Borate coinitiators for photopolymerization

Details Borate coinitiators for photopolymerization Borate coinitiators for photopolymerization

1999-05-19

2001-04-03

Baxter, Janet (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Imaging affecting physical property of radiation sensitive...

Radiation sensitive composition or product or process of making

C430S914000, C568S001000, C568S006000, C522S006000

Reexamination Certificate

active

06210863

ABSTRACT:

The invention relates to highly reactive borate photoinitiator compounds, to compositions comprising these compounds, and to the use of the compounds.
The use of borates as photoinitiators in combination with coinitiators is known in the prior art. For example, U.S. Pat. Nos. 4,772,530, 4,772,541 and 5,151,520 disclose triaryl alkyl borate anions with cationic dyes, for example cyanines, rhodamines, etc., as counterions. These compounds are employed as photoinitiators. In U.S. Pat. No. 4,954,414, cationic transition metal complexes are used together with triaryl alkyl borate anions in photopolymerizable compositions. From U.S. Pat. No. 5,055,372 it is also known to use quaternary ammonium compounds, for example tetramethylammonium, pyridinium, cetylpyridinium, etc., as cationic counterions to the triaryl alkyl borate. In this publication, the borates are employed in association with aromatic ketone initiator compounds as coinitiators in photocurable materials. In EP-A-555 058 and JP-A Hei 5 255347, borates, including trimesityl butyl borate among others, are used as coinitiators for (oxo)sulfonium complexes.
For the extensive range of applications of photoinitiators, there is a requirement in the industry for stable reactive compounds.
It has surprisingly now been found that monoborate compounds which are ortho-substituted on at least two aryl radicals possess these properties to a high degree. The invention therefore provides compounds of the formulae I and I′
in which
R
1
and R
2
independently of one another are phenyl or another aromatic hydrocarbon, with or without any heteroatom, which radicals are unsubstituted or are substituted 1-5 times by C
1
-C
20
alkyl, C
2
-C
20
alkyl which is interrupted by one or more radicals O, S(O)
p
or NR
5
, or are substituted by OR
6
, R
6
S(O)
p
, R
6
S(O)
2
O, R
7
R
8
N, R
6
OC(O), R
7
R
8
NC(O), R
9
C(O), R
9
R
10
R
11
Si, R
9
R
10
R
11
Sn, R
12
R
13
B, halogen, R
9
R
10
P(O)
q
, and/or CN,
with the proviso that the phenyl radical or the other aromatic hydrocarbon radicals are substituted in at least one o-position, or R
1
and R
2
independently of one another are C
1
-C
20
alkyl which is substituted by R
9
R
10
R
11
Si, or the radicals R
1
and R
2
form bridges to produce structures of the formula II, IIa or IIb
where the aromatic rings in the formulae II, IIa or IIb are unsubstituted or are substituted by C
1
-C
20
alkyl, C
2
-C
20
alkyl which is interrupted by one or more radicals O, S(O)
p
or NR
5
or are substituted by OR
6
, R
6
S(O)
p
, R
6
S(O)
2
O, R
7
R
8
N, R
6
OC(O), R
7
R
8
NC(O), R
9
C(O), R
9
R
10
R
11
Si, R
9
R
10
R
11
Sn, halogen, R
9
R
10
P(O)
q
and/or R
12
R
13
B;
R
2a
is phenylene or another divalent aromatic hydrocarbon, with or without any heteroatom, which radicals are unsubstituted or are substituted 1-5 times by C
1
-C
20
alkyl, C
2
-C
20
alkyl which is interrupted by one or more radicals O, S(O)
p
or NR
5
, or are substituted by OR
6
, R
6
S(O)
p
, R
6
S(O)
2
O, R
7
R
8
N, R
6
OC(O), R
7
R
8
NC(O), R
9
C(O), R
9
R
10
R
11
Si, R
9
R
10
R
11
Sn, R
12
R
13
B, halogen, R
9
R
10
P(O)
q
, and/or CN, or R
2a
is phenyl-C
1
-C
6
alkylene;
R
3
is C
1
-C
20
alkyl which is substituted by R
9
R
10
R
11
Si, or is phenyl or another aromatic hydrocarbon, with or without any heteroatom, where the phenyl radical or the other aromatic hydrocarbon radicals are unsubstituted or are substituted 1-5 times by C
1
-C
20
alkyl, C
2
-C
20
alkyl which is interrupted by one or more radicals O, S(O)
p
or NR
5
, or are substituted by OR
6
, R
6
S(O)
p
, R
6
S(O)
2
O, R
7
R
8
N, R
6
OC(O), R
7
R
8
NC(O), R
9
C(O), R
9
R
10
R
11
Si, R
9
R
10
R
11
Sn, R
12
R
13
B, halogen, R
9
R
10
P(O)
q
, and/or CN;
R
4
is phenyl, another aromatic hydrocarbon, C
1
-C
20
alkyl, C
2
-C
20
alkyl which is interrupted by one or more radicals O, S(O)
p
or NR
5
, or is C
3
-C
12
cycloalkyl, C
2
-C
8
alkenyl, phenyl-C
1
-C
6
alkyl or naphthyl-C
1
-C
3
alkyl, where the radicals phenyl, another aromatic hydrocarbon, C
1
-C
20
alkyl, C
3
-C
12
cycloalkyl, C
2
-C
8
alkenyl, phenyl-C
1
-C
6
alkyl or naphthyl-C
1
-C
3
alkyl are unsubstituted or are substituted by OR
6
, R
6
S(O)
p
, R
6
S(O)
2
O, R
7
R
8
N, R
6
O(O), R
7
R
8
NC(O), R
9
C(O), R
9
R
10
R
11
Si, R
9
R
10
R
11
Sn, R
12
R
13
B, halogen, R
9
R
10
P(O)
q
, and/or CN;
E is R
14
R
15
R
16
P, R
6
R
6a
S or R
8
R
8a
R
7
N;
Y is (CH
2
)
n
, CH═CH, C(O), NR
5
, O, S(O)
p
or
n is 0, 1 or 2;
m is 2 or 3;
p is 0, 1 or 2;
q is 0 or 1;
R
5
is hydrogen, C
1
-C
12
alkyl, phenyl-C
1
-C
6
alkyl or phenyl, where the radicals phenyl-C
1
-C
6
alkyl or phenyl are unsubstitued or are substituted 1-5 times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy and/or halogen;
R
6
and R
6a
independently of one another are C
1
-C
12
alkyl, phenyl-C
1
-C
6
alkyl or phenyl, where the radicals phenyl-C
1
-C
6
alkyl or phenyl are unsubstituted or are substituted 1-5 times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy and/or halogen;
R
7
, R
8
and R
8a
independently of one another are C
1
-C
12
alkyl, C
3
-C
12
cycloalkyl, phenyl-C
1
-C
6
alkyl or phenyl where the radicals phenyl-C
1
-C
6
alkyl or phenyl are unsubstituted or are substituted 1-5 times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy, R
6
OC(O), CN and/or halogen or R
7
and R
8
together with the N atom to which they are attached, form a 5- or 6-membered ring which may additionally contain O or S atoms;
R
9
, R
10
and R
11
independently of one another are C
1
-C
12
alkyl, C
3
-C
12
cycloalkyl, phenyl-C
1
-C
6
alkyl or phenyl, where the radicals phenyl-C
1
-C
6
alkyl or phenyl are unsubstituted or are substituted 1-5 times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy and/or halogen;
R
12
and R
13
independently of one another are C
1
-C
12
alkyl, C
3
-C
12
cycloalkyl, phenyl-C
1
-C
6
alkyl or phenyl where the radicals phenyl C
1
-C
6
alkyl or phenyl are unsubstituted or are substituted 1-5 times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy and/or halogen, or R
12
and R
13
, together with the B atom to which they are attached, form a 5- or 6-membered ring;
R
14
, R
15
and R
16
independently of one another are C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
3
-C
12
cycloalkyl, where the radicals C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
3
-C
12
cycloalkyl are unsubstituted or are substituted by R
6
OCO or CN, or R
14
, R
1
and R
16
are phenyl-C
1
-C
6
alkyl, which is unsubstituted or is substituted one to five times by C
1
-C
6
alkyl, C
1
-C
12
alkoxy or halogen, or are phenyl which is unsubstituted or is substituted one to five times by C
1
-C
6
alkyl, C
1
-C
12
-alkoxy or halogen; and
G is a radical which is able to form positive ions, with the proviso that, if R
1
, R
2
and R
3
are 2,4,6-trimethylphenyl, R
4
is not C
2
-C
20
alkyl or C
2
-C
8
alkenyl
In combination with coinitiators these compounds are highly reactive initiators for the photopolymerization of ethylenically unsaturated compounds.
In the compounds of the formula I, at least one of the radicals R
1
and R
2
, provided that they are not R
9
,R
10
R
11
Si substituted C
1
-C
20
alkyl, are each a phenyl ring which is substituted ortho to the bond to the boron atom or is another aromatic hydrocarbon radical which is sterically hindered ortho to the boron atom. Ortho-substitution here is generally understood to mean a bond in the o position of the aryl ring with respect to the boron central atom, thus including, for example, a fused-on ring. In accordance with this definition, therefore, some polycyclic aromatic hydrocarbons, for example naphthyl, are also rings (ring systems) which are substituted ortho to the bond to the boron central atom.
Aromatic hydrocarbons as may be present in the novel compounds may, for example, contain one or more, especially 1 or 2, heteroatoms. Examples of suitable heteroatoms are N, O, P or S, preferably N or O. Examples of aromatic hydrocarbon radicals are phenyl, &agr;-and &bgr;-naphthyl, stilbenyl, biphenyl, o-, m-, p-terphenyl, triphenylphenyl, binaphthyl, anthracyl, phenanthryl, pyrenyl, furan-2-yl or furan-3-yl, thiophen-2-yl or thiophen-3-yl, pyridin-2-yl, pyridin-3-yl or pyridin-4-yl quinolyl or isoquinolyl

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