Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified backing or protective layer containing
Reexamination Certificate
2001-01-25
2002-02-19
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified backing or protective layer containing
C430S531000, C430S533000, C428S420000, C428S423100, C428S423500, C428S423700, C428S425500
Reexamination Certificate
active
06348305
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to photographic elements having a film support carrying an adhesion promoting layer on at least one side thereof
2. Background of the Art
Polyester film-forming materials have been used as supports in photographic materials due to their many favorable properties, including their excellent transparency. Polyester supports, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), triacetyl cellulose, polystyrene, polycarbonate and polyolefin laminate are examples of common polyesters. However, such polymer films have a hydrophobic surface and therefore, when the polymer is employed as the base film of the support for a photographic material, it is difficult to firmly bond to the support a photographic emulsion layer comprising a hydrophilic polymer (hydrophilic colloid), especially where mainly containing gelatin.
Two processes have been utilized as conventional techniques to overcome the above difficulty:
(1) a process in which a photographic emulsion layer is directly formed on the support to obtain a high bonding strength after having provided the support with a surface activation treatment (such as a corona discharge treatment, a glow discharge treatment, an active plasma treatment, a chemical treatment, a mechanical treatment, a UV treatment and equivalent processes); and
(2) a process in which an adhesion promoting layer is provided on the support subjected to the above surface treatment by coating, and then a photographic emulsion layer is formed thereon.
The latter process is effective and is widely performed commercially.
It is assumed that surface treatments are effected by forming some polar groups on a surface of a base film (which is originally hydrophobic) and by increasing a cross linking density on that surface, and as a result, it is considered that the affinity of the components contained in the adhesion promoting layer with the polar group is increased or the bonding strength between the adhesion promoting layer and the base film is enhanced.
Some useful compositions for adhesion promoting layers include polymers containing vinylidene chloride such as vinylidene chloride/methyl acrylate/itaconic acid terpolymers or vinylidene chloride/acrylonitrile/acrylic acid and the like; butadiene-based copolymers, glycidyl acrylate or methacrylate containing copolymers; or maleic anhydride-containing copolymers. These and other suitable compositions described, for example, in U.S. Pat. Nos. 2,627,088; 2,698,240; 2,943,937; 3,143,421; 3,201,249; 3,271,178; 3,443,950 and 3,501,301 provide the required adhesion when applied before orientation but are not effective when applied on oriented support. The effectiveness of these adhesive materials may be enhanced by the use of swelling or attack agents in the compositions, such materials, for example, including resorcinol.
An alternative approach to improving the enhancement of adhesion between the film support and gelatin layers disclosed in U.S. Pat. No. 4,695,532 is described as a discharge-treated polyester film support having coated directly thereon a crosslinked layer of an aqueous vinyl acrylate copolymer and gelatin. Although this system has good adhesion before processing, the adhesion performance is severely degraded by photographic developing solutions.
U.S. Pat. No. 4,689,359 discloses a polymer composition comprising (a) 1 to 60 wt. % of recurring units derived from a vinyl monomer having a primary amine addition salt component and/or a vinyl monomer having an aminostyrene addition salt component; (b) 0 to 50 wt. % of recurring units derived from a hydrophilic vinyl monomer and (c) 20 to 98 wt. % of recurring units from a hydrophobic non-ionic vinyl monomer. The polymers are useful in aqueous coating compositions, particularly for coating onto discharge-treated polyester film supports to form cross-linked layers to promote adhesion between the film support and the other emulsion layers in photographic elements such as silver halide emulsion layers. U.S. Pat. No. 5,639,589 and EP Application 729,063 describe polyester photographic film supports comprising a surface coated with a subbing layer comprising a mixture of gelatin and the same polymer composition described in U.S. Pat. No. 4,689,359. High dry adhesion, even with a thinner subbing layer and/or a higher gelatin:polymer ratio, is obtained.
U.S. Pat. No. 5,532,118 discloses photographic elements comprising a polyester film support having coated thereon a self-crosslinking polyurethane derived from an isocyanate terminated prepolymer extended with an aliphatic polyamine and end-capped with N-methylol hydrazide groups, the prepolymer being derived from a diisocyanate and a polyester polyol and having carboxylic salt groups on the polymer chain. The photographic element disclosed therein exhibits good wet and dry adhesion, before and after photographic processing.
U.S. Pat. No. 5,510,233 discloses a photographic material having a first and a second adhesion promoting layer and an emulsion layer coated in this order on the same side of a polyester support base, in which the first adhesion promoting layer is a hardened layer comprising a polyurethane latex and an ethoxy compound or a dichloro-s-triazine derivative, and the second adhesion promoting layer is a hydrophilic colloidal layer substantially consisting of gelatin. The polyurethane latex has breaking elongation lower than or equal to 300% or a tensile stress of at least 130 kg/cm
2
at 100% elongation. The composition of the adhesion promoting layers improves adhesion between the emulsion layer and the support and prevents delamination even under prolonged storage at high humidity condition. It also prevents the coated emulsion from cracking even at extremely low humidity storage. An additional advantage is the resistance against reticulation at the processing and the background clarity of the processed images.
U.S. Pat. No. 5,378,592 discloses a photographic material comprising a support of a polyester film, a first subbing layer provided thereon, a second subbing layer comprising gelatin provided on the first subbing layer and a photographic layer provided on the second subbing layer. The first subbing layer is a layer of polymer latex cured with an epoxy-type compound or a dichloro-s-triazine derivative, or the first subbing layer comprises a polymer which has a breaking elongation lower than or equal to 300% or a tensile stress of at least 130 kg/cm
2
. In particular, the photographic material contains an epoxy compound having not less than 4 epoxy groups (preferably 4 to 5).
U.S. Pat. No. 5,726,001 discloses a composite support comprising a polymeric film having coated thereon an electrically conductive layer and an auxiliary layer coated over the electrically conductive layer, wherein the polymeric film comprises a surface which has been activated by energetic treatment, and wherein the composite support further comprises an adhesion promoting layer comprising an aqueous dispersible, aliphatic, anionic polyurethane binder having a breaking elongation of at least 350% either between the polymeric film and the electrically conductive layer or between the electrically conductive layer and the auxiliary layer, and the electrically conductive layer or adhesion promoting layer is in contiguous contact with the activated surface of the polymeric film. The invention provides composite supports and imaging elements containing an electrically conductive antistatic layer having excellent adhesion to energetic surface-treated polymer film supports, and of auxiliary layers to the electrically conductive antistatic layer.
U.S. Pat. No. 5,707,791 discloses a silver halide photographic light-sensitive material with excellent adhesive property and scratch-resistance comprising: (a) a polyester support; (b) a silver halide emulsion layer coated on one side of said polyester support; (c) a resin layer coated on the other side of said polyester support, said resin layer comprising an antistatic agent selected from the group co
Barlocco Carlo
Puppo Paola
Valsecchi Alberto
Ferrania S.p.A.
Mark A. Litman & Assoc. P.A.
Schilling Richard L.
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