference,
from 5 to 30
% by weight of compound a) and
from 0.5 to 99.5
% by weight, particularly preferably
from 60 to 99.5
% by weight and, with very particular
preference,
from 70 to 95
% by weight of compound b), based on the sum
of a) + b).
The novel photoinitiator mixture can be simply prepared by mixing the compounds a) and b) in either order.
The novel photoinitiator mixture is used in particular as a photoinitiator for the radiation curing of free-radically polymerizable, ethylenically unsaturated compounds.
The composition comprising the novel photoinitiator mixture and at least one polymerizable, ethylenically unsaturated compound is also referred to below as radiation-curable composition.
Suitable radiation-curable, free-radically polymerizable compounds are those having only one ethylenically unsaturated, copolymerizable group (compounds A).
Examples are C
1
-C
20
-alkyl (meth)acryl

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