Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2002-01-31
2004-01-13
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...
C522S015000, C522S006000, C522S025000, C522S113000, C522S122000, C522S121000, C522S071000, C522S150000, C522S168000, C522S170000, C522S182000, C522S154000
Reexamination Certificate
active
06677390
ABSTRACT:
TECHNOLOGICAL FIELDS
The present invention relates to novel iodonium salt compounds and photocurable compositions containing the said compounds. In more detail, it relates to cationically photocurable compositions that generate acids and cure in a short time when actinic energy rays, such as light, electron beams and X-rays, are irradiated. The cured products of the said compositions have excellent physical properties so that the compositions are preferably used in paints, adhesives, photoresists, inks, silicon releases and the like.
BACKGROUND ART
Japanese Patents Laid-open Nos. Sho 50-151996, Sho 60-47029 and others describe iodonium salt compounds similar to those of the present invention. They describe also that these iodonium salt compounds can be used as catalysts to cure cationically polymerizable compounds, such as epoxy compounds, with radiation, such as light, electron beams or X-rays.
Generally, iodonium salt compounds have such problems as low solubility in monomers and high toxicity.
It is known that the photocurable properties of iodonium salt compounds are extremely reduced if the counter anions of the compounds are those other than hexafluoroantimonate or tetraperfluorophenylborate, such as hexafluorophosphate or tetrafluoroborate. Therefore, iodonium salt compounds having these counter anions are not suitable to cure clear compositions or compositions containing pigments by light. Sensitizers effective to them have not yet been found either.
DISCLOSURE OF INVENTION
It is an object of the present invention to provide an iodonium salt compound which is colored little, can be easily synthesized in high yield, produces an acid thanks to being highly sensitive to irradiation with actinic energy rays such as light, electronic beams or X-rays, is highly soluble in monomers, and is less toxic. It is also an object to provide a photocurable composition that can cure in a short time even when the counter anion is hexafluorophosphate, tetrafluoroborate or the like, regardless of being clear or pigmented, and that produces a cured object having excellent properties. Particularly it is an object to provide a compound that is much less toxic, such as negative mutagenicity, than known compounds.
In other words, the present invention relates to a compound represented by Formula [I] shown below, and more preferably to an iodonium salt compound represented by Formula [II].
[wherein, R
1
is straight-chain or branched alkyl having 1 to 6 carbons;
R
2
is straight-chain or branched alkyl having 1 to 6 carbons;
m is an integer of 1 to 4, and R
2
groups may be each different when m is 2 or larger;
R
3
is straight-chain or branched alkyl having 1 to 6 carbons;
n is 0 or an integer of 1 to 4, and R
3
groups may be each different when n is 2 or larger;
Y is represented by the formula shown above, q is an integer of 1 to 5, and Y's may be each different when q is 2 or larger;
R
4
and R
5
are, each independently, hydrogen, straight-chain or branched alkyl having 1 to 6 carbons, phenyl or aralkyl;
p is an integer of 1 or 2, and R
4
and R
5
may be each different when p is 2;
R
6
and R
7
are, each independently, hydrogen, straight-chain or branched alkyl having 1 to 12 carbons, optionally substituted phenyl or optionally substituted aralkyl; and
X is a non-nucleophilic anionic residue.]
[wherein, R
11
, R
12
and R
13
are, each independently, straight-chain or branched alkyl having 1 to 6 carbons;
R
3
is straight-chain or branched alkyl having 1 to 6 carbons;
n is 0 or an integer of 1 to 4, and R
3
groups may be each different when n is 2 or larger;
Y is represented by the formula shown above, q is an integer of 1 to 5, and Y's may be each different when q is 2 or larger;
R
4
and R
5
are, each independently, hydrogen, straight-chain or branched alkyl having 1 to 6 carbons, phenyl or aralkyl;
p is an integer of 1 or 2, and R
4
and R
5
may be each different when p is 2;
R
6
and R
7
are, each independently, hydrogen, straight-chain or branched alkyl having 1 to 12 carbons, optionally substituted phenyl or optionally substituted aralkyl; and
X is a non-nucleophilic anionic residue.]
This invention also relates to an iodonium salt compound whose non-nucleophilic anionic residue is either SbF
6
, AsF
6
PF
6
, BF
4
or (F
5
C
6
)
4
B.
The present invention also relates to a photoacid generator and a photopolymerization initiator both of which contain at least one of the said iodonium salt compounds.
Furthermore, the present invention relates to a photocurable composition containing at least one of the said iodonium salt compounds and cationically polymerizable compounds, a photocurable compositions containing at least one of the said iodonium salt compounds, cationically polymerizable compounds and sensitizers, and a photocurable composition containing further pigments and radically polymerizable compounds in addition to at least one of the said iodonium salt compounds, cationically polymerizable compounds and sensitizers.
Actual examples of the straight-chain or branched alkyl groups having 1 to 6 carbons, of R
1
, R
2
, R
3
, R
4
, R
5
, R
11
, R
12
and R
13
of the said Formulae [I] and [II] include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, t-pentyl, neopentyl, n-hexyl and isohexyl.
Examples of the aralkyl groups of R
4
and R
5
include benzyl and phenethyl.
R
6
and R
7
are alkyl groups having up to 12 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, t-pentyl, neopentyl, n-hexyl, isohexyl, heptyl or octyl; or optionally substituted phenyl, or optionally substituted aralkyl such as benzyl or phenethyl. Examples of their substituents include halogen such as chlorine, bromine and fluorine, alkyl groups having ether bonds, and hydroxyl.
X is a non-nucleophilic anionic residue, and is preferred to be SbF
6
, AsF
6
, PF
6
, BF
4
, (F
5
C
6
)
4
B or the like.
Representative examples of the iodonium salt compounds of the present invention are shown in the following. X in the formulae represents a non-nucleophilic anionic residue, such as SbF
6
, AsF
6
, PF
6
, BF
4
or (F
5
C
6
)
4
B.
The iodonium salt compounds of Formula [I] of the present invention may be produced according to Reaction Equation A or B [wherein, M is an alkali metal] shown in the following. The reaction of Compounds [a] and [b] with a sulfuric-acid catalyst is carried out, in organic solvents such as acetic acid and acetic anhydride if required, at −20° C. to room temperature for an hour to several 10 hours. After the completion of the reaction, water is added to the reaction solution to stir. Compound [c] is separated by filtration if deposited, or extracted with organic solvents. A salt exchange reaction of Compound [c] obtained gives target Compound [d].
The iodonium salt compounds of the present invention may be used as photoacid generators, and also as photopolymerization initiators to cure cationically polymerizable compounds by irradiation with actinic energy rays such as light, electronic beams or X-rays. Examples of light sources used include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps and carbon arc lamps. The compounds may be easily cured by laser light such as semiconductor laser, argon laser or He—Cd laser, or ionizing radiation such as &agr;-rays, &bgr;-rays, &ggr;-rays, neutron rays, X-rays or accelerated electron beams. Besides, an iodonium salt compound used together with a sensitizer can cure a cationically polymerizable compound in a shorter time than that without a sensitizer.
Any cationically polymerizable monomers, oligomers and polymers, regardless of their types, can be used as cationically polymerizable compounds in the present invention. Their examples include epoxy compounds of glycidyl
Kimizuka Shinichi
Shirai Akihiro
Takahashi Eiji
Takahashi Hiroshi
LaPointe Dennis G.
Mason Law, P.A.
McClendon Sanza
Nippon Soda Co. Ltd.
Seidleck James J.
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