Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reissue Patent
2000-07-21
2003-01-07
Juska, Cheryl (Department: 1771)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S029000, C522S024000, C522S025000, C522S026000, C522S027000, C522S028000, C430S281100
Reissue Patent
active
RE037962
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a photopolymerizable composition, more particularly, it relates to a photopolymerizable composition highly sensitive to light rays in the visible light region and capable of showing good sensitivity also to Ar
+
laser, YAG-SHG laser or the like light source.
BACKGROUND OF THE INVENTION
A large number of image formation methods using a photopolymerization system have been conventionally known and used over a wide range of fields such as printing plate, printed circuit, paint, ink, hologram recording and three-dimensional formation. For example, there are known a method where a photopolymerizable composition comprising an addition-polymerizable compound having an ethylenic double bond and a photopolymerization initiator, further, if desired, an organic high molecular binder and a thermal polymerization inhibitor is provided on a support to form a film layer, the layer is imagewise exposed to a desired image to cure the exposed area by polymerization and then the unexposed area is removed by dissolution to form a cured relief image, a method where a layer comprising the above-described photopolymerizable composition is provided between two supports, with at least one support being transparent, the layer is imagewise exposed from the transparent support side to induce the change in adhesive strength by light and then the support is peeled off to form an image, a method where a photosensitive material having a layer containing microcapsules in which a photopolymerizable composition and a coloring material such as a leuco dye are encapsulated is prepared, and the photosensitive material is imagewise exposed to photocure the capsules on the exposed area, while the capsules on the unexposed area are ruptured by pressure or heat treatment to put their contents into contact with a coloring material developer to effect coloration, thereby forming a colored image, an image formation method using the change in toner adhesion property of the photopolymerizable composition due to light and an image formation method using the change in refractive index of the photopolymerizable composition.
The photopolymerizable composition applied to these methods uses in many cases benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine or benzophenone as a photopolymerization initiator. However, these photopolymerization initiators are extremely low in the photopolymerization initiation ability to visible light of 400 nm or more as compared with the photopolymerization initiation ability to ultraviolet light of 400 nm or less and accordingly, thus they are remarkably limited in their application range.
Recently, as the image formation technique has been developed, a photopolymer having high sensitivity to light rays in the visible region is being demanded. The photopolymer is, for example, a photosensitive material suitable for non-contact type plate-making using projection exposure or for plate-making using a visible light laser. The highly expected visible light laser includes an Ar
+
laser which emits light of 488 nm and a YAG-SHG laser which emits light of 532 nm.
With respect to the photopolymerization initiation system sensitive to light rays in the visible light region, many proposals have been hitherto made. Examples of the system include a certain kind of photosensitive dyes described in U.S. Pat. No. 2,850,445, a composite initiation system containing a dye and an amine (see, JP-B-44-20189 (the term “JP-B” as used herein means an “examined Japanese patent publication”)), a combination system containing hexaarylbiimidazole, a radical generating agent and a dye (see, JP-B-45-37377), a system containing hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (see, JP-B-47-2528 and JP-A-54-155292 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”)), a system containing a cyclic cis-&agr;-dicarbonyl compound and a dye (see, JP-A-54-84183), a system containing a substituted triazine and a merocyanine dye (see, JP-A-54-151024), a system containing 3-ketocoumarin and an activator (see, JP-A-52-112681, JP-A-58-15503), a system containing biimidazole, a styrene derivative and a thiol (see, JP-A-59-140203), a system containing an organic peroxide and a dye (see, JP-A-59-140203, JP-A-59-189340) and a system containing a dye having a rhodanine skeleton and a radical generating agent (see, JP-A-2-244050).
It is described in JP-A-59-152396, JP-A-61-151197, JP-A-63-10602, JP-A-63-41484 and JP-A-3-12403 that the titanocene is effective as a photopolymerization initiator and examples of its combination system include a system containing titanocene and a 3-ketocoumarin dye (see, JP-A-63-221110), a system where titanocene, a xanthene dye and further, an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group are used in combination (see, JP-A-4-221958 and JP-A-4-219756) and a system containing titanocene and a specific merocyanine dye (see, JP-A-6-295061).
These conventional techniques are surely effective to visible light rays, however, they are bound to problems such that the sensitivity is insufficient or even if high sensitivity is achieved, the storage stability is poor and hence, these systems cannot be used in practice.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a highly sensitive photopolymerizable composition, particularly, a photopolymerizable composition highly sensitive to visible light rays of 400 nm or more and to light of 488 nm or 532 nm corresponding to the output of an Ar
+
layer or YAG-SHG laser light source, respectively.
Another object of the present is to provide a photopolymerizable composition excellent in the storage stability.
As a result of intensive investigations to achieve the above-described objects, the present inventors have found that a combination system containing a dye having a specific structure and a titanocene compound capable of generating active radicals upon light irradiation in the presence of the sensitizing dye exhibits very high sensitivity to the visible light rays of 400 nm or more and is excellent in the storage stability and based on this finding, the present invention has been accomplished. According to the present invention, a photopolymerizable composition highly sensitive to light rays in the visible light region and excellent in the storage stability can be obtained.
More specifically, the present invention provides a photopolymerizable composition comprising an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a sensitizing dye represented by the following formula (I) and a titanocene compound:
wherein Z
1
and Z
2
each represents a nonmetallic atom group necessary for forming a 5- and/or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes; R
1
and R
2
each represents an alkyl group; Q
1
and Q
2
represent in combination therewith an atomic group necessary for forming a 4-thiazolidinone ring, a 5-thiazolidinone ring, a 4-imidazolidinone ring, a 4-oxazolidinone ring, a 5-oxazolidinone ring, a 5-imidazolidinone ring or a 4-dithiolanone ring; L
1
, L
2
, L
3
, L
4
and L
5
each represents a methine group; m represents 1 or 2; i and h each represents 0 or 1; l represents 1 or 2; j and k each represents 0, 1, 2 or 3; and X
−
represents a counter anion.
In one embodiment of the present invention, the photopolymerizable initiation system further contains at least one compound selected from the group consisting of the compounds 1) to 8):
1) a compound having a carbon-halogen bond;
2) a ketone compound represented by the following formula (II):
wherein Ar represents an aromatic group selected from those represented by the following formulae:
wherein R
5
, R
6
, R
7
, R
8
and R
9
, which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy grou
Fujita Kazuo
Kondo Syun-ichi
Burns Doane , Swecker, Mathis LLP
Fuji Photo Film Co. , Ltd.
Juska Cheryl
LandOfFree
Photopolymerizable composition containing a sensitizing dye... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Photopolymerizable composition containing a sensitizing dye..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Photopolymerizable composition containing a sensitizing dye... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3019325