Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1999-03-19
2001-11-06
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...
C522S030000, C522S070000, C522S081000, C522S168000, C522S170000, C522S181000
Reexamination Certificate
active
06313188
ABSTRACT:
FIELD OF INVENTION
The present invention is directed to a sensitized photocatalytic composition, and more specifically to a photocatalytic composition for cationic photopolymerization to be used for photocurable cationically-polymerizable compounds. The photocatalytic composition according to the present invention can cure cationically-polymerizable compounds when it is mixed with said compounds and is irradiated with an actinic radiation such as light, electron beam or X-ray, and because of its excellent property in the photosensitivity to long wavelength light, the composition is suitably applicable to photocurable coating materials, adhesives, inks, and photoresists, photosensitive resins for photomodeling, and so on.
BACKGROUND ART
As examples for aryl onium salts usable in the present invention, the ones disclosed in Japanese Patent Laid-opened Nos. Sho 50-151997, Sho 50-158680 and Sho 50-151996 are known, and wherein it is described that these salts can be used as a catalyst capable of curing cationically-polymerizable compounds, such as epoxy compounds, in the presence of any of light, electron beam and radiation, such as X-ray.
As said aryl onium salts have almost no absorbing property for rays having a wavelength longer than 360 nm, which rays are considered as effective range for the curing with ultraviolet radiation, it is known that photocatalytic activity tend to be remarkably deteriorated when such salts are used for photomodeling using lasers having a long wavelength and for photocurable compositions using additives, such as pigments. In particular, such deterioration is seriously disadvantageous in case of photocurable compositions which contain great amount of white pigments, such as titanium dioxide, of which absorption spectrum coincides with the UV absorption spectrum of aryl onium salts. For solving such a problem, investigation was made on use of sensitizers, thereby it is reported that compounds, such as phenothiadine, anthracene and perilene, are useful as such sensitizers for improving photocurable property. However, it is insufficient yet to improve the photocurable property by using said sensitizers mentioned above in case of photocurable compositions using additives, such as pigments.
Also, in case of an aryl iodonium salt represented by diphenyl iodonium salt, of which pair anions are SbF6 and an anion other than B(C6F5), such as PF6, it is known that photocurable property is found to be very bad when such a salt is used for a clear coating composition.
Aiming at solving the problems as described above, it is an objective of the present invention to provide a photocatalytic composition for cationic photopolymerization which can sufficiently cure even aryl iodonium salts represented by diphenyl iodonium salts of which pair aninons contain an anion, such as PF6, and compositions containing additives, such as pigments, within a short time, and is capable of providing excellent physical properties to the products cured by the inventive photocatalytic composition.
DISCLOSURE OF THE INVENTION
For aiming at solving the problems described above, the inventors of the present invention had keenly studied to find out a photocatalytic composition which can provide a solution for such problems by using a specific sensitizer in the photocatalytic composition.
Now, the present invention is further explained in detail in the following.
The present invention is directed to a photocatalytic composition comprising at least one compound, which is selected from a group consisting of polycyclic aromatic compounds and carbazole derivatives, both of which contain as substitutes at least any of hydroxy group, optionally-substituted aralkyloxy group or alkoxy group, and having an. UV absorption spectrum at a wavelength longer than 330 nm, and more specifically to a photocatalytic composition containing at least one compound selected from a group consisting of polycyclic aromatic compounds and carbazole derivatives, both of which contain as substituents at least one of hydroxy group, optionally-substituted aralkyloxy group or alkoxy group, and having an UV absorption spectrum at a wavelength longer than 330 nm and at least one aryl onium salt selected from a group consisting of diphenylalkylsulfonium salts, dinaphthylalkylsulfonium salts, triphenylsulfonium salts, diphenyliodonium salts, phenylnaphthyliodonium salts and dinaphthyliodonium salts, those which perform as a catalyst for cationic photopolymerization.
The compounds specified in the present invention are compounds selected from a group consisting of polycyclic aromatic compounds and carbazole derivatives, those which contain as substituents at least one of hydroxy, optionally-substituted aralkyloxy and alkoxy, and each of the compounds have an UV absorption spectrum at a wavelength longer than 330 nm and work mainly as a sensitizer for a catalyst to be used for cationic photopolymerization.
As examples for the aryl onium salts usable for the present invention, the ones disclosed in Japanese Patent Laid-opened Nos. Sho 50-15199 Gazette, Sho 50-158680 Gazetter and Sho 50-151996 Gazette can be given, and out of those examples, it is preferable to use particularly diphenylalkylsulfonium salts, dinaphthylalkylsulfonium salts, triphenylsulfonium salts, diphenyliodonium salts, phenylnaphthyliodonium salts, dinaphthyliodonium salts and derivatives of all these salts mentioned above.
For pair anions, any non-nucleophilic pair anions can be used irrespective of their types.
As examples for the sulfonium salts described above, the following compounds can be given.
In the following illustrated compounds, X represents an anion residue, and B(C
6
F
5
), SbF
6
, AsF
6
, PF
6
, BF
4
and the like can be given as examples for such residues.
It is particularly a diaryliodonium salt compound that shows its remarkable sensitizing effect when it is combined with the photocatalytic composition according to the present invention.
As examples for said diaryliodonium salts, diphenyliodonium salts, phenylnaphthyliodonium salts and dinaphthyliodonium salts, those which contain phenyl and naphthyl being optionally substituted with alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and decyl; cycloalkyl, such as cyclohexyl; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, decyloxy, and dodecyloxy; halogeno, such as fluorine, chlorine, bromine and iodine; carbonyl, such as benzoyl; phenyl, nitro and the like can be given, whereas as examples for the non-nucleophilic pair anions, B(C
6
F
5
), SbF
6
, AsF
6
, PF6, BF
4
and the like can be given.
As examples for the diallyliodonium salts, compounds as shown below can be given, wherein X represents an anion residue, and B(C
6
F
5
), SbF
6
, AsF
6
, PF
6
, BF
4
and the like can be given as the examples thereof.
The sensitizer used in the present invention is either a polycyclic aromatic compound or a carbazole derivative, which has an UV absorption spectrum at a wavelength longer than 330 nm and contains as substituents at least any of hydroxy, optionally-substituted aralkyloxy and alkoxy.
As examples for the polycyclic aromatic compound, it is preferable to use any of naphthalene derivatives, anthracene derivatives, chrysene derivatives and phenanthrene derivatives. As alkoxy as substituents, the ones containing 1-18 carbon atoms are preferable, and particularly the ones containing 1-8 carbon atoms are more preferable. As aralkyloxy, the ones containing 7-10 carbon atoms are preferable, and particularly the ones containing 7-8 carbon atoms, such as benzyloxy and phenethyloxy, are more preferable.
As examples for the sensitizer usable in the present invention, carbazole derivatives, such as carbazole, N-ethylcarbazole, N-vinylcarbazole and N-phenylcarbazole; naphthalene derivatives, such as 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 1-stearyloxynaphthalene, 2-methoxynaphthalene, 2-dodecyloxynaphthalene, 4-methoxy-1-naphthol, glycidyl-1-naphthyl ether, 2-(2-naphthoxy)ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-di
Berman Susan W.
Jacobson & Holman PLLC
Nippon Soda Co. Ltd.
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