Radiation imagery chemistry: process – composition – or product th – Post imaging processing – Developing
Reexamination Certificate
2002-07-09
2003-04-29
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Post imaging processing
Developing
C430S496000, C430S523000, C430S533000, C430S534000, C430S535000, C430S536000, C430S537000, C430S539000, C430S950000
Reexamination Certificate
active
06555301
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to photographic silver halide materials, and particularly to photographic silver halide materials that contain a matting agent on either or both sides of the support. This invention also relates to a method of providing an image using such photographic silver halide materials.
BACKGROUND OF THE INVENTION
It is conventional to incorporate fine particles of polymers or inorganic materials into the surface protective layers of photographic materials to increase surface roughness. This reduces the possibility that various materials will stick to each other or to processing equipment, and improves antistatic properties. Useful surface matting agent prepared from various crosslinked organic polymers are described, for example, in U.S. Pat. No. 5,342,733 (Kanetake et al.). Additional surface matting agents prepared from a crosslinked polymer latex are also described in U.S. Pat. No. 5,380,637 (Yamashita et al.).
Useful matting agents that exhibit improved adhesion in hydrophilic colloid layers are described in U.S. Pat. No. 5,563,226 (Muehlbauer et al.). Crosslinked matting agents for use in surface layers of photographic silver halide materials are described in U.S. Pat. No. 5,834,174 (Smith et al.) and U.S. Pat. No. 5,965,339 (Smith et al.).
It is also conventional to include matting agent in protective layers on either or both sides of a photographic material. For example, one surface protective layer is disposed over the one or more silver halide emulsion layers disposed on a support while another surface matte layer can be disposed on the “backside” of the support and over either emulsion layers or light-insensitive layers such as pelloid or anti-curl layers, as described for example in U.S. Pat. No. 4,409,322 (Ezaki et al.).
A number of commercial photographic film products have been manufactured and sold that include a non-crosslinked matting agent underneath the silver halide emulsion layers. Such matting agents are generally included in what is known as a hydrophilic subbing layer that is applied to subbed or unsubbed polymer film supports. When the film supports are coated in this matter, they can be more readily transported and handled for application of additional layers without static buildup. Such matting agents include non-crosslinked polymeric particles having an average particle size of about 1 to 2 &mgr;m and a glass transition temperature of from about 100° C. to about 105° C.
In addition, commercial films (for example, KODAK X-OMAT 2 Dental Duplicating Film) are known that comprise crosslinked matting age beneath the silver halide emulsion layers but the average size of the matting agent particles is about 0.5-0.8 &mgr;m. Such particles are generally inferior in reducing static buildup and have minimal crosslinking (up to 2 weight %) and are not useful in every manufacturing situation.
Photographic film base (or support) is often coated with various light-insensitive subbing layers, and the “subbed” polymeric supports may be heat treated to provide dimensional stability prior to application of the silver halide formulations. In certain situations, one or more subbing layers may include matting agents for improved web transport and improved electrical conductivity. The conditions of manufacture have become increasing severe in recent years because of the need for increased manufacturing speeds and the use of higher temperature.
It has been found that during such procedures, some matting agents are softened from the heat treatment and tend to flake off the coated support and to collect on transport rollers and other equipment. This debris increases with manufacturing speed and necessitates frequent equipment cleaning and downtime. In addition, the buildup of matting agent on the transport rollers may cause indentations or “impressions” in a passing web that create physical and image defects and other abnormalities during and after silver halide emulsion layers have been applied. The present invention is designed to address these concerns.
SUMMARY OF THE INVENTION
The present invention solves the problems noted above with a photographic silver halide material comprising a polymeric support and having on at least one side thereof, one or more silver halide emulsion layers, and disposed between the polymeric support and the one or more silver halide emulsion layers, a light-insensitive adhesion-promoting layer comprising a polymeric matting agent having an average particle size of at least 1 &mgr;m and up to about 10 &mgr;m and a glass transition temperature of at least 120° C.
In preferred embodiments, the useful polymeric matting agent is composed of a polymer represented by the following Structure I:
wherein A represents recurring units derived from one or more polyfunctional ethylenically unsaturated polymerizable monomers, and B represents recurring units derived from one or more monofunctional ethylenically unsaturated polymerizable monomers, x is from about 5 to 100 weight %, and y is from 0 to about 95 weight %.
In still another preferred embodiment, a photographic silver halide material comprises a polyester support and having on at least one side thereof, one or more silver halide emulsion layers, and disposed between the polyester support and the one or more silver halide emulsion layers, a first light-insensitive adhesion-promoting layer comprising a polymeric matting agent having a average particle size of from about 1.2 to about 3 &mgr;m and a glass transition temperature of at least 135° C., and disposed between the first light-insensitive adhesion-promoting layer and the polyester support, a polymeric latex subbing layer,
the polymeric matting agent is composed of a polymer represented by the following Structure I:
wherein A represents recurring units derived from one or more polyfunctional ethylenically unsaturated polymerizable acrylates or methacrylates, and B represents recurring units derived from one or more monofunctional ethylenically unsaturated polymerizable acrylates or methacrylates, x is from about 10 to 30 weight %, and y is from about 70 to about 90 weight %.
This photographic silver halide material may further comprise a protective surface layer over the one or more silver halide emulsion layers, a pelloid layer on the backside of the polyester support, and disposed between the polyester support and the pelloid layer, a second light-insensitive adhesion-promoting layer comprising a polymeric matting agent having a average particle size of from about 1.2 to about 3 &mgr;m and a glass transition temperature of at least 135° C.,
the polymeric matting agent in the second light-insensitive hydrophilic subbing layer being composed of a polymer represented by the following Structure I:
wherein
A represents recurring units derived from one or more polyfunctional ethylenically unsaturated polymerizable acrylates or methacrylates, and B represents recurring units derived from one or more monofunctional ethylenically unsaturated polymerizable acrylates or methacrylates having only one polymerizable site, x is from about 10 to 30 weight %, and y is from about 70 to about 90 weight %,
the polymeric matting agents in the first and second light-insenitive hydrophilic subbing layers being the same or different.
This invention also provides a method of providing an image comprising processing an imagewise exposed photographic silver halide material described above using one or more aqueous photographic processing compositions.
The present invention reduces the equipment maintenance and product waste in the manufacture of film “base” for various photographic silver halide materials. The matting agent particles used in this invention have a higher glass transition temperature from sufficient crosslinking so they have a reduced tendency to soften under the heat treatment conditions used to make such film “base”. Moreover, they are large enough in size so they adequately reduce static buildup on the support during manufacturing operations. In addition, the preferred matting agents are prepared from solely acr
Adsit Eric J.
Lynch Patrick M.
Quinones Pedro R.
Smith Dennis E.
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