DE60123912T2 - Color photographic diffusion transfer film unit - Google Patents

Abstract

An ultraviolet shielding filter agent, which contains fine-particle titanium oxide, and which satisfies the following condition (A), (B) or (C): (A) that the fine-particle titanium oxide has an average primary particle diameter or average primary short-axis particle diameter of 1 to 45 nm and is surface-treated with a specific amount of aluminum oxide and/or silicon dioxide, and that the ultraviolet shielding filter agent further comprises a polyhydric alcohol; (B) that the fine-particle titanium oxide has an average primary particle diameter or average primary short-axis particle diameter from 1 to 45 nm, and has rutile crystallinity from 20 to 70%, and that the ultraviolet shielding filter agent further comprises a polyhydric alcohol; or (C) that the fine-particle titanium oxide has a primary particle shape of a cylindrical shape or a spindle shape, and that among average primary particle diameters of the fine-particle titanium oxide, a short-axis diameter is from 1 to 45 nm, a long-axis diameter is from 3 to 200 nm, and a ratio of the long-axis diameter to the short-axis diameter is from 2 to 10. A color diffusion transfer photographic film unit, which uses the ultraviolet shielding filter agent.

Description

Territory of invention

The The present invention relates to a photographic film unit for Color diffusion transfer and in particular, a peel-off type photographic film unit, wherein an image pickup element of a photosensitive element according to detached from development becomes. About that In addition, the present invention relates to a photosensitive Material which has excellent light resistance, low dependence the image density fluctuation on the stripping time, a slight image haze or image color due to the treatment solution, which remains in the image pickup element at the time of detachment, and an outstanding surface gloss having. About that In addition, the present invention relates to an ultraviolet screening filter means, containing the titanium oxide, that can be used to photograph the above Produce a film unit that has a lower quality or Has property fluctuation after a period of time and a low chemical activity (Toxicity) having.

background the invention

Ultraviolet shielding, which is an ultraviolet absorber use, which is made of an organic material are widely known. Because the ultraviolet absorber contained therein used is made of an organic material, the absorbent has many problems such as staining a high pH, the decomposition by light or the reaction with a different chemical agent and low solubility in water. Thus, the method of manufacture or use of the absorbent in dependence limited by the uses. In addition, the absorbent does not necessarily satisfy Safety requirements regarding Chemicals or the like. In addition, an ultraviolet screening filter means, which is no absorption change after a period of time and what a high security has, desirable.

To now was a photographic process for color diffusion transfer, which is an azo dye imaging agent Substance, well known, wherein an image pickup element and a photosensitive element are combined such that a diffusive azo dye, which differs from the image-forming substance itself differs, after the development using a viscous alkaline solution, which between the image pickup element and the photosensitive Element is being developed is formed.

In This photographic process also well knows a stripping system in which the viscous solution between the elements are developed and the elements become different from each other after the development / transmission replaced, so that a picture is obtained. The dye-providing compounds, which are described in U.S. Patent No. 3,928,312 are known as dye-releasing compounds for the Use in this transmission system known.

Around to immobilize the anionic dye after release, It is known to use a polymer containing a quaternary ammonium salt contains as described, for example, in US Pat. Nos. 3,958,995, 3,898,088 as a mordant in the image receiving layer of the image pickup element is described. additionally are polymers with a tertiary Imidazole ring in the side chain, as described in US Pat. Nos. 4,115,124, 4,282,305 and 4,273,853, has been known to improve durability towards light improve the immobilized dyes. In addition, for example Copolymers of a tertiary imidazole, as disclosed in JP-B-4-17418 ("JP-B" means a Japanese Examined Patent Publication) and JP-A-862803 ("JP-A" means an unexamined published Japanese Patent Application); Copolymers with a quaternary Ammonium salt group and a tertiary imidazole group, as it JP-A-60-60643 is known for the mordanting performance and stability across from Intensify light of the dyes. About that In addition, JP-A-10-142765 discloses Examples of detachment type photographic film units, which use a mordant containing an imidazole group. Furthermore It is known that a polymer containing a pyridine ring in the side chain contains is used as a mordant.

These Polymeric mordants have been developed to enhance the power anionic dyes which are entrained during transfer, to hold and to stability of the dyes To amplify light.

Indeed are in the detachment system, in which a viscous alkaline solution is developed, the above-mentioned polymers, the one quaternary Ammonium salt, and the polymer containing a pyridine ring, the single polymeric mordant, which achieves practical application to have.

Even though the ones mentioned above Techniques described in JP-A-10-142765 and the like the cloudiness, discoloration and have reduced other problems to some extent, are the physical film properties after peeling and at the time of peeling yet not satisfactory and there was another improvement in this requires.

On the other side is the improvement in stability over that Light fading using fine particles of titanium oxide in JP-A-6-118591. However, the sphere equivalent particle diameter was of titanium oxide (the diameter of a mold with an equivalent volume with regard to one individual particles of titanium oxide) described in the examples in JP-A-6-118591, 50 nm or more, and later studies have shown that the use of titanium oxide particles with a Particle diameter that falls within the range specified above, with the problems of insufficient transparency and reduced image density being related. Besides this optical influence was also found that in a snap-on instant photography the titanium oxide-containing layer a diffusion path of the image-forming Dyes and thus the titanium oxide physically forms the diffusion of the dyes is delayed, whereby the image density is reduced. Also related to the particle diameter of titanium oxide, wherein the particle diameter of which falls within the range of about 50 nm or larger, it was found that this is a considerable one Reduction in image density caused. The aforementioned JP-A-6-118591 does not disclose a process for producing fine particles of titanium oxide, which exerts no influence on the photographic density. Corresponding JP-A-6-118591, titanium oxide is preferably dispersed and in a hydrophobic binder system used. However, in the case an instant color image photograph, the image-forming dyes are water soluble and these dyes are in the hydrophobic binder at all non-diffusive, as described in JP-A-6-118591, wherein satisfactory Photographs are not produced. Thus, JP-A-6-118591 no information that suggests an instant color photograph.

EP-A-1 193 550 represents the state of the art under Article 54 (3) EPC and relates to an aqueous Dispersion, the titanium oxide and a photographic film unit for Color diffusion transfer contains wherein the image-receiving element comprises a titanium oxide-containing layer, which is produced by coating this dispersion.

EP 0 801 941 A1 relates to cosmetics having a UV screening effect and containing spindle-shaped fine particles of titanium dioxide having a minor axis of 0.03 to 0.06 μm, a major axis of 0.08 to 0.12 μm and an aspect ratio (major axis / minor axis) of 2 to 4.

EP 0 957 139 A1 discloses a zinc oxide-based cosmetic preparation which may contain titanium dioxide as the inorganic UV screening component.

JP 01/056607 A discloses a cosmetic aerosol which is prepared by mixing a colloidal solution that by dispersing silica-treated titanium oxide in water, in alcohol or in a polyhydric alcohol with a propellant was obtained.

GB 714,412 B relates to an aqueous photographic processing composition for producing prints as pressure-receiving surfaces. This document discloses a non-sized paper wherein a thin coating of a mixture of sodium carboxymethyl cellulose, dimethyl tartrate, glycerine and water has been applied to the surface thereof. In addition, it is taught that addition to this mixture of barium sulfate or titanium dioxide or other white pigments in suitable proportions bleaches the surface of the sheet.

DE-A-196 13 992 relates to the use of iron oxide-containing TiO ₂ pigments as UV screening filter means for photography. The average primary diameter of the iron oxide-containing TiO ₂ pigment is 1 to 100 nm.

Summary the invention

Accordingly It is an object of the present invention to provide a titanium oxide-containing Ultraviolet shielding to provide its dispersibility and stability after a Time span to be improved. Another task of the present The invention resides in a film unit for color diffusion transfer of the transfer type with an improved discoloration prevention property, Light resistance and provide film physical properties. This and more Objects, features and advantages of the invention will become apparent from the following Description stronger seen.

detailed Description of the invention

When a result of studies has been found by the present inventor that the use of titanium oxide with a primary particle diameter of 45 nm or less, for example, the discoloration prevention in an image, the light resistance and considerably improves the film physical properties. Indeed there is a need for the stability of such a dispersion and about that an improvement in the photographic image properties. The present invention has been made on the basis of others considering intensive studies completed the above.

• (1) Eine fotografische Filmeinheit zur Farbdiffusionsübertragung, die umfasst: ein Bildaufnahmeelement, das auf einem Träger eine Schicht, die eine neutralisierende Funktion aufweist, eine Bildaufnahmeschicht und eine Ablöseschicht, sukzessive in dieser Reihenfolge vom Träger, ein lichtempfindliches Element, das zumindest eine Silberhalogenid-Emulsionsschicht, kombiniert mit zumindest einer ein Farbstoffbild bildenden Verbindung, auf einem Träger, der eine lichtabschattende Schicht aufweist, aufweist; und eine entwicklungsfähige alkalische Behandlungszusammensetzung zwischen dem Bildaufnahmeelement und dem lichtempfindlichen Element, und die durch Entwickeln der alkalischen Behandlungszusammensetzungen zwischen diesen Elementen nach der Belichtung, und dann Ablösen des Bildaufnahmeelements und des lichtempfindlichen Elements voneinander ein Bild ergibt; worin das Bildaufnahmeelement eine Ultraviolett-Abschirmschicht umfasst, die durch Auftragen eines Ultraviolett-Abschirmfiltermittels gebildet wird, worin das Ultraviolett-Abschirmfiltermittel Feinpartikel von Titanoxid in einer Dispersion umfasst, die weiterhin einen mehrwertigen Alkohol umfasst, wobei das Ultraviolett-Abschirmfiltermittel die folgenden Bedingungen (B) und (C) erfüllt:
• (B) dass die Feinpartikel von Titanoxid eine Spindelform und einen mittleren Primärpartikeldurchmesser oder mittleren Primär-Kurzachsen-Partikeldurchmesser von 1 bis 45 nm und eine Rutilkristallinität von 20 bis 70% aufweisen, oder
• (C) dass die Feinpartikel von Titanoxid eine zylindrische oder eine spindelförmige Primärpartikelform aufweisen, und dass unter den mittleren Primärpartikeldurchmessern der Feinpartikel des Titanoxids ein Kurzachsendurchmesser 1 bis 45 nm, ein Langachsendurchmesser 3 bis 200 nm, und ein Verhältnis des Langachsendurchmessers zum Kurzachsendurchmesser 2 bis 10 beträgt, und dass der mehrwertige Alkohol Glycerin und/oder Ethylenglykol ist.
• (2) Die fotografische Filmeinheit zur Farbdiffusionsübertragung gemäß Punkt 1, worin der mehrwertige Alkohol Glycerin ist.
• (3) Die fotografische Filmeinheit zur Farbdiffusionsübertragung gemäss Punkt 1 oder 2, worin die Ultraviolett-Abschirmschicht in dem Bildaufnahmeelement in der Bildaufnahmeschicht und/oder als Überzugsschicht der Bildaufnahmeschicht (im Bildaufnahmeelement weiter vom Träger entfernt) angeordnet ist.

According to the present invention, the objects of the invention can be achieved by the following items (1) to (3):

• (1) A color diffusion transfer photographic film unit comprising: an image-receiving element having on a support a layer having a neutralizing function, an image-receiving layer and a release layer successively from the support in this order, a photosensitive element containing at least one silver halide Emulsion layer combined with at least one dye image forming compound on a support having a light shading layer; and a viable alkaline processing composition between the image-receiving member and the photosensitive member, and forming an image by developing the alkaline processing compositions between these members after exposure, and then peeling the image-receiving member and the photosensitive member apart from each other; wherein the image-receiving element comprises an ultraviolet shielding layer formed by applying an ultraviolet shielding filter agent, wherein the ultraviolet shielding filter agent comprises fine particles of titanium oxide in a dispersion further comprising a polyhydric alcohol, the ultraviolet shielding filter agent having the following conditions (B) and (C) satisfies:
• (B) that the fine particles of titanium oxide have a spindle shape and an average primary particle diameter or average primary short-axis particle diameter of 1 to 45 nm and a rutile crystallinity of 20 to 70%, or
• (C) that the fine particles of titanium oxide have a cylindrical or a spindle-shaped primary particle shape, and that among the average primary particle diameters of the fine particles of titanium oxide, a short-axis diameter of 1 to 45 nm, a long-axis diameter of 3 to 200 nm, and a ratio of long-axis diameter to short-axis diameter 2 to 10 and that the polyhydric alcohol is glycerol and / or ethylene glycol.
• (2) The color diffusion transfer photographic film unit according to item 1, wherein the polyhydric alcohol is glycerol.
• (3) The color diffusion transfer photographic film unit according to item 1 or 2, wherein the ultraviolet shielding layer is disposed in the image-receiving element in the image-receiving layer and / or as a coating layer of the image-receiving layer (further from the support in the image-receiving element).

The The present invention will be described more specifically below.

First, will the ultraviolet screening filter means used in the present Invention is to be used, described in detail. The ultraviolet screening filter means is a dispersion wherein the above-mentioned titanium oxide is in a medium (preferably water), which preferably contains a polyhydric alcohol, dispersed is.

For the production of titanium oxide used in the present invention can, can numerous methods are used. These methods include the Neutralization hydrolysis of a titanium salt, neutralization sodium titanate, the hydrolysis of a titanium alkoxide and the gas phase decomposition a titanium alkoxide.

Especially includes according to the neutralization hydrolysis a titanium salt, the manufacturing process the steps of hydrolysis of titanium tetrachloride, burning (firing), pulverization followed by particle size regulation, Surface treatment, Washing, drying and final Pulverization. According to neutralization of sodium titanate, the manufacturing process comprises the steps the hydrolysis of sodium titanate, alkali bleaching treatment followed by acid bleaching treatment and surface treatment and thus concludes this manufacturing process does not require a firing step. Here is the manufacturing process, which does not include a firing step, as defines a wet process.

The Titanium oxide raw material used in the present invention can be made by a firing or wet process become. Titanium oxide in the form of a cylinder or a spindle is preferably over the wet process made. The difference in the particle diameter or in the aspect ratio of which, due to the purity of titanium tetrachloride as a raw material, by the hydrolysis rate, by the firing temperature, by the drying temperature, by the conditions (concentration, Time period and temperature) for Post-processing (bleaching) with an acid and an alkali, through a surface treatment agent (Type and amount thereof) or the like are controlled. titanium oxide, which results from a wet process can be easily dispersed become. On the other hand, according to the firing method, the crystal system of titanium oxide or the amount of surface treatment agent the firing temperature or the time can be set. titanium oxide, which results from a firing process is in weather resistance outstanding.

Of the mean primary particle diameter or mean primary short axis particle diameter of titanium oxide 1 to 45 nm, preferably 3 to 40 nm and more preferably 5 to 30 nm. The term "mean Primary particle diameter "means the mean of the sphere equivalent diameter of primary particles in the case if its shape is spherical or substantially spherical is. The term "mean primary short axis particle diameter" means the mean of the short-axis particle diameter of primary particles in the case when whose shape is a cylindrical shape or a spindle shape. in the Case of spindle-shaped or cylindrical particles (preferably spindle-shaped particles) is whose long-axis diameter is generally 3 to 200 nm, preferably 5 to 150 nm and stronger preferably 10 to 100 nm. The ratio of the long-axis diameter to the short axis diameter (hereinafter referred to as an aspect ratio) of which is generally 2 to 10, preferably 2.5 to 8, and more preferably 3 to 6.

following becomes rutile crystallinity described in the present invention.

The rutile crystallinity is calculated as follows. Titanium oxide which is measured, and Silicone (especially silicon oxide or the like is used) are each mixed together such that the mass ratio of the former to the latter is 1/5. After that, the ratio between the peak area the rutile (1,1,0) plane and the peak area of silicon oxide X-ray diffraction receive. Such a relationship is made against MT600B (trademark, fine particles of titanium oxide from Tayca Corp. and not surface-treated, mean primary particle diameter: 50 nm) as a standard sample. This value is considered 100% of the rutile crystallinity used to the ratio between this value and the value of the sample to be measured. The resulting value (ratio) is called the rutile crystallinity in of the present invention.

If the rutile crystallinity of the crystal is big, the crystal is firmly formed, such that the chemical resistance, the weather resistance and the like thereof, but the refractive index of it is high. Thus, the optical transparency thereof may be disadvantageous be worsened. On the other hand, if the rutile crystallinity is low is, be the chemical resistance and the weather resistance diminished, but the refractive index becomes smaller. Thus be an unfavorable refraction, interference, total reflection and the like in the interface between the crystal and the surrounding medium (air, water or the like) is hardly influenced, so the transparency of the resulting film can be advantageous high. In the present In the invention, rutile crystallinity is in the range of generally 20 to 70%, preferably from 30 to 60%, and more preferably from 35 to 55%. If this value is too high in the present invention, can the movie in dependence look like a rainbow-colored film from the viewing angle. If the value is too low, the film can be influenced by active oxygen or the like can be broken or the movie may be due be discolored by oxidation of a coexisting organic compound, when the film is irradiated with intense light.

The rutile crystallinity can be described by the following in the process for the preparation be controlled by fine particles of titanium oxide, what later describes: firing temperature after the surface treatment, Drying temperature and time, temperature and time of aftertreatment (Bleaching) with an acid and an alkali and concentration of the acid and alkali. In connection thus, the rutile crystallinity can Also controlled by the particle diameter of titanium oxide.

As the titanium oxide which can be used in the present invention, a titanium oxide whose surface has been treated with a surface-treating agent may also preferably be used, and the surface-treating agent may be one of an inorganic material or an organic material. Preferred examples of the inorganic surface-treating agent include include alumina, zirconia, silica and zinc oxide.

When Fine particles of titanium oxide used in the present invention can, can, stronger preferably, a titanium oxide whose surface with alumina and / or Silica treated is used. The to be used Amount of alumina preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the mass of titanium oxide. The amount of Silicon oxide is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. When the amount of surface treatment agent too small can cause a bad dispersion or sedimentation the dispersed objects after a period of time. If the amount is too big, will the amount of titanium oxide considerably diminished, so that the desired Ultraviolet absorption property is worsened. The above-mentioned alumina and / or Silicone dioxide may also be preferred in combination with another Surface treatment agent be used, which consists of an inorganic material or can be made of an organic material. Preferred examples of inorganic surface treatment agents shut down Zirconia and zinc oxide. Examples of organic surface treatment agents shut down Siloxane, stearic acid and trimethylolpropane. The total amount of all surface treatment agents, which are used is preferably 3 to 45% by mass, more preferably 5 to 35% by mass, based on the mass of titanium oxide. Because the amount of used Treatment agent is larger, the dispersibility and the like become better. However will the amount of titanium oxide is relatively small, so that the absorption of Ultraviolet light decreases. As a result, one deteriorates desired stability across from Light. For this reason, the quantity should be suitably selected to match the two embodiments.

For example titanium oxide can be surface treated as follows.

synthesized Titanium oxide is dispersed with a phosphate such as sodium hexametaphosphate. The pH value of it becomes dependent from solubility of a surface treatment agent to be used. For this purpose, a suspension of alumina and / or silicon oxide added. After the addition, the pH of it becomes a pH adjusted to the solubility of the surface treatment agent reduce. this leads to to a sedimentation and adhesion of the surface treatment agent on the surface of titanium oxide. If necessary, the quantity or shape of the adhesion changed be determined by the concentrations of the surface treatment agent and Titanium oxide can be adjusted or by the reaction under a High reaction temperature or high temperature treatment or the like performed after the reaction becomes.

The coating amount of the ultraviolet screening filter means of the present invention may be appropriately selected. Preferably, the ultraviolet screening filter agent is used in such a manner that the coated amount of the aforementioned titanium oxide (which may be the above-mentioned surface-treated titanium oxide; the same applies to the following) is from 0.01 to 20 g / m ² . When the amount to be used is high, ultraviolet light is largely absorbed, but the transparency deteriorates. When the ultraviolet screening filter agent of the present invention is used in a color diffusion transfer photographic film unit, it is preferred that the titanium oxide be used in a coated amount of 0.01 to 20 g / m ² . As the amount to be used increases, the absorption of the ultraviolet light becomes larger. However, the drawback associated therewith is that the amount used is increased and the photographic density is slightly reduced. For this reason, it is preferable to select the amount appropriately. The coated amount of titanium oxide is preferably 0.02 to 10 g / m ^2, and more preferably 0.05 to 2 g / m ² .

The Titanium oxide described above may be commercially available be. For example, the titanium oxide may consist of TTO-51, 55, S, M and D series (trade names, manufactured by Ishihara Sangyo Kaisha Ltd.) and can be used in the present invention.

titanium oxide may be by dispersing the solid particles in a dispersion getting produced. The amount of water used is preferably 0.67 to 32, stronger preferably 1 to 19 times the mass of titanium oxide. As a dispersant may be, for example, a polyanionic compound and / or use of a condensed phosphate.

Specific examples of the polyanionic compound which can be used in the present invention include polyacrylic acid salts (eg, poly (sodium acrylate)), polymethacrylic acid salts (eg, poly (sodium methacrylate)), polymaleic acid salts (eg, poly (sodium maleate)), copolymers of an acrylic acid salt (eg, sodium acrylate) and methyl acrylate, copolymers of maleic acid and methyl vinyl ether, carboxyme methyl cellulose, carboxyethyl cellulose and carboxyl-modified polyvinyl alcohol. The polyanionic compound is preferably a polyacrylic acid salt or a polymethacrylic acid salt. Examples of the condensed phosphate include sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate. In addition, surfactants conventionally used (eg, sodium dodecylbenzenesulfonate and polyoxyethylene nonylphenyl ether), water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxymethyl cellulose, and polysaccharide) and the like can also be used together with the polyanionic compound and / or condensed phosphate. The amount of the polyanionic compound and / or the condensed phosphate used is preferably within the range of 0.5 to 50 mass% based on the amount of titanium oxide. When the amount of the polyanionic compound and / or the condensed phosphate used is increased, the ultraviolet light shielding effect decreases because the proportion of titanium oxide is considerably reduced. On the other hand, if the amount is too small, dispersion stability can not be ensured. Although the amount varies depending on the desired degree of dispersion and the desired state of dispersion, the amount of the polyanionic compound and / or the condensed phosphate used is more preferably 1 to 30 mass%, and most preferably 3 to 25 mass%. ,

In In the present invention, a polyhydric alcohol such as glycols as a dihydric alcohol, glycerol as a trihydric alcohol, Pentitol as a pentavalent Alcohol or hexitol as a hexavalent alcohol for the prevention the coagulation of titanium oxide used after the dispersion. Under Polyhydric alcohol is an alcohol that has a relatively low molecular weight and having a high hydrophilicity is preferred. Preferably, glycerol or ethylene glycol. The polyhydric alcohol may too the time when the titanium oxide is dispersed or alternatively the polyhydric alcohol may be after completion the dispersion of titanium oxide are added. The amount of The polyhydric alcohol to be used is preferably 1 to 100% by mass, more preferably 5 to 50 mass% and the strongest preferably 10 to 30% by mass, based on the amount of titanium oxide.

For dispersing of titanium oxide may be any dispersant, which in general for dispersion of solid particles is used. Examples of the dispersant which can be used include one dissolver, a ball mill, a paint shaker device, a sand mill, a horizontal disperser for the medium using dispersing media (commercialized under such brand names as DYNO-Mill, Eiger Mill and the like), a kneader, an ultrasonic disperser and a roller mill.

The Ultraviolet shielding layer for the use in the present invention may be by any known method applied (applied). It is preferable as a binder, a water-soluble Polymer such as gelatin, polyvinyl alcohol or carboxymethylcellulose to use. The amount of binder may vary depending on a required Purpose freely selected become. This amount is preferably 0.1 to 10 times, stronger preferably 0.2 to 6 times the mass of titanium oxide. As a coating aid For example, a known surfactant may be selected and used. Examples thereof include anionic dispersants such as alkylphenoxyethoxysulphonates, alkylbenzenesulphonates, alkylnaphthalenesulphonates, alkylsulfuric, Alkyl sulfosuccinates, sodium oleyl methyl tauride, formaldehyde condensates of naphthalenesulfonic acid, polyacrylic acid, polymethacrylic Copolymers of maleic acid and acrylic acid, carboxymethylcellulose and cellulose sulfate; nonionic dispersants, such as polyoxyethylene alkyl ethers, Esters of sorbitan fatty acids, Esters of polyoxyethylene sorbitan fatty acids; cationic dispersants; Betainserien dispersant; and nonionic, cationic and anionic surfactants containing fluorine. The ultraviolet shielding layer can be independent can be applied or by simultaneous double-layer coating be applied together with a dressing layer. The mordant layer may contain fine particles of titanium oxide.

The photographic film unit for color diffusion transfer of the present Invention will be explained below.

The photographic film unit for color diffusion transfer of the present The invention has an ultraviolet shielding layer in the image pickup element formed by a coating solution containing the Ultraviolet shielding of the present invention. The ultraviolet shielding layer (titanium oxide-containing layer) may may be a single layer or may be in two or more layers be divided. The ultraviolet shielding layer is preferably as a layer of the image-receiving layer and / or as an overlayer the image-receiving layer (namely a layer coming from the carrier further away than the image-receiving layer).

In The photographic film unit of the present invention can use the Ultraviolet screening layer and / or the image receiving layer in addition to the fine particles of titanium oxide, if necessary, an ultraviolet absorber (Ultraviolet shielding agent) of an organic substance such as a Hydroxyarylbenzotriazole compound, a benzoxazole compound, a Hydroxyaryltriazine compound, a benzophenone compound, a cinnamic acid ester compound or a butadiene compound. For the reason of a lesser coloring in the yellow hue up to a high pH range at completion Image formation is a hydroxyarylbenzotriazole compound and a hydroxyaryltriazine compound is particularly preferred.

The Mordant used in the photographic film unit of the present This invention will be described in detail below.

The Mordant used in the photographic film unit of the present Invention may be used alone or together with a hydrophilic binder such as gelatin or polyvinyl alcohol in the image-receiving layer of the image-receiving element may be added. The mordant is generally a polymer which is aligned is to diffusive dyes that were produced imagewise, to immobilize.

When Pickling agent is preferably a polymer used as a Constituent unit contains a repeating unit which by the following formula (I) and at least one repeating one Unit, selected from the group that consists of repeating units that by the following formula (II), formula (III), formula (IV) or formula (V) is shown:

Formula (I)

In the formula (I), R ₁ , R ₂ and R ₃ each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents a divalent linking group having 1 to 20 carbon atoms and M is 0 or 1;

Formula (II)

In the formula (II), R _{1 has} the same meaning as R ₁ in the formula (I), R ₄ represents an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and n is 0 or 1;

Formula (III)

In the formula (III), R _{1 has} the same meaning as R ₁ in the formula (I); R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and p and q are each 0 or 1;

Formula (IV)

In the formula (IV), R _{1 has} the same meaning as R ₁ in the formula (I), and D represents a divalent linking group necessary for the formation of a 5- to 7-membered ring together with the nitrogen atom and the carbonyl group is;

Formula (V)

In the formula (V), R ₁ , L and m each have the same meanings as those in the formula (I); and E represents a divalent linking group necessary for formation of a 5- to 7-membered ring together with C, and M represents a hydrogen atom or an alkali metal element.

The polymeric mordants for The use in the present invention may be two or more contain repeating units that are in different formulas, from the formula (II), the formula (III), the formula (IV) and the Formula (V) selected are included.

alternative may be the polymeric mordant for the use in the present invention two or more themselves Contain repeating units that are included in a formula are selected from the formulas will be given above.

In the formula (I), R ₁ , R ₂ and R ₃ each represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Examples of the lower alkyl group include methyl, ethyl, n-propyl, n-butyl, n- Amyl and n-hexyl groups. R ₁ , R ₂ and R ₃ are each more preferably a hydrogen atom, a methyl group or an ethyl group.

L represents a divalent linking group having 1 to 20 carbon atoms. An example of the group represented by L includes alkylene groups (eg, methylene, ethylene, trimethylene, and hexamethylene groups), phenylene groups (eg, o-, p-, or m-phenylene groups), arylenealkylene groups, -CO ₂ -, -CO ₂ -R ₂₃ - (wherein R _{23 represents} an alkylene group, a phenylene group or an arylenealkylene group), -CONH-R ₂₃ - (wherein R _{23 represents} the same group as above ) and -CON (-R ₂₁ ) -R ₂₃ - (wherein R _{21 represents} the same group as R ₁ ; and R _{23 represents} the same group as R ₂₃ above). The following groups are particularly preferred.

preferred special examples of the repetitive unit, which is through the Formula (I) are shown below.

In the formulas (II) and (III), R ₄ , R ₅ and R ₆ each represent an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, eg an unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, n-butyl group, iso Butyl group, n-amyl group, hexyl group, n-nonyl group, n-decyl group, n-dodecyl group and the like) and a substituted alkyl group (methoxyethyl group, 3-cyanopropyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydroxyethyl group, 2-butenyl group and the like), an alkoxy group ( Methoxy group, ethoxy group and the like), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, eg phenyl group, tolyl group, naphthyl group and the like) or an aralkyl group (preferably an aralkyl group having 7 to 30 carbon atoms, eg an unsubstituted aralkyl group (benzyl group, phenethyl group, Diphenylmethyl group, naphthylmethyl group and the like) and a substituted aralkyl group (4-methylbenzylg groups, 4-isopropylbenzyl group, 4-methoxybenzyl group, 4- (4-methoxyphenyl) benzyl group, 3-chlorobenzyl group and the like). Among these groups, for example, a methyl group, an ethyl group, an n-butyl group, an iso-butyl group, a phenyl group or a benzyl group is particularly preferred. R ₅ and R ₆ each represent a hydrogen atom besides the groups given above, and a hydrogen atom is particularly preferable in some cases.

preferred special examples of the repetitive unit, which is through the Formula (II) are shown below.

Examples of the repeating unit represented by the formula (III) include those repeating units having a structure described by the polymerization of the N-vinyl compounds described in "Gosei Kobunshi III", pages 1 to 51, published by Murahashi, Imoto and Tani, Asakura Shoten, 1971. Preferred specific examples of the repeating unit represented by the formula (III) are shown below.

In the formula (IV), D represents a divalent linking group necessary for producing a 5- to 7-membered ring together with the nitrogen atom and the carbonyl group. Examples of the repeating unit represented by the formula (IV) include the repeating units having a structure described by the polymerization of the N-vinyl compounds described in "Gosei Kobunshi III" mentioned above; getting produced. Examples of linking group D include a divalent linking group consisting of carbon atoms (eg, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ , CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - CH ₂ -CH ₂ -, -C (= O) -CH ₂ CH ₂ -, -C (= O) -CH ₂ CH ₂ CH ₂ -, and the like) is a divalent linking group consisting of carbon and Nitrogen atoms (eg, -NHCH ₂ CH ₂ -, -C (= O) -NH-C (CH ₃ ) ₂ -, -C (= O) -NHCH ₂ CH ₂ - and the like), a divalent linking group is composed of carbon and oxygen atoms (eg, -OCH ₂ CH ₂ -, -C (= O) -OCH ₂ CH ₂ -, -C (= O) -OC (CH ₃ ) ₂ -, and the like), and a divalent linking group which is composed of carbon and sulfur atoms (eg -SCH ₂ CH ₂ -, -C (= O) -S-CH ₂ CH ₂ - and the like).

Especially preferred is a divalent linking group consisting of carbon and nitrogen atoms.

preferred special examples of the repetitive unit, which is through the Formula (IV) are shown below.

In of Formula (V) is the divalent linking group E used for formation a 5- to 7-membered ring is necessary, preferably one, which forms a benzene ring. M is preferably hydrogen, potassium or sodium.

In the polymeric mordant used in the photographic film unit of the present invention occupies the repeating unit represented by formula (I), preferably 10 to 98 mol%, stronger preferably 40 to 90 mole percent of the total repeating units. The repeating unit represented by the formula (II), (III), (IV) or (V) occupies preferably 2 to 60 mol%, stronger preferably 3 to 50 mol% of the total repeating units. It is also preferred that the mordant be a different repeating one Contains unit, different from the above, repeating units different, and that the proportion of other repetitive unit preferably 40 mol% or less of the total repeating Units is.

Under the repeating units represented by the formula (II), (III) or (IV) is the repeating unit, selected from those represented by the formula (IV), particularly preferred.

Besides For example, the terminal ends of these polymers are not particularly limited and the terminal ends can a hydrogen atom, an alkyl group and the like.

The molecular weight of the polymeric mordant for use in the photographic film unit of the present invention is preferably 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too low, the polymer becomes easily mobile, whereas if the molecular weight is too large, coating of the mordant on an image-receiving material can be prevented.

The molecular weight of the polymeric mordant is more preferably 1 × 10 ⁴ to 2 × 10 ⁶ .

preferred specific examples of the polymeric mordant for use in the photographic Film unit of the present invention are given below. The Terminal ends of this polymeric compound are not particularly limited and the terminal ends can a hydrogen atom, an alkyl group and the like.

The mentioned above polymeric mordants are described in JP-B-4-17418 and the like, and other connections can according to the described Method synthesized in this patent literature or the like become.

In of the present invention can be used as a coating aid of a dispersant and a surfactant such as anionic Dispersants, e.g. Alkylphenoxyethoxysulphonates, alkylbenzenesulphonates, Alkylnaphthalenesulfonates, alkylsulfuric ester salts, alkylsulfosuccinates, Sodium oleylmethyltauride, naphthalenesulfonic acid / formaldehyde condensation products, polyacrylic acids, Polymethacrylic acids, maleic acid / acrylic acid copolymers, Carboxymethyl cellulose and cellulose sulfates; nonionic dispersant, e.g. Polyoxyethylene alkyl ethers, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters; cationic dispersant; and beta-type dispersants as well as fluorine-containing nonionic, cationic or anionic Surfactants use to be made.

In The photographic film unit of the present invention is the ratio of Mass of the coating aid, which in the polymeric mordant is used, preferably 0.01 to 0.5, and more preferably 0.1 to 0.3.

In the present invention, the method of dispersing the polymeric mordant is not particularly limited, and known methods can be used. For example, the polymeric Mordants may be used exclusively with gelatin (including a derivative thereof) or it may be used with a combination of gelatin and another binder in a mordant layer of the image receiving material. A hydrophilic binder can be used as this binder. Examples of the hydrophilic binder other than gelatin are typically transparent or transparent hydrophilic colloids, which include naturally occurring materials such as polysaccharides, eg, cellulose derivatives, starch and gum arabic, and synthetic polymers such as polyvinylpyrrolidone, acrylamide polymers and water-soluble polyvinyl compounds of polyvinyl alcohol.

In the present invention, the mixing ratio of the polymeric mordant / binder and the amount of the polymeric mordant to be coated can be easily determined by those skilled in the art with reference to the amount of the dyes to be dyed and the type or composition of the polymeric mordant. The ratio of the polymeric mordant / binder is preferably 20/80 to 90/10 (by mass). The amount of the polymeric mordant to be coated is preferably 0.2 to 15 g / m ^2, and more preferably 0.5 to 8 g / m ² .

The Layer containing the polymeric mordant can be formed by a usual coating method can also be dried in a usual way (i.e. the gelatin film at low temperature, followed by gradual Removal of water at 30 to 50 ° C) can be performed. However, that is in order to enhance the influence of the present invention, it prefers drying start the layer at a high temperature of 80 to 120 ° C, when the layer is coated.

One ordinary hardener (Such as aldehyde, vinyl sulfone, epoxy or active halogen compounds) in the layer containing the polymeric mordant. The Amount of curing agent to be used in the present invention is preferably 0.01 to 15 Mass%, stronger preferably 0.1 to 5% by mass, based on the amount of gelatin in the dressing layer.

The epoxy group-containing curing agents, the vinylsulfone group-containing curing agent and the aldehyde group-containing curing agent, each of which in the photographic film unit of the present Invention are explained below. The purpose of use of these connections lies in a cross linking between the polymeric mordant, between the polymeric mordant and a Binders such as gelatin and / or between binders such as To effect gelatin, so that the water resistance and the film physical Properties of the layer containing the polymeric mordant be satisfactory.

preferred specific examples of epoxy series curing agents, which in the photographic film unit of the present invention can be used are given below.

Specific Examples of the vinyl sulfane series curing agents include following compounds.

The Quantity (or the total amount of curing agent if two or more hardeners used together) of the curing agent, which in the photographic film unit of the present invention is used is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass on the amount of gelatin in the dressing layer.

In the present invention, it is preferable to use hydrophobic particles in the image-receiving element because the use of the hydrophobic particles can improve the adhesion properties of the surface of the photographic material. Especially suitable as hydrophobic particles are matting agents, which roughen the surface. Examples of the matting agent include particles of polymethyl methacrylate, particles of a methyl methacrylate / methacrylic acid copolymer, particles of silica (silica), particles of strontium barium sulfate, and light-insensitive silver halide fine grains. Although a fluorochemical surfactant, a silicone series compound, a liquid paraffin or the like may be a surface modifier that chemically changes surface properties, a matting agent that physically modifies surface properties provides more preferred effects in the present invention. The larger the particle diameter of a matting agent, the more preferable. In particular, a matting agent having a particle diameter larger than the thickness of the image-receiving layer to which the matting agent is added is preferable. The preferred amount of matting agent added, for example, depends on the material or particle diameter of the matting agent to be used. If the amount of the matting agent added is too large, haze will occur and feel will be inferior, and undesirable effects such as a rough surface feel will occur although the adhesion properties mentioned above have been improved. For these reasons, a preferable amount of the matting agent to be used is in the range of 0.003 to 0.10 g / m ² .

In of the present invention the hydrophobic particles also to the ultraviolet shielding layer (titanium oxide-containing layer) obtained by using a coating solution, the the ultraviolet screening filter means of the present invention contains is generated, and the release layer be added next to the image-receiving layer. In the photographic Film unit of the present invention is the thickness of the image-receiving layer preferably 2 to 15 microns and stronger preferably 4 to 8 microns.

The Ultraviolet screening filter means of the present invention not limited to use in photography, and the ultraviolet screening filter means may also be used as a filter material, which is mixed in a plastic can be used.

The Constituent elements present in the photographic film unit of the present Invention are explained below successively.

I. Photosensitive element

A) carrier

When carrier of the photosensitive element for use in the present invention Invention may be any of the smooth supports commonly used for photographic photosensitive materials are used. For example, paper, cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate and the like. The support is preferably provided with a primer layer provided. The carrier contains preferably, in general, a minute amount of a dye or pigments such as titanium oxide to prevent light transmission.

The Thickness of the carrier is generally 50 to 350 μm, preferably 60 to 210 microns and more preferred 70 to 150 μm.

If necessary, can on the back of the carrier a crimp compensation layer or an oxygen shielding layer as described in JP-A-56-78833 is to be provided.

B) light shielding layer

A Light-shielding layer containing a light-shielding agent and a hydrophilic Contains binder, will be between the carrier and the photosensitive layer.

When Light shielding means may be any material having a light shielding function be used and soot becomes particularly preferred. Decomposable dyes, for example in U.S. Patent No. 4,615,966 may also be used.

When Binders used to add the light shielding agent For example, any binder can be used as long as it can disperse the light-shielding agent such as carbon black, and becomes gelatin prefers.

When Raw materials of carbon black may be those by any method such as a tunneling method, thermal process and furnace process as it is for example of Donnel Voet, "Carbon Black ", Marcel Dekker, Inc. (1976).

Even though there is no special restriction at the size of one carbon black particle are those with a particle size of 30 to 180 microns are preferred. The amount of a black pigment which acts as a light-shielding agent is added, according to the sensitivity of the photosensitive material, which is shielded to be controlled, but the amount is preferably about 5 times to about 10 times, based on the optical Density.

C) Photosensitive layer

In the present invention provides a photosensitive layer, a silver halide emulsion layer coated with a dye image-forming Substance is combined as an overcoat of the aforementioned Light shielding provided. Structural elements of Photosensitive layer will be explained in retrospect.

(1) Dye image-forming substance

The dye-image forming substance for use in the present invention is a non-diffusion compound which releases a diffusive dye (which may be a dye precursor) or a compound which is changed in diffusibility in the context of silver development, and is described in "The Theory of the Photographic Process ", Macmillan, Fourth Edition. These compounds can each be represented by the following formula (X): (DYE-Y) _n -Z formula (X) wherein DYE represents a dye group, a dye group having a short wavelength for a short time, or a dye precursor group, Y represents a single bond or a linking group; Z is a group having a property of producing a difference in diffusibility between the compounds represented by (DYE-Y) _n -Z or to release a DYE to account for a difference in diffusibility between the released dye and the (DYE -Y) _n -Z, which corresponds to a photosensitive silver salt or inversely corresponds with a picture-like latent image; and n is 1 or 2, where two (DYE-Y) groups may be the same or different when n is 2.

In dependence from the function of the Z group, these compounds are roughly in Divided compounds of the negative type, which are changed to become diffusible in a silver-developed surface, and in positive-type compounds that are altered to not in one developed surface to become diffusible.

When special examples of the negative type Z are included, that are capable of being oxidized and divided to a diffusible Release dye as a result of development.

Specific Examples of Z are described, for example, in US Pat. Nos. 3,928,312, 3,993,638, No. 4,076,529, No. 4,152,153, No. 4,055,428, No. 4,053,312, No. 4,198,235, No. 4,179,291, No. 4,149,892, No. 3,844,785, No. 3,443,943, No. 3,751,406, No. 3,443,939, No. 3,443,940, No. 3,628,952, no. 3,980,479, No. 4,183,753, No. 4,142,891, No. 4,278,750, No. 4,139,379, No. 4,218,368, No. 3,421,964, No. 4,199,355, No. 4,199,354, No. 4,135,929, No. 4,336,322 and No. 4,139,389, JP-A-53-50736, JP-A-51-104343, JP-A-54-130122, JP-A-53-110827, JP-A-56-12642, JP-A-56-16131, JP-A-57-4043, JP-A-57-650, JP-A-57-20735, JP-A-53-69033, JP-A-54-130927, JP-A-56-164342 and JP-A-57-119345.

Examples the particularly preferred group under Z of the redox compounds, the negative-type dyes release N-substituted sulfamoyl groups (Examples of the N-substituent include groups derived from aromatic Hydrocarbon rings and heterocycles are derived, a) one. Examples of typical groups of Z are given below, but not limited to the following groups.

The Positive type compounds are described in "Angew Chem. Int. Ed. Engl.", 22, 191 (1982). described.

When Specific examples of the positive-type compound may be compounds (Dye Developing Agents) mentioned at startup in an alkaline state are diffusible and in the development oxidized to become non-diffusible. Typical examples from Z who for Compounds of this type are suitable include such as described in U.S. Patent No. 2,983,606.

A another type is one which, for example, a diffusible dye Self-closing closure releases in an alkaline environment, the but essentially the release of the dye stops when it is oxidized together with the development. Special examples of Z having such a function are described, for example, in US Pat No. 3,980,479; JP-A-53-69033; JP-A-54-130927; and U.S. Patent Nos. 3,421,996 and No. 4,199,355.

One another type closes those that do not release any dye themselves, but release a dye during reduction. Connections from this one Species are used in conjunction with an electron donor, making them a diffusible Dye can deliver imagewise due to the reaction with the remaining electron donor, by the silver development is oxidized imagewise. Examples of atomic Groups having such a function are described, for example, in US patents No. 4,183,753, No. 4,142,891, No. 4,278,750, No. 4,139,379 and No. 4,218,368, JP-A-53-110827, in U.S. Patent Nos. 4,278,750, no. 4,356,249 and No. 4,358,525, JP-A-53-110827, JP-A-54-130927, JP-A-56-164342, Published Technical Report ("Kokai-Giho") 87-6199 and EP-A-220,746 (A2).

Specific Examples of the above are exemplified below, but not limited to the following groups.

If a compound of this kind is used, it is preferred in combination with an anti-diffusible electron donating Compound (known as an ED compound) or a precursor thereof used. Examples of the ED compound are described, for example U.S. Patent Nos. 4,263,393 and 4,278,750 and JP-A-56-138736.

When specific examples of yet another type of dye imaging agent Substance can also the following compounds are used.

In In the formulas, DYE represents a group containing a dye the same meaning as described above, or a group, the one forerunner of the dye.

The Details of this dye-forming substance are disclosed in U.S. Patent Nos. 3,719,489 and No. 4,098,783. On the other hand are special ones Examples of the dye represented by the formula "DYE" are described in the following literatures.

Examples of yellow dyes:

Such, U.S. Patent Nos. 3,597,200, No. 3,309,199, No. 4,013,633, U.S. Pat. No. 4,245,028, No. 4,156,609, No. 4,139,383, No. 4,195,992, No. 4,148,641, No. 4,148,643 and No. 4,336,322; JP-A-51-114930, JP-A-56-71072; Research Disclosures No. 17630 (1978) and No. 16475 (1977) are.

Examples of Magenta Dyes:

Such, US Pat. Nos. 3,453,107, 3,544,545, 3,932,380, US Pat. No. 3,931,144, No. 3,932,308, No. 3,954,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104 and No. 4,287,292; JP-A-52-106727, JP-A-53-23628, JP-A-55-36804, JP-A-56-73057, JP-A-56-71060, JP-A-55-134.

Examples of cyan dyes:

Such, U.S. Patent Nos. 3,482,972, 3,929,760, 4,013,635, U.S. Pat. No. 4,268,625, No. 4,171,220, No. 4,242,435, No. 4,142,891, No. 4,195,994, No. 4,147,544, No. 4,148,642; UK Patent No. 1,551,138; JP-A-54-99431, JP-A-52-8827, JP-A-53-47823, JP-A-53-143323, JP-A-54-99431, JP-A-56-71061; European patents (EP) Nos. 53,037 and 53,040; Research Disclosures No. 17,630 (1978) and No. 16,475 (1977).

These Connections can using the method described in JP-A-62-215,272, pages 144-146 is to be dispersed. In these dispersions, the Compounds described in JP-A-62-215,272, pages 137-144 be.

(2) Silver halide emulsion

The Silver halide emulsion for the use in the present invention may be either an emulsion of the negative type, which has a latent image mainly on the surface of a silver halide grain, or a direct positive emulsion internal latent image type which has a latent image within one Silver halide grain forms.

Examples The internal latent image type direct positive emulsion includes one so-called "conversion type" emulsion, which is prepared is made by making use of the difference between the solubility between silver halides; a "core / shell type" emulsion that is prepared by at least the photosensitive side of an inner core particle a silver halide with an external shell of a silver halide is prepared, wherein the inner core particles with a metal ion is doped, chemically sensitized or with both treatments provided; and other emulsions. These emulsions are in U.S. Patent Nos. 2,592,250 and 3,206,313, UK Patent No. 1,027,146, U.S. Patents No. 3,761,276, No. 3,935,014, No. 3,447,927, No. 2,297,875, U.S. Pat. No. 2,563,785, No. 3,551,662 and No. 4,395,478, West German Patent No. 2,728,108, U.S. Patent No. 4,431,730 and the like.

If an internal latent image type direct positive emulsion is used it is necessary to have a surface fog core by using light or a nucleating agent after imagewise Provide exposure.

Examples of the nucleating agent who for hydrazines used in the above purpose include those described in U.S. Pat U.S. Patents Nos. 2,563,785 and 2,588,982; Hydrazines and hydrazones, for example, described in U.S. Patent No. 3,227,552; heterocyclic quaternary Salt compounds described in U.K. Patent No. 1,283,835, JP-A-52-69613, in the U.S. Patent Nos. 3,615,615, 3,719,494, 3,734,738, 4,094,683, and 4,115,122 are described; Sensitizing dyes with a Substituent capable of nucleation in the dye molecule, as described in U.S. Patent No. 3,718,470; thioharnstoffartige Types of compounds of acylhydrazine series, for example in U.S. Patent Nos. 4,030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013 and 4,276,364, in which UK Patent No. 2,012,443 is described; and compounds of acylhydrazine series to which a thioamido ring or a heterocyclic group such as triazole or tetrazole as one Adsorption group is bound, as described in US Pat. Nos. 4,080,270 and 4,278,748, UK Patent No. 2,011,391B and the like is.

In the present invention, a spectral sensitizing dye may be used in combination with the negative type emulsion and / or the internal latent image type direct positive emulsion. Specific examples of the spectral sensitizing dye are disclosed in JP-A-59-180550, JP-A-60-140335, Research Disclosure (RD) No. 17029, US Patent No. 1,846,300, US Patent No. 2,078,233, US Pat 2,089,129, U.S. Patent No. 2,165,338, U.S. Patent No. 2,231,658, U.S. Patent No. 2,917,516, U.S. Patent No. 3,352,857, U.S. Patent No. 3,411,916, U.S. Patent No. 2,295,276, U.S. 2,481,698, U.S. Patent No. 2,688,545, U.S. Patent No. 2,921,067, U.S. Patent No. 3,282,933, U.S. Patent No. 3,397,060, U.S. Patent No. 3,660,103, U.S. Patent No. 3,335,010, U.S. Patent No. 3,352,680 US Pat. No. 3,384,486, US Pat. 3,623,881, U.S. Patent No. 3,718,470, U.S. Patent No. 4,025,349, and the like.

(3) Structure of Photosensitive layer

Around a natural one Color can be reproduced by a subtractive color process a photosensitive layer comprising at least two combinations the emulsion which is spectrally indicated by the above spectrally sensitizing dye is sensitized and it may be the aforementioned dye-image-forming substance, which a dye with a selective spectral absorption in the same wavelength range as the emulsion has been used. The emulsion and the Dye-forming substance can be coated in such a way that they overlap as separate layers or can be coated as a single layer by mixing it. when the dye-forming substance has an absorption in the spectral sensitive Area of the emulsion that is combined with, under the Condition that the dye-image forming substance coat is the separate layer system is preferred. Also, the emulsion layer from a large number of emulsion layers with different sensitivities to one another be assembled and above In addition, an optional layer between the emulsion layer and the color image forming substance layer. For example, a layer containing a nucleation development accelerator, as described in JP-A-60-173541 described, or a supporting wall layer, as described in JP-B-60-15267, to increase the density of a resulting color image and it is also possible to provide a reflective layer, about the sensitivity of the photosensitive element.

The reflective layer is a layer that generally comprises a white pigment and a hydrophilic binder. The white pigment is preferably titanium oxide and the hydrophilic binder is preferably gelatin. The amount of titanium oxide to be coated is generally 0.1 g / m ² to 8 g / m ^2, and preferably 0.2 g / m ² to 4 g / m ² . Examples of the reflective layer are described in JP-A-60-91354.

In A preferred multilayer structure is a combination unit from a blue-sensitive emulsion, a combination unit from a green-sensitive Emulsion and a combination unit of a red-sensitive emulsion arranged in this order from the coating exposure side.

It may any layer, if necessary, between the emulsion layer units are provided. Especially Preferably, an intermediate layer is provided to one undesirable To prevent influence, such that the effect due to the Development of a particular emulsion layer another emulsion layer unit affected.

If a developing agent in combination with a non-diffusive one Dye-forming substance is used, contains the intermediate layer preferably a non-diffusive reducing agent for diffusion an oxidized product of the developing agent. Specific examples of the non-diffusive reducing agent do not close diffusive hydroquinones, sulfonamidophenols, sulfonamidonaphthols and the like. About that In addition, specific examples are disclosed in JP-A-50-21249, JP-A-50-23813, JP-A-49-106329 and JP-A-49-129535. U.S. Patent Nos. 2,336,327, 2,360,290, 2,403,721, 2,544,640, 2,732,300, 2,782,659, 2,937,086, 3,637,393 and 3,700,453, UK Patent No. 557,750, JP-A-57-24941, JP-A-58-21249 and the like. The proceedings of dispersing these substances are described in JP-A-60-238831 and JP-B-60-18978.

If a compound containing a diffusive dye through a silver ion, as disclosed in JP-B-55-7576, is used, For example, it is preferred that the intermediate layer contains a compound which the silver ion supports.

If necessary, an irradiation prevention layer, a layer, which is a UV absorber contains a protective layer and the like in the present invention to be provided.

II. Image pickup element

A) carrier

In The present invention can be used as a support for the image pickup element to be made by a wearer, which is able to withstand the development temperatures.

in the General close Examples of the carrier Paper and a synthetic polymer (film). Special examples of usable vehicle shut down Polyethylene terephthalates, polycarbonates, polyvinyl chlorides, polystyrenes, Polypropylenes, polyimides and cellulose (e.g., triacetylcellulose) as well as films thereof containing a pigment such as titanium oxide therein one. additional Examples of the carrier shut down synthetic film treatment papers made of polypropylene or similar; different papers, made from one Pulp of a synthetic resin such as polyethylene and a natural one Cellulose; Yankee paper, Baryta papers, coated papers (in particular cast coated papers), metals, fabrics, glasses and the like. The above materials can individually for the preparation of the carrier or alternatively, the carrier may be any of these Materials composed of one side or both sides laminated with a synthetic polymer such as polyethylene. About that In addition, polyethylene containing carbon black kneaded therein may intervene the paper sheets added to provide a light-shielding effect. Besides can also carriers, which are described in JP-A-62-253159, pages (29) to (31) become.

The surface this carrier can with an antistatic agent such as carbon black, a semiconductor metal oxide, including Tin oxide or alumina sol and with a hydrophilic binder be coated.

B) release layer

In The present invention provides a release layer which can be used in any Arrangement on the image pickup element within the unit development is over will be provided. Thus, it is necessary that the release layer is easily detached after processing.

When Materials of the release layer can those described, for example, in JP-A-47-8237, JP-A-59-220727, JP-A-59-229555, JP-A-49-4653, in U.S. Patent Nos. 3,220,835 and 4,359,518, JP-A-49-4334, JP-A-56-65133, JP-A-45-24075 and U.S. Patent Nos. 3,227,550, No. 2,759,825, No. 4,401,746 and No. 4,366,227 and the like are to be used. As a specific example of the material can water-soluble (or alkali-soluble) Cellulose derivatives are given.

Examples of cellulose derivatives Hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, Ethylcellulose, cellulose nitrate and carboxymethylcellulose. Other examples include a variety of natural Polymers, for example alginic acid, Pectin, gum arabic and the like. Also can be different modified gelatin, for example acetylated gelatin, phthalated gelatin and the like mentioned become. About that can out as other examples, water-soluble synthetic polymers are used. Examples thereof include polyvinyl alcohols, Polyacrylates, polymethyl methacrylates, polybutyl methacrylates or Copolymers of these compounds and the like.

The release layer can be a single layer or one made up of a variety of Layers as described in JP-A-59-220727, JP-A-60-60642 or the like is described, is composed.

It it is preferred that the dye diffusion transfer photosensitive Material according to the present Invention a neutralizing function between the carrier and the photosensitive layer or between the support and the image receiving layer or on the image pickup element.

C) Layer with a neutralizing function

The Layer having a neutralizing function for use in the present Invention is a layer that is generally an acidic substance contains in an amount which is sufficient to provide alkali delivery of treatment compositions to neutralize, and it may be one with a multilayer structure, the one neutralizing rate-controlled layer (timing layer), an adhesion-enhanced layer and the like according to need includes. A preferably acidic substance is a substance that an acidic group with a pKa of 9 or less (or a Precursor group which provides such an acidic group by hydrolysis). More preferred Examples of the acidic substance include higher fatty acids such as oleic acid, as described in U.S. Patent No. 2,983,606; and polymers of acrylic acids, methacrylic or maleic acid and their half esters or acid anhydrides, as disclosed in U.S. Patent No. 3,362,819; copolymers an acrylic acid and an acrylate as described in French Patent No. 2,290,699 is disclosed; and latex-type acidic polymers as disclosed in US Pat No. 4,139,383 or Research Disclosure No. 16102 (1977) is.

In addition to the above compounds, acidic substances disclosed in US Pat. 4,088,493, JP-A-52-153739, JP-A-53-1023, JP-A-53-4540, JP-A-53-4541, JP-A-53-4542 and the like are given as examples.

Specific Examples of the acidic polymer include a copolymer of a vinyl monomer such as ethylene, vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl ester, Copolymer of butyl acrylate and acrylic acid, cellulose, acetate / hydrogen phthalate and the like.

The previously mentioned polymer acid can be used by mixing with a hydrophilic polymer becomes. Examples of such a polymer include polyacrylamide, polymethylpyrrolidone, Polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, Hydroxyethylcellulose, polymethylvinylether and the like. Among these compounds, polyvinyl alcohol is preferable.

Also can be a polymer such as cellulose acetate, which differs from the hydrophilic Polymer, mixed with the above-mentioned polymer acid become.

The Amount of polymer acid, which is applied is according to the amount of an alkali, that between the photosensitive element and the image pickup element is developed, controlled. The equivalence ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of polymer acid is too low is, the hue of a transferred dye may change or it can be a coloring on a white Background section occur, whereas if the amount is too large, this brings a disadvantage in such a way that a change in the hue or reduced light resistance occurs. The equivalence ratio is more preferred 1.0 to 1.3. The quality of Photographs can also be diminished when the amount of hydrophilic Polymer, which is mixed, too large or too small. The mass ratio of Hydrophilic polymer to the polymer acid is generally 0.1 to 10 and preferably 0.3 to 3.0.

In Any of the additives in. can be used in the present invention the layer with a neutralizing function for different Purposes are incorporated. For example, a curing agent, which is known to a person skilled in the art for the purpose of film hardening Layer are added and a polyvalent hydroxyl compound such as polyethylene glycol, polypropylene glycol or glycerol can for Purposes of improving brittleness be added to the film. additionally may, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor or its precursor and the like are added become.

When Material for the timing layer, which in combination with the neutralization layer can be used, a polymer is suitable which reduces the alkali permeability such as gelatin, polyvinyl alcohol, partially acetylated polyvinyl alcohol, Cellulose acetate or partially hydrolyzed polyvinyl acetate; one Latex polymer obtained by the copolymerization with a small Amount of a hydrophilic comonomer such as an acrylic acid monomer and which is an active energy for permeation an alkali; and a polymer having a lactone ring.

Under These polymers are cellulose acetates used for the generation of the timing layer as disclosed in JP-A-54-136328 and in U.S. Patents No. 4,267,262, No. 4,009,030, No. 4,029,849 and the like is; Latex polymers prepared by the copolymerization a small amount of a hydrophilic comonomer such as acrylic acid in JP-A-54-128335, JP-A-56-69629, JP-A-57-6843 and U.S. Patent Nos. 4,056,394, 4,061,496, 4,199,362, No. 4,250,243, No. 4,256,827, No. 4,268,604, and the like is; Polymers having a lactone ring as disclosed in US Pat. 4,229,516; and other polymers as disclosed in JP-A-56-25735, JP-A-56-97346, JP-A-57-6842, European Patent (EP) No. 31,957A1, EP No. 37,724A1 and EP No. 48,412A1 and the like is particularly suitable.

In addition to those described above, those described in the following references can also be used:
U.S. Patent No. 3,421,893, U.S. Patent No. 3,455,686, U.S. Patent No. 3,575,701, U.S. Patent No. 3,778,265, U.S. Patent No. 3,785,815, U.S. Patent No. 3,847,615, U.S. Patent No. 4,088,493, U.S. Patent No. 4,123,275, U.S. Patent No. 4,148,653, U.S. Patent No. 4,201,587, U.S. Patent No. 4,288,523, U.S. Patent No. 4,297,431, West German Patent Application (Laid-Open) No. 1,622,936, ibid. 2,162,277 and Research Disclosure 15162, No. 151 (1976).

The Timing layer that uses these materials can be a single Layer or a combination of two or more layers.

To the timing layer, which consists of any of these materials has been prepared, a development inhibitor and / or its precursor as for example in the US Patent No. 4,009,029, West German Patent Application (Laid-Open) No. 2,913,164, ibid. No. 3,014,672, JP-A-54-155837, JP-A-55-138745 and the like discloses a hydroquinone precursor as described in US Pat No. 4,201,578 and other suitable photographic additives or their precursor be incorporated.

Furthermore, because the layer is present with a neutralizing function to one neutralizing auxiliary layer as described in JP-A-63-168648 and JP-A-63-168649 to provide an influence on the Reduction of change a transferred one Density due to the time after processing.

D) Image recording layer

A Layer containing the aforementioned Polymerbeizmittel can be used effectively.

E) Others

in the Difference to the layer with a neutralization function can a backing layer, an intermediate layer and the like as a layer having auxiliary functions to be provided.

The backing is provided to the ripple and to control a lubricant capability or function to provide the light shield.

III. Alkaline treatment composition

sThe Treatment composition for the use in the present invention is intended to that they are even between the photosensitive element and the image pickup element developed the exposure of the photosensitive element, so that the development of the photosensitive layer is performed. For that contains the composition for example, an alkaline agent, a viscosity-enhancing agent, a developer, about it addition, a development accelerator or a development inhibitor for the Control of development, an antioxidant to prevent the deterioration of the developing agent and the like.

The Alkaline agent is one that is sufficient to maintain the pH a solution within a range of 12 to 14. Examples of alkaline Close funds Hydroxides of an alkali metal, (e.g., sodium hydroxide, potassium hydroxide and lithium hydroxide), phosphates of an alkali metal (e.g., potassium phosphate), guanidines and hydroxides of a quaternary Amine (e.g., tetramethylammonium hydroxide). Among these compounds For example, potassium hydroxide and sodium hydroxide are preferred.

The Viscosity enhancing agent is for the development of the treatment solution used evenly and for the maintenance of adhesion between the photosensitive layer and the cover layer. For example, as a viscosity-enhancing agent an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose, and preferably an alkali metal salt of hydroxyethyl cellulose or sodium carboxymethyl cellulose used.

When a preferred developing agent may use any one of them which cross-oxidize a color image forming substance and essentially no staining cause even if it is oxidized. The development agent can be either alone or in a combination of two or more Development agents are used. The developing agent can in the form of a precursor used of it. The developing agent may be in a particular Layer of the photosensitive element or in an alkaline treatment solution be included. As specific examples of the developing agent can aminophenols and pyrazolidinones. Among these compounds are Pyrazolidinone particularly due to the lower occurrence of staining prefers.

As examples of these pyrazolidinones are exemplified 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3- Pyrazolidinone, 1-phenyl-4-Me methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and the like.

Also, the alkaline processing composition (eg, an alkaline solution composition) is preferably transferred to the photosensitive material in a developed thickness (the amount of the processing solution per m ² after the processing solution is transferred) of 20 to 200 μm.

In of the present invention the development temperature in the development of the photosensitive Materials for the use in the present invention preferably 0 to 50 ° C and more preferred 0 to 40 ° C.

any one the photosensitive element, the image-receiving element and the alkaline processing composition, for example, a development accelerator, described on pages 72-91 is, contain, a curing agent, this on pages 146-155 is described, a surface active Means that on pages 201-210 described, a fluorine-containing compound described on pages 210-222 is a viscosity enhancing agent, that on pages 225-227 described, an antistatic agent described on pages 227-230 a polymer latex described on pages 230-239 is a matting agent, which is described on page 240, each of which is disclosed in JP-A-62-215272 are described.

The titanium oxide-containing ultraviolet screening filter agents of the present invention Invention is in the dispersibility and stability in the course the time has improved and is for the photograph prefers. This color diffusion transfer film unit of the transfer type of the present invention using this ultraviolet screening filter agent is, is in anti-coloring property, Light resistance and outstanding in the film-physical properties.

Furthermore indicates the photographic film unit for the color diffusion transfer not only improved lightfastness of the present invention, film physical properties and anti-staining property on, but also an outstanding photographic image quality of the resulting image in some cases. About that In addition, the photographic film unit for the color diffusion transfer the present invention improved production stability Incorporating a special polyhydric alcohol in the ultraviolet screening filter means, which is used to achieve the stability of the filter medium after a period of time to improve.

The The present invention will be explained in more detail by the following examples explained, but the invention is not limited thereto. Therein, "part" and "%" mean parts by mass or mass%, as far as it is concerned not stated otherwise.

EXAMPLE

Example 1-1

To 35 parts of fine particles of titanium oxide TI-A01 (with a medium Primary particle diameter of 15 nm, which were surface treated with 10% alumina), 5.2 Divide poly (sodium acrylate) as a dispersant (trade name: POIZ-530, manufactured from Kao Corporation), 10.5 parts glycerin as a coagulation inhibitor 49.3 parts of water were added and mixed, and the resulting mixture was allowed to stand for 30 minutes at 3000 rpm by means of a dissolving device (manufactured by Tokushu Kika Kogyo Co., Ltd.). After that, the Mixture passed through a horizontal sand mill 5 times at 250 rpm. In this way, a dispersion A01 was obtained.

The Dispersion A01 was mixed with gelatin such that the ratio of Titanium oxide to gelatin was 2 to 1, and then the mixture is applied to a polyethylene terephthalate support so that the optical density at 350 nm is 1 (sample A01).

It a sample B01 was prepared in the same way as sample A01, with the exception that the above-mentioned fine particles of titanium oxide TI-A01 by those with an average primary particle diameter of 55 nm were exchanged and surface treated with 10% alumina were.

Two grams of each of the following compounds A and B were mixed with 4 g of tricresyl phosphate, 5 ml of ethyl acetate and 2 g of gelatin. The mixture was emulsified and stirred at 5000 rpm for 5 minutes a dissolution apparatus (Tokusyu Kika Kogyou Co., Ltd.). In the same manner as in the preparation of Sample A01, the resulting emulsion was coated on a polyethylene terephthalate support so that the optical density at 350 nm became 1 (Sample C01).

A Sample D01 was prepared in the same manner as sample A01 with the exception that glycerin was removed from sample A01 (it was not used).

Connection A

Compound B

The optical density of the respective samples at 400 nm, the density change ratio (resistance) of which, if the samples exposed to xenon light (100,000 lux) for 3 weeks were and the state change of it, the one with the bare one Eye was determined, was measured. The results are in table 1 indicated.

Table 1

Out The table shows that the samples containing the filter medium of the present invention, in the fine particle of titanium oxide were used, respectively the samples of Comparative Examples in both the ultraviolet light shielding ability, the visible beam transparency and the resistance were better. Furthermore will be apparent that an increase in the cloudiness, those at sample C01 or fine cracks, those at sample D01 were observed in the sample A01 were not observed and that is, the ultraviolet screening filter means, which was used in Sample A01 was outstanding.

Example 1-2

The The following layer structure was prepared by coating on a support of a 90 μm thick transparent polyethylene terephthalate film provided to photosensitive element (101) produce.

Backing layer side:

• (a) A light-shielding layer containing 6.0 g / m ^{2 of} carbon black and 2.0 g / m ^{2 of} gelatin.
• (b) protective layer containing 0.5 g / m ² gelatin.

Emulsion side:

• (1) Layer containing 3.7 g / m ^{2 of} titanium dioxide and 0.5 g / m ^{2 of} gelatin.
• (2) A coloring material layer containing 0.46 g / m ^{2 of} the following cyan dye-releasing redox compound, 0.07 g / m ^{2 of} tricyclohexyl phosphate, 0.05 g / m ^{2 of} the following dispersant (A), 0.06 g / m ² of the following dispersant (B) and 0.5 g / m ^{2 of} gelatin. Cyan dye-releasing redox compound
  
  Dispersing aid (A)
  
  Dispersing aid (B)
  
  (average molecular weight 100,000)
• (3) Layer containing 0.5 g / m ² gelatin.
• (4) Red-sensitive emulsion layer containing a red-sensitive internal latent image type direct silver bromide emulsion (average grain diameter 0.65 μm, 0.11 g / m ² in terms of silver amount), 0.3 g / m ^{2 of} gelatin, 0.003 g / m ^{2 of} the following nucleating agent and 0.02 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. nucleating agents
  
• (5) A red-sensitive emulsion layer containing a direct positive silver bromide emulsion from rotempfindli internal latent image type (mean grain diameter: 0.98 μm, 0.23 g / m ² , based on the amount of silver), 0.4 g / m ² gelatin, 0.04 g / m ² 2-sulfo-5-n Pentadecylhydrochinonnatriumsalz and 0.005 mg / m ² nucleating agent, which is the same of the layer (4) contains.
• (6) A color mixing prevention layer containing 0.61 g / m ^{2 of} 2,5-di-t-pentadecylhydroquinone, 0.33 g / m ^{2 of} the following polymer dispersant and 0.33 g / m ^{2 of} gelatin.
  
  (Molecular weight 300,000)
• (7) Interlayer containing 0.2 g / m ² gelatin.
• (8) Colorant layer containing 0.46 g / m ^{2 of} the following magenta dye-releasing redox compound, 0.04 g / m ^{2 of} dispersant (A), the same as that of layer (2) and 0.7 g / m ^{2 of} dispersant (B), which contains the same as that of the layer (2) and 0.7 g / m ^{2 of} gelatin. Magenta dye-releasing redox compound
  
• (9) Green-sensitive emulsion layer containing a green positive internal latent image type direct silver bromide emulsion (mean grain diameter: 0.65 μm, 0.11 g / m ² in terms of silver amount), 0.2 g / m ² gelatin, 0.005 mg ² A nucleating agent which contains the same as that of the layer (4) and 0.02 g / m ^{2 of} 2-sulfo-5-n-pentadecylhydroquinone sodium salt.
• (10) Green-sensitive emulsion layer containing a green positive internal latent image type direct silver bromide emulsion (average grain diameter: 0.98 μm, 0.26 g / m ² in terms of silver amount), 0.6 g / m ^{2 of} gelatin, 0.004 mg / m ² nucleating agent which is the same as the layer (4) and contains 0.04 g / m ^{2 of} 2-sulfo-5-n-pentadecylhydroquinone sodium salt.
• (11) A color mixing prevention layer containing 0.91 g / m ^{2 of} 2,5-di-t-pentadecylhydroquinone, 0.29 g / m ^{2 of} the following polymer dispersant and 0.4 g / m ^{2 of} gelatin.
  
  (Molecular weight 200,000)
• (12) Same layer as layer (7).
• (13) A coloring material layer containing 0.53 g / m ^{2 of} a yellow dye-releasing redox compound having the following structure, 0.16 g / m ^{2 of} tricyclohexyl phosphate, 0.05 g / m ^{2 of} dispersant (A), the same as that of US Pat Layer (2), 0.03 g / m ² dispersing agent (B), the same as that of layer (2), 0.035 g / m ^{2 of} the following dye-releasing accelerator (Q), 0.018 g / m ^{2 of} the following dyestuff releasing accelerator (R) and 0.5 g / m ² gelatin. Yellow dye-releasing redox compound
  
  Dye-releasing accelerator
  
• (14) Blue-sensitive emulsion layer containing a blue-sensitive internal latent image type direct silver bromide emulsion (average grain diameter: 0.65 μm, 0.15 g / m ² in terms of silver amount), 0.2 g / m ^{2 of} gelatin, 0.006 mg / m ² nucleating agent, which contains the same as that of the layer (4), 0.0014 g / m ^{2 of} the following compound (S) and 0.01 g / m ^{2 of} 2-sulfo-5-n-pentadecylhydroquinone sodium salt. Connection (S)
  
• (15) Blue-sensitive emulsion layer containing a blue-sensitive internal latent image type direct positive silver bromide emulsion (average grain diameter: 0.98 μm, 0.23 g / m ² in terms of silver amount), 0.3 g / m ^{2 of} gelatin, 0.005 mg / m ^{2 of} the nucleating agent, the same as that of the layer (4) and 0.01 g / m ^{2 of} 2-sulfo-5-n-Pentadecylhydrochinonnatriumsalz contains.
• (16) An ultraviolet shielding layer containing 0.12 g / m ² of each of the following ultraviolet absorbers (A) and (B) and 0.5 g / m ^{2 of} gelatin. Ultraviolet absorber (A)
  
  Ultraviolet absorber (B)
  
• (17) Protective layer containing 0.2 g / m ^{2 of} a matting agent (PMMA), 0.11 g / m ^{2 of} the following curing agent (A), 0.03 g / m ^{2 of} the following curing agent (B) and 0.4 g / m ² gelatin. Hardening agent (A)
  
  Hardening agent (B)
  

Subsequently was a layered structure shown below provided by on a 150 μm thick Paper support the one with a 20 microns thick polyethylene coated on each of the two surfaces thereof was to produce an image pickup element (0101).

Backing layer side:

• (a) Light-shielding layer containing 2.8 g / m ^{2 of} carbon black and 4.8 g / m ^{2 of} gelatin.
• (b) White layer containing 4.1 g / m ^{2 of} titanium dioxide and 1.0 g / m ^{2 of} gelatin.
• (c) protective layer containing 0.5 g / m ² gelatin.

Image-receiving layer side:

• (1) Neutralizing layer containing 5.9 g / m ^{2 of} diacetylcellulose (acetylation degree: 54.5%), 5.9 g / m ^{2 of} a methyl vinyl ether / maleic anhydride copolymer (molar ratio: 1: 1, average molecular weight: 20,000), 0.09 g / m ^{2 of} the following compound (B), 0.17 g / m ^{2 of} the following compound (C), 0.12 g / m ^{2 of} the following compound (D), 0.08 g / m ^{2 of} the following compound ( E) and 0.40 g / m ^{2 of} the following compound (F).

• (2) Eine Zeitsteuerschicht, die 5,3 g/m² Diacetylcellulose (Acetylierungsgrad: 51,3%), 0,16 g/m² eines Styrol/Maleinsäureanhydridcopolymers (Molverhältnis: 1:1, durchschnittliches Molekulargewicht: 10000) und 0,35 g/m² der folgenden Verbindung (G) enthält. Verbindung (G)
  
• (3) Eine Zeitsteuerschicht, die 0,05 g/m² eines Polymerlatex (wenn hergestellt durch Emulsionspolymerisation von Styrol/Butylacrylat/N-Methylolacrylamid in einem Massenverhältnis von 49,7/42,3/8) und 0,05 g/m² eines Polymerlatex (wenn hergestellt durch Emulsionspolymerisation von Methylmethacrylat/Acrylsäure/N-Methylolacrylamid in einem Massenverhältnis von 93/3/4) enthält.
• (4) Eine Beizschicht, die 3,0 g/m² des folgenden Beizmittels (H), 0,6 g/m² des folgenden Beizmittels (I), 0,05 g/m² des folgenden Antiausbleichmittels (J), 0,2 g/m² des folgenden Härtungsmittels (K), 0,10 g/m² des folgenden (L) und 2,8 g/m² Gelatine enthält. Beizmittel (H)
  
  Beizmittel (I)
  
  Härtungsmittel (K) Eine Mischung von K-1 und K-2 in 3:1 (Gewichtsverhältnis)
  
• (5) Eine Titanoxidschicht, welche durch Verwendung der Beschichtungslösung, die die Titanoxiddispersion A01 des Beispiels gemäß der vorliegenden Erfindung enthält, das in Beispiel 1-1 hergestellt wurde, gebildet wurde und welche 0,6 g/m² Titanoxid, 0,5 g/m² Gelatine und 0,01 g/m² des folgenden oberflächenaktiven Mittels (M) enthält. C₁₆H₃₃ (CH₂CH₂O) ₁₀H
• (6) Eine Ablöseschicht, die 0,04 g/m² eines Acrylsäure/Butylmethacrylatcopolymers (Molverhältnis: 85:15, durchschnittliches Molekulargewicht: 100.000) enthält.

In the above formulas (B) to (F), Bu represents a butyl group.

• (2) A timing layer containing 5.3 g / m ^{2 of} diacetylcellulose (degree of acetylation: 51.3%), 0.16 g / m ^{2 of} a styrene / maleic anhydride copolymer (molar ratio: 1: 1, average molecular weight: 10,000) and 0, 35 g / m ^{2 of} the following compound (G). Compound (G)
  
• (3) A timing layer containing 0.05 g / m ^{2 of} a polymer latex (when prepared by emulsion polymerization of styrene / butyl acrylate / N-methylolacrylamide in a mass ratio of 49.7 / 42.3 / 8) and 0.05 g / m ^{2 of} a polymer latex (when prepared by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylolacrylamide in a mass ratio of 93/3/4).
• (4) A mordant layer containing 3.0 g / m ^{2 of} the following mordant (H), 0.6 g / m ^{2 of} the following mordant (I), 0.05 g / m ^{2 of} the following anti-bleaching agent (J), 0 , 2 g / m ^{2 of} the following curing agent (K), 0.10 g / m ^{2 of} the following (L) and 2.8 g / m ² gelatin. Mordant (H)
  
  Mordant (I)
  
  Curing Agent (K) A mixture of K-1 and K-2 in 3: 1 (weight ratio)
  
• (5) A titanium oxide film formed by using the coating solution containing the titanium oxide dispersion A01 of Example according to the present invention prepared in Example 1-1 and containing 0.6 g / m ^{2 of} titanium oxide, 0.5 g / m ² gelatin and 0.01 g / m ^{2 of} the following surfactant (M). C ₁₆ H ₃₃ ( CH ₂ CH ₂ O ) ₁₀ H
• (6) A peel layer containing 0.04 g / m ^{2 of} an acrylic acid / butyl methacrylate copolymer (molar ratio: 85:15, average molecular weight: 100,000).

In addition, 1 g of each developing solution having the following composition was filled in a container made of an aluminum foil on which vinyl chloride was laminated under a nitrogen atmosphere to prepare an alkaline processing composition. hydroxyethyl 42 g Zinc nitrate · 6H ₂ O 0.9 g 5-methylbenzotriazole 5.4 g benzyl alcohol 3.4 ml Titanium dioxide 1.2 g Aluminum nitrate · 9H ₂ O 15 g potassium 1.0 g 1-phenyl-4-hydroxy-4-hydroxymethyl-3-pyrazolidone 13.0 g potassium hydroxide 63 g water 854 ml

Imaging elements (0102) to (0107) were processed in the same manner as the image pickup element (0101) made, with the exception that the fine particles of titanium oxide TI-A01 in the image-receiving element 0101 by titanium oxides TI-B01 or TI-G01 changed were as shown in Table 2. In addition, an image capture element (0108) are made in the same manner as the image pickup element 0101, with with the exception that added to the dispersion TI-A01 no glycerol has been.

Separated were used to measure the spectral absorption of the titanium oxide layer, Samples in which the titanium oxide was applied in the same way applied to a transparent as in the image pickup element Base made.

Subsequently was the photosensitive element (101) imagewise exposed to light and then any one of the image pickup elements (0101) to (0108) superposed on the exposed photosensitive member (101). Subsequently The alkaline treatment composition was between the resulting developed two elements to give a thickness of 51 microns.

The Development was at 25 ° C carried out. 90 seconds after the onset of development, the photosensitive Element detached from the image capture element. The detached image pickup element was with xenon light (85,000 lux) at 30 ° C in an atmosphere of 40% RH for 3 days irradiated. Thereafter, a drop in magenta density was measured (Density before irradiation: 1.0). It became an automatic recording densitometer from Fuji (manufactured by Fuji Photo Film Co., Ltd.), to measure the minimum density. Regarding spectral absorption was the relationship between the absorbance at 400 nm and the absorbance calculated at 350 nm, and the ratio was used as an index both the shielding of ultraviolet light as well as the rise of Absorption of visible light, which is a significant effect for the shielding of ultraviolet light is used. Since this ratio is larger, is the coloring weaker, so that the shielding of ultraviolet light is preferably higher The results of the aforementioned minimum density, resistance across from Light fading (light resistance) and the relationship between the absorptions are shown in Table 2.

Out It is clear from the results of Table 2 that if any of image pickup elements 0101-0103 and 0105-0107 (according to the present Invention) was used, the ratio between the degrees of absorption was high, the minimum density was low, and the xenon light resistance was high, which are outstanding features.

In TI-D01, wherein the amount of the surface-treating agent was too large, the amount of titanium oxide was considerably small, so that its xenon light resistance was low. In the sample (0108) to which no glycerol was added, fine cracks occurred when the color of the sample became faint due to xenon light. Thus, it is clear that the fine cracks result from a low resistance to Lichtausblei occur. Even if peeling was performed after 5 minutes or 10 minutes instead of peeling after 90 seconds, it was confirmed that an improvement in the resistance to light bleaching was observed in the examples of the present invention.

Example 1-3

Imaging elements (0109) to (113) were set in the same manner as the image pickup element 0101 manufactured, with the exception that in the light receiving element 0101 the fine particles of titanium oxide TI-A01 to TI-H01 or TI-L01 changed were as shown in Table 3.

On the same manner as in Example 1-2 were samples wherein the titania was applied in the same amount in the image pickup element, applied on a transparent base.

Subsequently was The development was carried out in the same way as in Example 1-2 to measure the minimum density and the maximum density of the samples. The results of the minimum density, the maximum density, the resistance across from a light bleaching (light resistance) and the ratio between the degrees of absorption are shown in Table 3.

Out Table 3 makes it clear that in the samples according to the invention high photographic properties are maintained and the durability across from a light bleaching could be improved.

Example 1-4

It was an image pickup element (0114) in the same way as the Image pickup element 0101, with the exception that the Titanium oxide dispersion A01 (UV screening filter agent) according to the present Invention was added to the pickling layer, with the same amount as in the element 0101, and that the titanium oxide in the titanium oxide layer was omitted in element 0101 (not added). The resistance across from a light bleaching of the sample (0114) was in the same manner as in example 1-2, to give the value of 85%. Of these Facts can be understood that the same beneficial effects even when titanium oxide is in the image-receiving layer is incorporated.

Comparative Example 1-1

It an image-receiving element was prepared with glycerol in the Titanium oxide dispersion in the image pickup element 0101 omitted and then the resulting element was tested. As a result, it was confirmed that the durability across from the light bleaching was improved, but it was a considerable Increase in viscosity in the titanium oxide dispersion at room temperature after one month. Thus, the long-term productivity stability was insufficient.

Example 1-5

It For example, a photosensitive element (502) was prepared by providing the following layer structure made on a 90 micron thick opaque polyethylene terephthalate film.

1. Undercoating layer

• Cellulose sulfate · sodium salt (amount to be coated: 19 mg / m ² )

2. Cyan dye development layer

The layer contained the following cyan dye developer (960 mg / m ² ), gelatin (540 mg / m ² ), cellulose sulfate, sodium salt (12 mg / m ² ) and phenylnorbornenylhydroquinone (245 mg / m ² ).

Cyan dye-developing agent

3. Red-sensitive silver iodobromide emulsion layer

The layer contained silver iodobromide emulsion grains having an average grain diameter of 0.6 μm and a silver iodide content of 1 mol% (780 mg / m ² ), silver iodobromide emulsion grains having a mean Grain diameter of 1.5 μm and a silver iodide content of 3 mol% (420 mg / m ² ) and polyvinyl hydrogen phthalate (18 mg / m ² ).

4. Interlayer 1

The layer comprised a copolymer of butyl acrylate / diacetone acrylamide / methacrylic acid / styrene / acrylic acid (2325 mg / m ² ), polyacrylamide (97 mg / m ² ), a hydantoin curing agent (124 mg / m ² ) and succinine dialdehyde (3 mg / m ² ). ,

5. magenta dye development layer

The layer contained the following magenta dye developer (455 mg / m ² ), gelatin (298 mg / m ² ), 2-phenylbenzimidazole (234 mg / m ² ), phthalocyanine blue dye (14 mg / m ² ) and cellulose sulfate · Sodium salt (12 mg / m ² ).

6. Interlayer 2

The intermediate layer contained a carboxylated styrene / butadiene latex (Dow 620 latex (trade name): 250 mg / m ² ), gelatin (83 mg / m ² ) and polyvinyl hydrogen phthalate (2 mg / m ² ).

7. Green sensitive Silberiodbromidemulsionsschicht

The layer contained silver iodobromide emulsion grains having an average grain diameter of 0.6 μm and a silver iodide content of 1 mol% (540 mg / m ² ), silver iodobromide emulsion grains having a mean grain diameter of 1.3 μm and a silver iodide content of 3 mol% (360 mg / m ² ), gelatin (418 mg / m ² ) and polyvinyl hydrogen phthalate (23 mg / m ² ).

8. Interlayer 3

The layer contained phenylnorbornenylhydroquinone (263 mg / m ² ), gelatin (131 mg / m ² ) and cellulose sulfate sodium salt (4 mg / m ² ).

9. Interlayer 4

The layer contained a copolymer of butyl acrylate / diacetone acrylamide / methacrylic acid / styrene / acrylic acid (1448 mg / m ² ), polyacrylamide (76 mg / m ² ) and succinine dialdehyde (4 mg / m ² ).

10. scavenger layer

The layer contained 1-octadecyl-4,4-dimethyl-2- {2-hydroxy-5-N- (7-caprolactamido) sulfonamido} thiazolidine (1000 mg / m ² ), gelatin (405 mg / m ² ), cellulose sulfate Sodium salt (12 mg / m ² ) and Quinacridone Red-ξ (7 mg / m ² ).

11. Yellow filter layer

The layer contained benzidine yellow (241 mg / m ² ), gelatin (68 mg / m ² ) and cellulose sulfate sodium salt (3 mg / m ² ).

12. Yellow Dye-releasing layer

The layer contained the following compound which released yellow dye (1257 mg / m ² ), gelatin (503 mg / m ² ) and cellulose sulfate · sodium salt (20 mg / m ² ).

13. Interlayer 5

The layer contained phenyl, t-butylhydroquinone (450 mg / m ² ), 5-t-butyl-2,3-bis {(1-phenyl-1H-tetrazol-5-yl) thio} -1,4-benzenediol Bis {(2-methanesulfonylethyl) carbamate} (100 mg / ^m2 ), gelatin (250 mg / ^m2 ), and polyvinyl hydrogen phthalate (33 mg / ^m2 ).

14. Blue-sensitive Silberiodbromidemulsionsschicht

The layer contained silver iodobromide emulsion grains having a mean grain diameter of 1.3 μm and a silver iodide content of 1 mol% (37 mg / m ² ), silver iodobromide emulsion grains having a mean grain diameter of 1.6 μm and a silver iodine content of 3 mol% (208 mg / m ² ), gelatin (78 mg / m ² ) and polyvinyl hydrogen phthalate (7 mg / m ² ).

15. UV filter layer

The layer contained Tinuvin (trade name, manufactured by Ciba-Geigy Corp., 500 mg / m ² ), benzidine yellow (220 mg / m ² ), gelatin (310 mg / m ² ) and cellulose sulfate · sodium salt (23 mg / m ² ).

16. protective layer

The layer contained gelatin (300 mg / m ² ) and polyvinyl hydrogen phthalate (9 mg / m ² ).

It became an image pickup element (0501) by providing the following Layer structure on a 160 μm made of thick opaque polyethylene-coated paper backing.

1st neutralization layer

The layer contained a blend (22219 mg / m ² ) of the following Polymer A and Polymer B in a mass ratio of 9:11.
Polymer A: Copolymer of methyl vinyl ether / maleic anhydride (GANTREZ 5-97, trade name, manufactured from GAF Corp.)
Polymer B: vinyl acetate / ethylene latex (AIRFLEX 465, trade name, manufactured by Air Products Co.)

2nd timing shift

The layer contained a mixture of (2691 mg / m ² ) Hycar 26349 (trade name, manufactured by BF Goodrich Co.) and the following Polymer C in a mass ratio of 1.3.
Polymer C: Copolymer of polyvinyl alcohol, graft-polymerized with diacetone alcohol and acrylamide (mass ratio of the three components: 1: 8.2: 1.1).

3. Image acquisition layer

The layer contained a mixture (3983 mg / m ² ) of a polymer D having the following structural formula, ultra-hydrophilic polyvinyl alcohol (AIRVOL 165, trade name, manufactured by Air Products Co.) and butanediol in a mass ratio of 2: 1: 1.

Polymer D;

4. Release layer

The layer contained polyacrylic acid (162 mg / m ² ). An alkaline developing composition (501) of the composition shown in Table 4 was prepared.

Table 4

An image-receiving element (0502) was prepared in the same manner as the image-receiving element 0501, except that 600 mg / m ^{2 of} the fine particles of titanium oxide TI-A01, the same ones used in Example 1-2, became the image-receiving layer was added.

Subsequently was the photosensitive element (502) imagewise exposed and the Image pickup element (0501) or (0502) was exposed on the exposed superimposed on photosensitive element 502. The alkaline processing composition (501) was in the gap between the two superimposed Elements designed to give a thickness of 60 microns. Subsequently was the same rating as in Example 1-2. It was confirmed, that in the image pickup element 0502, which is an example according to the invention was, the consistency across from a light bleaching could be improved.

Example 2-1

To 35 parts fine particles of titanium oxide TI-A11 (with a spherical Shape, a mean primary particle diameter of 12 nm and a rutile crystallinity of 44%, which is 10% of Aluminum oxide surface treated were (amount with respect to titanium oxide)), 5.2 parts of poly (sodium acrylate) as a dispersant (trade name: POIZ-530, manufactured by Kao Corporation), 10.5 parts glycerin as coagulation preventing agent 49.3 parts of water were added and mixed, and the resulting Mixture was prepared by means of a dissolution device (manufactured Tokushu Kita Kogyo Co., Ltd.) for 30 minutes at 3000 rpm dispersed. Thereafter, the mixture was passed through a horizontal sand mill 5 times passed through at 2500 revolutions / minute. This way was obtained a dispersion A11.

The Dispersion A11 was mixed with gelatin such that the ratio of Titanium oxide to gelatin 2 to 1 and then the mixture was on a polyethylene terephthalate support such that the optical density at 350 nm was 1 (Sample A11).

It Sample B11 was prepared in the same manner as sample A11, with the exception that the above-mentioned fine particles of titanium oxide TI-A11 by the one with an average primary particle diameter of 55 nm and surface treated 10% alumina changed were.

Two Grams of each of the above Compounds A and B were mixed with 4 g of tricresyl phosphate, 5 ml of ethyl acetate and 2 g of gelatin in the same manner as in Example 1-1. The resulting mixture was emulsified at 5000 rpm for 5 minutes in a dissolving device (Tokusyu Kika Kogyou Co., Ltd.). In the same way as in the preparation of Sample A11, the resulting emulsion applied to a polyethylene terephthalate support such that the optical density at 350 nm 1 (a sample C11) was.

It a sample D11 was prepared in the same way as sample A11, with the exception that glycerol was omitted in sample A11 (not used).

The optical density of the respective samples at 400 nm, the density change ratio (resistance) thereof; when the samples were exposed to xenon light (100,000 lux) for 3 weeks and the state change thereof, the one with the bare one Eye was observed was measured. The results are in table 5 indicated.

Table 5

Out Table 5, it is clear that the samples containing the filter medium of the invention in which the fine particles of titanium oxide were used, in terms of the samples of Comparative Examples in both of. Ultraviolet-shielding, the visible beam transparency and durability were better. Furthermore it is clear that an increase in the observed turbidity in sample C11 or the fine cracks observed in sample D11 were observed in the sample A11 and thus that the ultraviolet screening filter agent used in Sample A11 was, was outstanding.

Example 2-2

• (5) Eine Titanoxidschicht, welche gebildet wurde, indem die Beschichtungslösung, die die Titanoxiddispersion A11 von einem Beispiel gemäß der vorliegenden Erfindung enthält, verwendet wurde, wie in Beispiel 2-1 hergestellt, und welche 0,6 g/m² Titanoxid, 0,5 g/m² Gelatine und 0,01 g/m² des folgenden oberflächenaktiven Mittels (M) enthielt. C₁₆H₃₃ (CH₂CH₂O) ₁₀H

An image pickup element (1101) was fabricated in the same manner as the image pickup element (0101) of Example 1-2, except that the fifth layer on the image receiving layer side was changed by the following layer.

• (5) A titanium oxide film formed by using the coating solution containing the titanium oxide dispersion A11 of an example according to the present invention as prepared in Example 2-1 and containing 0.6 g / m ^{2 of} titanium oxide , 5 g / m ² gelatin and 0.01 g / m ^{2 of} the following surfactant (M). C ₁₆ H ₃₃ ( CH ₂ CH ₂ O ) ₁₀ H

It For example, image pickup elements (1102) to (1106) were the same as the image pickup element (0101) made, with the exception that the fine particles of titanium oxide TI-A11 in the image-receiving element 1101 were changed by any of the titanium oxides TI-B11 and TI-F11, as shown in Table 6. In addition, an image capture element (1107) in the same way as the image pickup element (1101) with the exception that to the dispersion of TI-A11 no glycerol was added.

Separated to measure the spectral absorption of the titanium oxide layer, Samples in which the titanium oxide is coated in the same amount as it is applied in the image pickup element, on a transparent Base made.

Subsequently was the photosensitive element (101) exposed to light almost imagewise, and then any of the image pickup elements (1101) to (1107) superimposed on the exposed element (101). The alkaline development composition was superimposed between the two Elements designed to give a thickness of 51 microns. The photosensitive Element (101) and the alkaline processing composition which were prepared in the same manner as in Example 1-2 used.

The development was carried out at 25 ° C. 90 seconds after the beginning of the development, the Photosensitive element detached from the image pickup element. The detached image-receiving element was exposed to xenon light (85,000 lux) at 30 ° C in an atmosphere of 40% RH for 3 days. Thereafter, a drop in magenta density was measured (density before radiation: 1.0). An automatic recording densitometer manufactured by Fuji (manufactured by Fuji Photo Film Co., Ltd.) was used to measure the minimum density. In consideration of the spectral absorption, the ratio between the absorbance at 400 nm and the absorbance at 350 nm was calculated, and the ratio was used as an index of the shielding of ultraviolet light and an increase in the absorption of visible light caused to be Result of a strong influence due to the shielding of ultraviolet light.

There this ratio is bigger, is the cloudiness less, so that the shielding of ultraviolet light preferably is larger.

The Results of the aforementioned minimum density, resistance across from a light bleaching (light resistance) and the ratio between the degrees of absorption are shown in Table 6.

Out It is clear from the results in Table 6 that in the samples, in any of the image pickup elements 1101-1105 (according to the present invention) was used, the ratio between the degrees of absorption was high, the minimum density low was, and the consistency across from Xenon light was pretty high, which are outstanding features.

In TI-F11 was rutile crystallinity too small and the film was denatured. (This was probably because that its reactivity was high). As a result, TI-F11 was in weatherability low. It also became a cloudiness in the surface caused. In the sample (1107), to which no glycerine was added, stepped fine jumps when the color of the sample faded by xenon light. Consequently became the consistency across from the light bleaching deteriorates accordingly. Even if a peeling off 5 minutes or 10 minutes was performed instead of peeling off 90 seconds was confirmed that the improvement in the resistance to light bleaching in the example according to the present invention was observed. From this fact can be understood that the anti-dyeing properties were also improved.

Example 2-3

Imaging elements (1109) to (1112) became the same as the image pickup element 1104 made, with the exception that the fine particles of titanium oxide TI-D11 in the image pickup element 1104 by any one of TI-G11 or TI-I11 changed were as shown in Table 7.

On in the same way as in Example 2-2, samples containing titanium oxide is applied, in the same amount as in the image pickup element is applied, produced on a transparent base.

Subsequently was Development as in Example 2-2 performed to the minimum density and to measure the maximum density of the samples.

The Results of minimum density, maximum density, durability across from a light bleaching (light resistance) and the ratio between the degrees of absorption are shown in Table 7.

Out Table 7 shows that in the samples according to the invention a high photographic performance is maintained and the consistency across from a light bleaching could be improved.

Example 2-4

It An image pickup element 1111 was made in the same manner as that Image pickup element (1101), with the exception that the Titanium oxide dispersion A11 was added in the same manner as in the element 1101, to the mordant layer, and that the titanium oxide in the titanium oxide layer in the element 1101 has been omitted. The resistance across from The light-bleaching was done in the same way as in Example 2-2 rated. As a result, the value thereof was 85%. From this fact it will be seen that the same beneficial effects are shown even when the titanium oxide is in the image-receiving layer is incorporated.

Comparative Example 2-1

It became an image pickup element in the same manner as the image pickup element 1101, with the exception that glycerol in the titanium oxide dispersion in the image pickup element 1101 has been omitted. Subsequently was tested the resulting element. As a result, it was confirmed that the durability across from a bleaching was improved, but an increase in the viscosity was in the titanium oxide dispersion, which at room temperature for a Stored for a month. Thus, long-term production stability was insufficient.

Example 2-5

An image-receiving element (1502) was prepared in the same manner as the image-receiving element 0501 in Example 1-5, except that 600 mg / m ^{2 of} fine particles of titanium oxide TI-A11, the same as used in Example 2-1 were added to the image-receiving layer instead of the fine particles of titanium oxide added in the image-receiving element 0501 of Example 1-5.

Subsequently was the photosensitive element (502) imagewise exposed and the Image pickup element (0501) or (1502) was exposed on the exposed superimposed on photosensitive element 502. The alkaline developing composition (501) was in the gap superimposed between the two Elements designed to give a thickness of 60 microns. The review, which is the same as in Example 2-2, was then performed. The photosensitive element (502) and the alkaline developing composition (501) prepared in the same manner as in Example 1-5 were used.

It was confirmed, in the image pickup element 1502, which is an example according to the present invention Invention was, the resistance across from a light bleaching was improved.

Example 3-1

It were made into 5 parts of spindle-shaped Fine particles of titanium oxide TI-A21 (short-axis diameter according to the mean Primary particle diameter: 8 nm (short-axis diameter at both ends of the particles: 5 nm), Long axis diameter thereof: 32 nm and an aspect ratio: 4), 5.2 parts of poly (sodium acrylate) as a dispersant (trade name: POIZ-530, manufactured by Kao Corporation), 10.5 parts of glycerin as Coagulation preventing agent and 49.3 parts of water were added and mixed, and the resulting mixture was allowed to stand for 30 minutes at 3000 revolutions / minute by means of a dissolving device (manufactured by Tokushu Kika Kogyo Co., Ltd.). After that, the mixture became through a horizontal sand mill 5 Time passed at 2500 revolutions / minute. This way was obtained a dispersion A21.

The Dispersion A21 was mixed with gelatin such that the ratio of Titanium oxide to gelatin was 2 to 1, and moreover the resulting Mixture applied to a polyethylene terephthalate such that the optical density at 350 nm is 1 (a sample A21).

Subsequently was a sample B21 is prepared in the same way as sample A21, with the exception that the above-mentioned fine particles of titanium oxide TI-A21 by having a short-axis diameter of the mean primary particle diameter of 50 nm, a long axis diameter of the mean primary particle diameter of 200 nm and an aspect ratio changed from 4 were.

Two grams of each of the above-mentioned compounds A and B were mixed with 4 g of tricresyl phosphate, 5 ml of ethyl acetate and 2 g of gelatin in the same manner as in Example 1-1. The mixture was emulsified and dispersed at 5000 rpm for 5 minutes in a dissolver (Tokusyo Kika Kogyou Co., Ltd.). In the same manner as in the preparation of sample A21, the resulting Emulsion applied to a polyethylene terephthalate support such that the optical density at 350 nm is 1 (a sample C21).

The optical density of the respective samples at 400 nm and the density change ratio (durability of which) when the samples xenon light (100,000 lux) for 3 weeks are shown in Table 8.

Table 8

Out Table 8 is clear that the samples containing the filter medium of the present Use invention by using the fine particles of titanium oxide were, respectively the samples of Comparative Examples in both the ultraviolet light shielding ability, the visible beam transparency as well as the film physical Properties (resistance) were better. About that In addition, there was an increase in turbidity in sample C21 was not observed in the sample A21 and thus was the ultraviolet screening filter agent used in Sample A21 outstanding.

Example 3-2

• (5) Eine Titanoxidschicht, welche gebildet wurde unter Verwendung der Beschichtungslösung, die die Titanoxiddispersion A21 eines Beispiels gemäß der vorliegenden Erfindung enthält, wie es in Beispiel 3-1 hergestellt wurde und welche 0,6 g/m² Titanoxid, 0,5 g/m² Gelatine und 0,01 g/m² des folgenden oberflächenaktiven Mittels (M) enthielt. C₁₆H₃₃ (CH₂CH₂O) ₁₀H

The image pickup element (2101) was fabricated in the same manner as the image pickup element (0101) of Example 1-2, except that the fifth layer on the image receiving layer side was changed by the following layer.

• (5) A titanium oxide film formed using the coating solution containing the titanium oxide dispersion A21 of an example according to the present invention as prepared in Example 3-1 and containing 0.6 g / m ^{2 of} titanium oxide, 0.5 g / containing (m) m ² of gelatin and 0.01 g / m ² of the following surface active agent. C ₁₆ H ₃₃ ( CH ₂ CH ₂ O ) ₁₀ H

It Image pickup elements (2102) to (2106) were the same way as the image pickup element (2101) is made, with the exception that the spindle-shaped Fine particles of titanium oxide TI-A21 in the image-receiving element (2101) by any of the spindle or cylindrical fine particles of titanium oxide TI-B21 until TI-F21 as shown in Table 9 were changed.

Separated were added to the spectral absorption of the titanium oxide layer Measure samples with titania applied to the same Applied as in the image pickup element, on a transparent Base generated.

Subsequently was the photosensitive element (101) imagewise exposed to light and then any one of the image pickup elements (2101) to (2106) superimposed on the exposed element 101. The alkaline development composition was superimposed between the two Elements designed to give a thickness of 51 microns. The photosensitive Element (101) and the alkaline processing composition, was prepared in the same manner as in Example 1-2 used.

The development was carried out at 25 ° C. 90 seconds after the start of development, the photosensitive member was peeled off the image-receiving member. The detached image-receiving element was exposed to xenon light (85,000 lux) at 30 ° C in an atmosphere of 40% RH for 3 days. Thereafter, a drop in magenta density was measured (pre-irradiation density: 1.0). An automatic recording densitometer from Fuji (manufactured by Fuji Photo Film Co., Ltd.) was used to calculate the minimum density to eat. With respect to the spectral absorption, the ratio between the absorbance at 400 nm and the absorbance at 350 nm was calculated, and the ratio was used as an index of ultraviolet shielding and as a sharp increase in the absorption of visible light as a result of a marked influence due to the shielding of ultraviolet light. Since this ratio is larger, the haze is weaker, so that the shielding of ultraviolet light is preferably larger. The results of the above-mentioned minimum density, the resistance to light-fading (light resistance) and the ratio between the absorptances are shown in Table 9.

From the results of Table 9, it is clear that in the samples in which any of the images Although the ratio between the absorptions was quite high and the resistance to xenon light was high.

Furthermore was confirmed, that even when peeling off was performed after 5 minutes or 10 minutes instead of detaching after 90 seconds, an improvement in durability compared to the Light bleaching was observed in the inventive example. From this fact, it can be understood that the anti-staining property was also improved.

Example 3-3

Imaging elements (2107) to (2108) became the same as the image pickup element 2101 prepared, except that the spindle-shaped fine particles of titanium oxide TI-A21 by spindle-shaped Fine particles of titanium oxide TI-G21 or TI-H21 in the image-receiving element 2101, as shown in Table 10.

On in the same manner as in Example 3-2, the samples in which the titanium oxide was applied in the same amount as in the image-receiving element applied, made on a transparent base.

Subsequently was development and measurement as in Example 3-2 performed to to measure the maximum density of the samples.

The Results of minimum density, maximum density, durability across from Light bleaching (light resistance) and the relationship between the absorptions are shown in Table 10.

Out Table 10 can be understood that in the samples according to the invention a high photographic performance can be kept and the resistance across from a light bleaching could be improved.

Example 3-4

It was an image pickup element (2109) in the same manner as the Image pickup element 2101 is made, with the exception that the Titanium oxide dispersion A21 in the same manner as in element 2101 was added to the pickling layer and that the titanium oxide in the Titanium oxide layer was omitted in the element 2101. The durability across from a light bleaching was tested and in the same way as evaluated in Example 3-2. As a result, the value of it was 84%. From this fact can be understood that the same advantageous effects as shown in Example 3-2, even when the titanium oxide is incorporated into the image-receiving layer is.

Example 3-5

It became an image pickup element in the same manner as the image pickup element 2101, with the exception that glycerol in the titanium oxide dispersion in the image pickup element 2101 has been omitted. Then that became formed element in the same manner as in Example 3-2 tested. As a result, good results were obtained as in Example 3-2.

In In this case, a long-term test was conducted in which the viscosity of the titanium oxide dispersion (UV screening filter agent) was carried out. after one month was measured, during which period the temperature this dispersion was kept continuously at room temperature. As a result, it was confirmed that the viscosity the titanium oxide dispersion increased. This fact shows that in the photographic film unit for the color diffusion transfer the present invention, a production stability on by incorporating glycerol into this unit.

Example 3-6

An image-receiving element (2502) was prepared in the same manner as the image-receiving element 0501 in Examples 1-5, except that 600 mg / m ² fine particles of titanium oxide TI-A21, the same as used in Example 3-1 were added to the image-receiving layer in place of the fine particles of titanium oxide used in the image-receiving element 0501 of Example 1-5.

Subsequently was the photosensitive element (502) imagewise exposed and the Image pickup element (0501) or (2502) was exposed on the exposed superimposed photosensitive element. Subsequently was the alkaline developing composition (501) in the space between the resulting two superimposed Elements designed to give a thickness of 60 microns. Subsequently was the same evaluation as in Example 2-2.

When Result was confirmed that in the image pickup element 2502, which is an example according to the invention was, the consistency across from improved light bleaching, as well as similar good results in example 3-2 were shown.

Claims (3)

A color diffusion transfer photographic film unit comprising: an image-receiving element comprising, on a support, a layer having a neutralizing function, an image-receiving layer, and a release layer successively in this order from the support; a photosensitive element comprising at least one silver halide emulsion layer combined with at least one dye image forming compound on a support having a light shading layer; and a viable alkaline processing composition between the image-receiving member and the photosensitive member, and forming the image by developing the alkaline processing compositions between these members after exposure, and then peeling the image-receiving member and the photosensitive member apart, wherein the image-receiving member comprises an ultraviolet shielding layer, which is formed by applying an ultraviolet screening filter means, wherein the ultraviolet screening filter means comprises fine particles of titanium oxide in a dispersion further comprising a polyhydric alcohol, the ultraviolet screening filter means satisfying the following conditions (B) or (C): (B) that the fine particles of titanium oxide have a spindle shape and an average primary particle diameter or average primary short-axis particle diameter of 1 to 45 nm and a rutile crystallinity of 20 to 70% or (C) that the fine particles of titanium oxide have a cylindrical or spindle-shaped primary particle shape, and that among the average primary particle diameters of fine particles of titanium oxide, a short-axis diameter of 1 to 45 nm, a long-axis diameter of 3 to 200 nm, and a ratio of long-axis diameter to short-axis diameter 2 to 10, and that the polyhydric alcohol is glycerol and / or ethylene glycol. Photographic film unit for color diffusion transfer according to Claim 1, wherein the polyhydric alcohol is glycerol. Photographic film unit for color diffusion transfer according to Claim 1 or 2, wherein the ultraviolet shielding layer in the image-receiving element in the image-receiving layer and / or as a coating layer of the image-receiving layer (In the image pickup element further away from the carrier) is arranged.